CN101454264A - System and method for converting biomass to ethanol via syngas - Google Patents

Abstract

A method and apparatus for synthesizing ethanol using synthetic routes via synthesis gas are disclosed. A method and apparatus for gasifying biomass, such as biomass, in a steam gasifier that employs a fluidized bed and heating using hot flue gases from the combustion of synthesis gas is described. Methods and apparatus for converting synthesis gas into ethanol are also disclosed, using stepwise catalytic reactions to convert the carbon monoxide and hydrogen into ethanol using catalysts including iridium acetate.

Description

Change biomass into the alcoholic acid system and method by synthetic gas

Cross reference to related application

The application requires the right of priority of temporary patent application of submitting on April 5th, 2,006 60/789,067 and the temporary patent application of submitting on January 19th, 2,007 60/881,189.

Technical field

The present invention relates to the processing of synthetic gas, and particularly, relate to by biomass and produce the alcoholic acid method.This method relates to by biological material generation ethanol (ethanol).Catalytic step makes the maximization of alcoholic acid yield by selecting efficiently.

Background technology

Synthetic gas (Synthesis gas), or " synthetic gas (syngas) " are to the oxycarbide (such as carbon monoxide) that comprises multiple amount and the given title of gaseous mixture of hydrogen.This title comes from their purposes as intermediate in producing synthetic Sweet natural gas, ammonia, methyl alcohol (methyl alcohol) or fuel.

Can produce synthetic gas by many methods, for example, by being other product with calorific value, for example gasification of coal, biomass or municipal waste material with carbonaceous fuel gasification.Other example comprises Sweet natural gas, from the steam reforming of the methane or the liquid hydrocarbon in multiple source.Synthetic gas is inflammable, and usually as fuel source or as the intermediate that produces other chemical.Synthetic gas also in the synthetic petroleum of producing by the katalysis that utilizes fischer-tropsch (Fisher-Tropsch) catalyzer as fuel or lubricant, uses as intermediate.The most frequent gasification by coal or municipal waste produces the synthetic gas as fuel.

During intermediate in synthetic as the large-scale industry of hydrogen and ammonia, it also produces (passing through steam reforming reaction) by Sweet natural gas.Synthetic gas at large-scale refuse-produce in-the energy equipment for gasification generates electricity as fuel.Gasification of coal is quite efficiently, and is used for making the material that is called " illumination " gas or coal gas in the past for many years, before widely-used electricity, is used for street lamp and domestic lighting.

Synthetic gas is widely used in generation methyl alcohol.Synthetic gas from coal also is used to produce a collection of chemical preparations.Can carry out catalysis to it and produce a class diesel oil fuel, be called " fischer-tropsch (Fisher-Tropsch) fuel ".

Recently, developed the special bacterium that is used for synthetic gas is changed into ethanol and acetate mixture.In these one step methods, changing the alcoholic acid chemistry route into is not efficiently.

Many utilization fermentations or other biological method method from the direct synthesizing alcohol of biomass is also disclosed.Though these methods have been used for the cellulose raw producing and ethanol that comprises from biomass, this method seriously is subjected to, except other, they can not change the xylogen that comprises in the lignocellulose biomass into the restriction of useful products.

Disclose such method, by described method, synthetic gas will change ethanol into efficiently, and it needs purifying hardly and removes and anhydrate.This ethanol is suitable for the alternative fuel as industrial application, as the chemical precursor, or as the additive of medicine or beverage.

Ethanol (alcohol) is to be used for beverage, commercial run and the conduct of the more recent ground global product than the cleaner incendiary automotive fuel of gasoline.

Because the world need be so huge to alcoholic acid, and, also can shockingly increase at present, so utilize the method for complete biomass can increase the alcohol production ability in the whole world owing to attempt to use on a large scale its additive that acts as a fuel in the North America.

The invention describes such method,, can change ethanol efficiently into by the synthetic gas that biological material produces by this method.

Summary of the invention

The present invention produces the alcoholic acid method from synthetic gas, and this method comprises the following steps:

Synthetic gas is provided;

Change synthetic gas into methyl alcohol, thereby produce methyl alcohol and carbon monoxide and hydrogen;

Catalyzer and promotor and methyl alcohol, carbon monoxide and hydrogen are reacted, thereby produce the mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water;

Separate described mixture to separate described promotor, the mixture of methyl acetate and methanol mixture and acetate and water;

Hydrogen is added in methyl acetate and the carbinol mixture, and make this mixture and hydrogenation catalyst reaction produce ethanol.

Disclose another kind of method, this method changes synthetic gas into ethanol.Synthetic gas is changed into the mixture of methyl alcohol, carbon monoxide and hydrogen; Described methyl alcohol and carbon monoxide mixtures utilize catalyst reaction to produce acetate and carbon monoxide, and the reaction under the condition that catalyzer exists of acetate and ethanol produces the mixture that comprises ethyl acetate and water; Utilize the hydrogenation catalyst reaction to produce ethanol with described ethyl acetate and described hydrogen.

Disclose such method, described method will change ethanol into by the synthetic gas (synthesisgas) (synthetic gas (syngas)) that biological material produces.Gasified bio-matter produces synthetic gas in the steam gasification device, compresses this synthetic gas, and makes itself and one or more catalyst reaction produce ethanol.Gasifying biomass device among the present invention is the box describe device with bottom, and described bottom is dispenser panel and pipe, thereby wherein said pipe transmits the hot gas heated fluidized bed.Each catalytic step should utilize the available best approach to realize, and is to need catalyzer, container and the suitable heat and the catalytic step of pressure.

Disclose the steam gasification that utilizes by fluidized-bed, produced the method for synthetic gas from the exsiccant biomass.This bed is a box-shaped container, and it has dispenser panel as base plate, and hot gas is through pipe transmission, thereby and the gasification of injection biomass be synthetic gas.In another embodiment of the invention, the low BTU synthetic gas by burning produces in the second air blowing gasifier heats described gasification.

Also disclose and be used for producing the alcoholic acid device from synthetic gas, wherein said device comprises methanol reactor, methyl acetate reactor with metal catalyst, the ethanol synthesis device that is used for separating the water distilling apparatus of ethyl acetate, acetate, hydrogen and methyl-iodide and produces methyl alcohol.In another embodiment of the invention, be used to produce alcoholic acid and load the synthetic gas that receives from the steam gasification device, described steam gasification utensil has fluidized-bed, and described fluidized-bed has the dried biomass that acts as a fuel.

Also disclose and be used for producing the alcoholic acid method from biomass, described method comprises provides synthetic gas, described synthetic gas is changed into comprise methanol mixture, makes describedly to comprise the methanol mixture reaction, thereby obtains to comprise methyl acetate and methanol mixture; Describedly comprise methyl acetate and methanol mixture and H-H reaction produces ethanol with making.

The accompanying drawing summary

By with reference to following detailed description about accompanying drawing, should be more readily understood above-mentioned feature of the present invention, wherein:

Figure 1A is the method that is used for producing from biomass synthetic gas, i.e. the preferred embodiment synoptic diagram of method of the present invention.

Figure 1B is the method that is used to compress and transform synthetic gas, i.e. the preferred embodiment synoptic diagram of method of the present invention.

Fig. 1 C is used for from synthetic gas generation alcoholic acid method compression and that transform, i.e. the preferred embodiment synoptic diagram of method of the present invention.

Fig. 2 shows steam gasification device, the i.e. end view of device of the present invention.

Fig. 2 A shows steam gasification device, the i.e. side-view of device of the present invention.

Fig. 3 shows air blowing gasifier, the i.e. view of device of the present invention.

Fig. 4 is the figure of the dispenser panel used in the air blowing used in the inventive method and the steam gasification device.

Fig. 5 is the cylindrical figure that adds a cover in the dispenser panel of using in air blowing of the present invention and the steam gasification device.

Fig. 6 is used for producing ethanol, the i.e. synoptic diagram of the preferred embodiment of method of the present invention from synthetic gas.

Fig. 7 is the sectional view of steam gasification device heating tube.

Fig. 8 shows to use the liquid heat transfer medium to distribute the synoptic diagram of hot-fluid in all method.

The detailed description of specific embodiments

Definition.When being used for this specification sheets and claims, unless context needs in addition, following term should have specified implication:

When being used for this paper, term " comprises (comprises) " and " comprising (comprising) " is interpreted as comprising with open, and non-exclusive.Especially, in the time of in being used in this specification sheets that comprises claim, term " comprises (comprises) " and " comprising (comprising) " and variant thereof mean and comprise this characteristic specified, step or composition.This term is not interpreted as getting rid of the existence of further feature, step or composition.

As first embodiment preferred, change biomass into ethanol.With reference to Figure 1A, biomass treatment apparatus 101 and moisture eliminator 102 are the first steps of this method.Biomass treatment apparatus 101, for example shredder is handled coarse biometric matter and it is processed as the size that is suitable for gasifying.In most of situations, biomass must be cut, grind, arched upward and shred to being of a size of 2 inches or littler cubes.

Utilize pressurized vapor moisture eliminator 102, for example the steam-heated oven that is provided by BMA (Niro) can be dried to these biomass humidity 30%-1% (preferably, 20% or lower).It is the steam of about 275kPa (scope with 225-325kPa) that moisture eliminator 102 provides pressure.Then, have the dried biomass that is lower than 30% humidity and be discharged into (not shown) in the dried feed bin by forwarder.

From the steam-heated oven 102 that is in 275kPa, retrieve water vapour, and make it overheated, thereby provide fluidization steam vapor 105 for steam gasification device 106 from the humidogene material.This can realize through heat recovery steam generator 103 by making it, in heat recovery steam generator 103, by the hot flue gases of discharging from steam gasification device 106 110 it is heated.

A part of dried biomass is fed in the air blowing gasifier 107, and produces low BTU synthetic gas 107a.Can in two cyclonic separator 108a and 108b, purify and to hang down BTU synthetic gas 107a, thereby remove any particulate matter.Then, the low BTU synthetic gas 107b of purification burns in low BTU gas burner 109, thereby produces high-temperature flue gas 110.This stack gas, it leaves burner with about 1090 degrees centigrade (in 1000-1200 degree centigrade scopes), provides heating by 202 pairs of steam gasification devices of inner heat exchanger.As alternate embodiment, can burn other fuel of burner 109 produces stack gas, comprises methane, landfill gas, Sweet natural gas or methane and other light hydrocarbon that is produced by the anaerobic digestion of fertilizer or biosolids.

An embodiment of air blowing gasifier used herein, as shown in Figure 3, the Quincy of Florida State (Quincy) with 1,000 ton/day equipment for gasification in, proved business success.The air blowing gasifier can be a container 301, and it is enough to withstand the internal refractory lining formation of internal stability by the outside of metal such as carbon steel.In one embodiment, container 301 is columniform, and it has vertical wall 310 and top board 306.Embodiment preferred is the cheese top board.Typical container should be 40 feet of 8 feet of diameters and height, although this design can amplify or dwindle in proportion.

In preferred embodiments, container 301 has dispenser panel 305 as its base plate and the outlet 304 that is arranged in top board or vertical wall 310 tops.Reactor has the mineral bed 303 of silica sand or class in the bottom, described silica sand typically has the granular size of 300-400 micron.Load the gasifier chamber with the bed material, between fuel assembly top and top board, reserve freeboard (freeboard space) 307.

Dispenser panel 305 has a series of holes that pierce wherein, and what each hole connected (by screw thread (threading), welding or some other secure fixation technology) metal adds a cover right cylinder 309.In these right cylinders each is hollow in the bottom, thus suction air pressurized 308a in the plemum 308 below the slave plate 305.

Plemum 308 is such chambers, in described chamber with the forced air charging below dispenser panel 305.In typical embodiment, this should be the cheese chamber of turning upside down, and it comprises complete dispenser panel, and has gas inlet.

Direct pressurized air 308a enters in the plemum below the dispenser panel, and forces it to enter described bed through adding a cover right cylinder 309, causes this fluidisation.Cylindrical arrangement on the dispenser panel 305 is designed, so that its described material of fluidisation in whole bed equably.There are many configurations that can be used to realize this.A kind of method is with the trellis pattern, promptly can be linear, leg-of-mutton or other pattern, and right cylinder 309 is installed on the plate 305.

The air blowing gasifier can also be the feature that starts burner 302a, 302b and 302c, and described startup burner 302a, 302b and 302c heat described container to about 750-900 degree centigrade, the working range of the gasifier of promptly blowing.Can the outside that burner 302a and 302b are oriented in gasifier wall will be started, and burner 302c is located immediately in the described bed.When described bed reached the temperature of its working temperature, these start burner closed, and by add the temperature that exsiccant biomass and air keep bed to container.The air blowing gasifier preferably at normal atmosphere or near under the normal atmosphere, is promptly worked in the scope of 100-175kPa.

Can pass through conical screw feeder 303, biomass are fed in the air gasification container 301, and when bed 302 was fluidizing, described screw feeder was fed to the exsiccant biomass at this middle part, and when this bed is not fluidizing, be fed on this top.Conical screw feeder 311 is designed, be compressed so that biomass are passed through when this screw rod advances, cause that thus being arranged near the stopper 311a of its opening enters into container, this prevents the counterpressure to this container.

When bed 303 was fluidizing, it remained below the level of top board 306, thereby kept competent freeboard 307, so that there is not a material, such as silica sand, leaked through outlet 304 with low BTU synthetic gas.Ideally, keep the condition of container, so that the eluting gas that produces is in the residence time that has at least 2 seconds before outlet is left in freeboard, its scope is 1-5 second.In typical embodiment, wherein diameter is 8 feet and highly is 40 feet, when this fluidisation, should have the height less than 15 feet, and when for static state, less than 6 feet.

Get back to the preferred systems embodiment, as shown in Figure 1A, the stack gas 110 that is produced by burner 109 is passed in the inner heat exchanger 202 of steam gasification device 106.

The preferred embodiment of biomass steam gasifier 106 is fluidised bed systems of patent, as shown in Figure 2.DESIGN OF REACTOR is a box describe device 201, and it has wall 210 and top board 206, although have many other configurations and ratio, it is 20 feet that typical embodiment has length, and width is 10 feet and highly is the 30-40 foot.Dispenser panel 205 is base plates.In typical embodiment, top board 206 is dome-shaped or semi-cylindrical.Be the hole of boring in dispenser panel 205, the right cylinder 209 of adding a cover wherein be installed, right cylinder 209 can with the parallel plane direction of dispenser panel, the plemum 208 of steam from dispenser panel 205 below is drawn onto beds 203.Be similar to the air blowing gasifier, these right cylinders of adding a cover have the hollow import that is communicated with space below the dispenser panel, and have the outlet opening of one or more these cylindrical longitudinal axis of crosscut.In this embodiment, be in superheated vapour in the 500-600 degree centigrade of scope and be forced in the plemum 208 below the dispenser panel, and be forced to leave and add a cover right cylinder 209 and enter bed 203, by the mode of the described bed of even fluidisation.In other embodiments, non-superheated vapour can be used for fluidized-bed and promote gasification.Can with add a cover right cylinder threading, welding or otherwise secure fixation in the opening of dispenser panel.

Plemum 308 is such chambers, in described chamber with the superheated vapour charging below dispenser panel 305.In typical embodiment, this should be the cheese chamber of turning upside down, and it comprises complete dispenser panel, and has the steam-in.

The right cylinder example that can use in air blowing or steam gasification device can be referring to Fig. 5, promptly shown in the cross section of dispenser panel and plemum.Plate 503 has the gap, is wherein filled by the right cylinder 501 that is fixed in this plate.Typically, right cylinder 501 has about 6 inches length, and 1-4 inch wherein is fixed on the dispenser panel top.Dispenser panel is made of carbon steel usually, has about 0.5 inch thickness.The right cylinder that utilizes screw thread (threading) 502 to fix in this embodiment is although can use other fixing means, such as welding.This right cylinder has the lid 506 of threading on this right cylinder.Be plemum 508 below the plate 503, superheated vapour or air are assigned to right cylinder through described plemum 508.Steam or air enter hollow area 505 through right cylinder.This hollow area has the internal diameter of 1/4-1 inch scope, preferably, and 0.5 inch.This hollow parts points to the little outlet opening 506 that this cylinder axis of one or more crosscuts gets out, thereby allows that steam or air enter into bed 507 with the direction parallel with dispenser panel 505.In this embodiment, cylindrical lid 509, and outlet opening thus 506 extends 1 inch-5 inches Anywhere above dispenser panel 503.It is the 1/16-1/4 inch that outlet opening in the embodiment preferred has internal diameter.Flow out by pressurized gas, described right cylinder provides the enough strength of fluid bed material.

Get back to Fig. 2, bed is 203 by mineral, and for example, granular silica sand and/or rhombspar (it suppresses the formation of tar) or peridotites or their combination are formed, and on this top Ceramic Balls can also be arranged, thereby silicon-dioxide is remained on appropriate location in the container.Utilize conical screw feeder 211, biomass material is expelled in the steam gasification device bed 203.This conical screw feeder by the effect of its briquetting biomass, produces biomass plug 211a in its exit, it prevents that air admission is in container 201 and prevent counterpressure from gas in the container.Importantly be that in order to prevent to relate to undesirable chemical reaction of nitrogen in the entire method process, biomass are airfree basically.This screw feeder is directed, like this when bed during fluidisation, biomass is injected at the middle part of bed, and when bed not during fluidisation, is injected on beds 203 the top.

Add bed and wood material, so that the gasifier container remains on optimum level.The amount of the freeboard 207 between bed 203 and the top board 206 remains on such level, and promptly when being fluidisation, the mineral from this are not ejected this container.Ideally, the residence time of gas in freeboard in the 1-5 scope of second, preferably 2 seconds.The residence time homologation reaction that prolongs such as the generation of water-gas shift (it changes CO into H2 and CO2) and steam reforming, makes the output maximization of hydrogen thus.Importantly be that in order to prevent to relate to undesirable chemical reaction of nitrogen in the process of entire method, biomass are airfree substantially.

The superheated vapour 105 that will be heated to 500-600 degree celsius temperature (preferred 550 degrees centigrade) is added a cover right cylinder 209 through plemum 208 and process below the dispenser panel 205, be expelled in the steam gasification device bed, described superheated vapour 105 can be from heat recovery steam generator 103.With competent pressure injection steam, thus the described bed of fluidisation equably.Non-superheated vapour also can be used for the described bed of fluidisation and promote gasification.

The example of adding a cover right cylinder 209 orientations on the dispenser panel 205 sees among Fig. 4, and it is the top view of dispenser panel 205.With the trellis pattern with bolt 209 be arranged in equably plate around, this trellis pattern can be linear, as shown, or leg-of-mutton, or the arrangement of some Else Rules.Typically, described 1 inch-6 inches of right cylinder phase mutual edge distances, preferably 2 inches of adding a cover.In this mode, all zones of described bed is even fluidizing.Can use similar pattern to the dispenser panel 305 of air blowing gasifier.

Get back to Fig. 2, add hott bed 203 by inner heat exchanger 202, described inner heat exchanger 202 is made up of a plurality of stainless steel tubes that pass the extension of fluidized-bed axle, thereby will be from hot flue gases 110 heat passage fluidized-beds 203 to the steam gasification device, described hot flue gases leaves described burner with the temperature of about 1090 degrees centigrade (in 1000-1200 degree centigrade of scopes).In this mode, described bed is maintained at about 815 degrees centigrade temperature, and its scope is 750-900 degree centigrade.In Fig. 2 (side-view), visible heat exchanger tube 202 extends the length of gasifier, and transports the hot flue gases from burner 109.

Fig. 2 A, promptly the end view of steam gasification device shows how described pipe is arranged in this bed.To manage 202 and be arranged among the bundle 202a, the width that described bundle 202a crosses over container 201 extends.By upholder 202b these bundles are kept together, upholder 202b is anchored on wall and the top board, and keeps described pipe to be in suitable position.Described upholder will guarantee by this way and be held in together that described mode is easily they to be shifted out from gasifier as group, thereby cleans and safeguard.Described pipe typically is made up of stainless steel or materials similar.It is the 0.5-4 inch that described pipe has internal diameter, is preferably the 1.5-3 inch.

In preferred embodiments, tube bank 202a is made up of pipe row, wherein said rows of mutually staggered, and when overlooking pipe terminal, this pipe relative to each other forms trilateral like this.In this configuration, the heating of the not only auxiliary fluidized-bed of described pipe, and assist gas this bed of flowing through.This is to realize by such fact, and the described fact is that the gas that rises must clash into described tube-surface frequently when they are up, thereby smashes air pocket and form small bubbles, and this improves mixing of gas and a material in whole bed.

In preferred the arrangement, first tube bank is placed in apart from the about 2-4 foot in bottom of described bed, as dispenser panel institute mark.Second bundle if desired, is placed on the first bundle top 2-4 foot, and three beams (if desired) 2-4 foot above second bundle.The quantity of required bundle depends on many factors, comprises size, heat transfer coefficient, the effluent gas temperature of container.In this mode, on the degree of depth of whole fluidized-bed, it is heated.In typical the arrangement, described row is at interval, so that the center of described pipe is separated by about 6 inches, therefore 10 feet wide gasifier container should have the row of 20 pipes.Described tube bank can have 2-6 among these rows anywhere, and is interlaced with each other as mentioned above, thereby makes the surface contact maximization of ascending gas.

The quantity height of the pipe that needs depends on the temperature of inlet flue duct gas, and biological qualitative attribution, described pipe and the heat transfer coefficient of bed material and required bed tempertaure.As shown in Figure 7, by in pipe, inserting band, can reduce the quantity of the pipe that needs.In the figure, as seen manage 701 section and comprise band 702, band 702 reverses with helical pattern via the length of pipe.The band of this insertion can be made by any heat-transfer metal, and the heat transfer coefficient of pipe can be increased 2-10 doubly, reduces the required pipe quantity of fully conducting heat thus.

Described container is remained under about normal atmosphere, and scope is at 100-175kPa.Many fluid coal incendiary steam boilers are such as by Babcock ﹠amp; Those that Wilcox and ABB/ combustion enginnering (ABB/Combustion Engineering) are produced use heat-transfer pipe generation steam in the bed.In the steam gasification device, any volatile organic matter that exists is changed into the composition of environmental safety.Get back to Fig. 2, the synthetic gas 114 that is produced by the steam gasification device leaves via the outlet in the top board 206 206 with 815 degrees centigrade (in 750-900 degree centigrade of scopes).

Get back to Fig. 1, will be now be fed in the heat recovery steam generator 103, as shown in Figure 1A with the stack gas 110 of the inner heat exchanger that leaves steam gasification device 106 202 of about 815 degrees centigrade (in 750-900 degree centigrade of scopes).This producer 103 utilizes the heat that is provided by described stack gas to produce and heating steam.This steam can be used to be used to the steam 104 generation superheated steam 105 of self-desiccation device, and perhaps it can produce the steam 113 of middle pressure for the use in moisture eliminator 102.Alternatively, or additionally, the steam of formation can be used for outside the use, or is used for synthesis step after a while, such as steam converter 117 or methanol reactor 120.

Synthetic gas 114 leaves the steam gasification device via outlet 206, and through two cyclonic separator 111a and 111b, thereby remove whole particulate matters substantially.The agranular synthetic gas of cooling in second heat recovery steam generator 112, thus other process steam produced.This process steam can with the steam that acts on moisture eliminator 113, be used for steam gasification device 106 steam, be used for the conversion steam of steam converter 117 or be used for the water-gas shift steam of methanol reactor 120, perhaps can be used for the processing of device external.In preferred embodiments, will send to first producer 103 by the steam 112a that second producer 112 produces, thereby further be heated to being used for the superheated vapour of steam gasification device 106.

Then, via washing device 113, further purify hot synthesis gas.This can utilize Venturi (Venturi)-type wet washing device or apron or they some make up and realize.Wash by this way, described mode allows synthetic gas not contain particulate matter and is the compound of genotoxic potential to the catalyzer that uses in the composition sequence.Particularly, not sulfur-bearing, metal and nitrogen compound of synthetic gas.Also be that syngas compositions contains a high proportion of carbon monoxide and hydrogen and the least possible carbonic acid gas, methane and other hydrocarbon ideally.If desired, all right dry synthetic gas is to remove water-content.At last, can in caustic rubber 113a, handle synthetic gas, thereby remove more pollutent.

When cleaning, mainly by carbon monoxide and hydrogen, and the synthetic gas that more a spot of carbonic acid gas and little hydrocarbon such as methane are formed is suitable for as fuel, or as the parent material of many synthetic routes.

Consequent synthetic gas can be used to utilize many known synthetic route synthesizing alcohols.In one embodiment, the synthetic gas that is produced by this biomass gasification method contacts with the catalyzer of Fischer-Tropsch type, thereby produces the mixture of ethanol and hydrocarbon product, utilizes the known technology separating alcohol from this mixture.The catalyzer that can be used for this embodiment comprises well-known cobalt and iron catalyst, also comprises other compound, such as moly-sulfide, tungsten sulfide, sulfuration rhenium, molybdenum carbide.

In another embodiment, the synthetic gas that is produced by this biomass gasification method contacts with catalyzer, thereby produces the mixture of methyl alcohol, carbon monoxide and hydrogen.Then, the mixture of this methyl alcohol, carbon monoxide and hydrogen is at the methyl alcohol homogeneous catalyst, and the existence reaction down such as ruthenium acetate comprises the alcoholic acid mixture thereby produce.With U.S. Patent number 4,954,665,4,133,966,4,111,837,4,233,466 and 4,239,924 are incorporated herein as a reference.

Some examples that can be used for the catalyzer of this method are Ir ₄(CO) ₁₂, IrCl3, dicarbapentaborane two iodate rhodiums, RhCl3, RhI3, RhI2 (CO) 2.

As the alternatives of this further embodiment, the mixture of methyl alcohol, carbon monoxide and hydrogen reacts in the presence of carbonylating catalyst, thereby produces the mixture that partly comprises acetate and hydrogen.Carbonylating catalyst can be based on the heterogeneous or homogeneous catalyst of VIII family metal.U.S. Patent number 5.488,143 is incorporated herein as a reference.Then, acetate and hydrogen react generation ethanol at hydrogenation catalyst down such as the existence of Degussa catalyzer.

In another alternatives, syngas mixture can with the reaction of halogenation rhodium catalyst, produce acetaldehyde at 150-300 degree centigrade temperature and the pressure of 6900-17000kPa, and acetaldehyde can catalytically contact with hydrogenation catalyst then, thereby produces ethanol.With U.S. Patent number 4,482,647 are incorporated herein as a reference.

In preferred embodiments, shown in Figure 1B and 1C, utilize the synthetic gas of steam reforming, change it into methyl alcohol, change methyl acetate (with acetate in a small amount) into by carbonylation then by the gasification generation of biomass.This methyl acetate in the presence of hydrogenation catalyst with H-H reaction, produce methyl alcohol and ethanol.

In the method, synthetic air 115 (mainly, CO and the H after the further processing cleaning ₂, and more a spot of CO ₂And methane), thus make ethanol yield maximization.Utilize compressor apparatus 116 that synthetic gas is compressed to pressure and be 2400-3500kPa, be preferably 3200kPa, and utilize heat exchanger 116b to be heated temperature to be 220-450 degree centigrade (being preferably 225 degrees centigrade).This compressor is 4 grades of reciprocation compressors that have interstage cooling on all grades.Each level has been equipped water separator, thus the water of condensation in removing every grade.The electric motor of two specified 2240kW provides power for this compressor.This process produces condensed fluid 116a, for recirculation, further processing or discharging, removes this liquid from described stream.

Synthetic gas enters in the steam converter 117 then, and this steam converter changes methane and other light hydrocarbon that exists in the synthetic gas into additional carbon monoxide and hydrogen by adding steam.This steam reforming takes place in the presence of base metal catalysts, and at pressure [scope: 2900-3500kPa] and the 225C[scope 220-450C of 3200kPa] operation.Steam reforming is known technology, can be selected from many known commercial designs, and can be available from the known contractor of this equipment, such as Haldor Topsoe A/S, Lurgi AG or ICI.The catalyzer that is suitable for this purpose comprises well-known VIII family conversion catalyst in the periodic table of elements, comprises nickel and/or cobalt, manganese-Zirconium oxide.With U.S. Patent number 7,090,789 and 7,074,347 are incorporated herein as a reference.In other embodiments, according to forming of the synthetic gas that produces by concrete biomass material, needn't use steam converter.

In this stage, according to the composition of synthetic gas, can utilize carbon dioxide removal system 119, remove system such as the Praxair thanomin, synthetic gas is carried out co 2 removal.In this stage, from synthetic gas, remove the as many carbonic acid gas 119a that can realize, and according to circumstances, it is sent to storage by prior-art devices, other local use in the method, or be discharged in the atmosphere.In another embodiment, this co 2 removal step occurs in after second compression step 118.

After leaving from steam converter 117, synthetic gas further is compressed to 4700-5500kPa (preferably then, pressure 4900kPa), and be heated 220-300 degree centigrade (preferably, 225 degrees centigrade) temperature, and for recirculation, further processing or discharging and remove any condensed fluid 118a.Be similar to compressor 116, this compressor 118 is four utmost point reciprocation compressors that have interstage cooling on all grades.Each level has been equipped water separator, thereby removes the water of condensation in every grade.The electric motor of two specified 2240kW provides power for this compressor.Heat exchanger 118a is used for gas heating to working temperature.

In this point, the compressed synthesis gas 116a that breaks away from compressor 116 is in 4900kPa[scope: 4700-5500kPa] pressure and 220-300 degree centigrade of 225C[scope], this synthetic gas is in the temperature and pressure to first catalytic step the best now.Then synthetic gas is fed in the first step of chemical reaction sequence, described chemical reaction sequence is to change synthetic gas into methyl alcohol 120.Synthetic gas is the process of fully determining to the transformation of methyl alcohol, and can finish by gas phase or liquid phase reaction.Methyl alcohol produces from the synthetic gas that produces by the Sweet natural gas steam reforming usually, and a lot of now business equipment is on-stream.

In this embodiment of methanol reactor, carbon monoxide and hydrogen with the ratio combination of 1:2, form methyl alcohol respectively.In preferred embodiments, use slurry reactor.In the embodiment of slurry, methanol reactor 120 is the methanol reactors that can be purchased from air products (Air Products), and it should provide the added benefit with commercial manufacturers slip-stick artist, and guarantees its performance.Air products (Air Products) reactor process is very effective, and is used to be positioned at Kingsport, the maximum in the world coal of Tenn-to-methanol plant.In preferred embodiments, reactor 120 is the vertical containers with internal vertical pipe.Catalyzer in the methanol reactor is made up of basic metal, and at pressure 4900kPa[scope: 4700-5500kPa] and 225 degrees centigrade [scope 220-300 degree centigrade] work.Embodiment comprises cupric oxide and the zinc oxide on the aluminum oxide, and it is suspended in the inert mineral oil.The synthetic gas process of pressurization contains the container bubbling of mineral oil catalyzer, and spills through the top of vertical container.In preferred embodiments, the synthetic gas that enters this container should comprise some methyl alcohol.These extra methyl alcohol are by providing from the methyl alcohol recirculation of reclaiming in the ethanol synthesis device.With U.S. Patent number 3,888,896,4,031,123,4,639,470,4,910,227,4,628,066,4,567,204 and 4,628,066 enters this paper as a reference.Because this reaction is heat release, so, provide water coolant in order in pipe, to produce steam.

The information disclosure of announcing by air products (Air Products) hydrogen: carbon monoxide is than being used to produce methyl alcohol for 0.6-4.0.This methanol reactor can obtain such yield, promptly changes the carbon monoxide of 20-90% into methyl alcohol in this reactor, although typically be in the scope of 40-70%.

In the embodiment of this methanol reactor, interim when synthetic gas rests in this methanol reactor, by adding steam to the gas that enters methanol reactor and passing through to remove carbonic acid gas, the concentration that can regulate required hydrogen.This step may be an ideal, because the hydrogen in the synthetic gas may not be best to the ratio of carbonic acid gas for high produced in yields ethanol.In this embodiment, catalyst for methanol should, in the presence of steam, change carbon monoxide into hydrogen and carbonic acid gas, increase the ratio of hydrogen thus to carbon monoxide.This reaction occurs in methyl alcohol and changes under the similar pressure and temperature condition, and known its can be finished in a step mode.U.S. Patent number 4,946,477 disclose the methyl alcohol/shift reaction of such combination, and it is introduced as reference.Also with U.S. Patent number 4,980,145 as the reference introducing.

In the embodiment of combination methyl alcohol and shift reaction, co 2 removal equipment 121 is inserted into the exit of methanol reactor 120, thereby removes the carbonic acid gas that forms in the water-gas shift.By removing the amount of the steam that carbon monoxide and control supplies with, and be recycled to the methyl alcohol of methanol reactor 127 ingresss and the amount of hydrogen, can control the hydrogen concentration in methanol reactor exit by control.

There is methanol reactor in other embodiment.For example, can use the filling Solid Bed of the catalyzer on the inert material, and synthetic gas is through this packed bed.Can use common catalyst for methanol in the method.

Alternative catalyzer can be used for other embodiment.The methanol synthesis catalyst that uses in the inventive method can comprise a kind of oxide compound that is selected from by at least a element in the following group of forming: copper, silver, zinc, boron, magnesium, aluminium, vanadium, chromium, manganese, gallium, palladium, osmium and zirconium.Catalyzer can be based on the catalyzer of copper, such as cupric oxide.This method can be used the catalyzer based on copper, and it also comprises a kind of oxide compound that is selected from by at least a element in the following group of forming: silver, zinc, boron, magnesium, aluminium, vanadium, chromium, manganese, gallium, palladium, osmium and zirconium.

The mixture of the methyl alcohol in this embodiment, CO and hydrogen, it can also comprise the water vapor from water-gas shift reaction, is delivered to the methyl acetate reactor 122 from methanol reactor.Methyl acetate reactor in this embodiment is a packed bed reactor, and it comprises the vertical tube of one or more about 1 inch wide (scope 0.5-2 inches) and 20 feet long (scope 15-30 feet).The catalyzer that uses in the preferred embodiment of reactor 122 is made up of the iridium acetate that adsorbs on the activated carbon, and fills it in the vertical tube.Reactor is in the temperature and 1000-1200kPa (pressure work 1034kPa) best, of 200-300 degree centigrade (220 degrees centigrade best).Methyl-iodide gas is added to wherein as promotor, and they enter the import of reactor afterwards, and react in described pipe, mainly are methyl acetates thereby produce in the exit, and the mixture of hydrogen and small amount of acetic acid and water.This reaction is heat release, and utilizes via in the pipe of container or as the heat exchange medium around the chuck operation of filling pipe, cools off this reactor vessel indirectly such as dowtherm.

In other embodiments, can use heterogeneous catalyst widely.These catalyzer are useful in the carbonylation of methyl alcohol: RhX ₃, RhX _3.3H ₂O, Rh ₂(CO) ₄X _2,[Rh (CO) X ₄] Y, Rh ₂(CO) ₈, Rh (NO ₃, [Rh (CO) ₂X ₂] Y, Rh ₂O ₃, Rh (CH ₃COO) _3,[Rh (C ₂H4) ₂X] ₂, Rh[(C ₆H ₅) ₃P] ₂(CO) X, Rh metal, RhX[(C ₆H ₅) ₃P] ₂(CH ₃X) ₂, Rh (SnX ₃) [(C ₆H ₅) P] _3,RhX (CO) [(C ₆H ₅) ₃Q] ₂, (R ₄Z) [Rh (CO) ₂X] ₂, (R ₄Z) ₂Rh (CO) X ₄], RhX[(C ₆H ₅) ₃P. ₉] ₃, RhX[(C ₆H ₅). ₃P] H ₂, [(C ₆H ₅) ₃P] 3Rh (CO) H and Y ₄Rh ₂X ₂(SnX ₃) ₄, wherein X is Cl, Br or I; Y is Na, Li or K; Z is N, As or P; Q is As, P or Sb; And R is C ₁-C ₁₂The alkyl or aryl group.

In other embodiments, can also use second promotor.Described second catalyzer can be selected from CoCl ₂, RuCl ₃, PdCl ₂, PtCl ₂, CuCl ₂, AgNO ₃, AuCl ₃, CdCl ₂, ZnCl ₂, OsCl ₃, IrCl ₃, NiCl ₂, MnCl ₂, ReCl ₅, CrCl ₃, MoCl ₃, WCl ₆, VCl ₃, NbCl ₅, TaCl ₅, TiCl ₄, ZrCl ₄, HfCl ₄, LiI, NaI, KI, RbCl, BeCl ₂, MgCl ₂, CaCl ₂, SrCl ₂, BaCl ₂With U.S. Patent number 5,414,161 as the reference introducing.

Promotor widely except that methyl-iodide can be used for other embodiment.These promotors include but not limited to CH ₃Br, CH ₃Cl, I ₂, Br ₂, Cl ₂, HI, HBr, HCl.

In other alternative embodiment, reactor can be a Liquid-phase reactor.In one embodiment, solid catalyst, such as listed above those, can be suspended in inert liq, in mineral oil.In this embodiment, gaseous reactant can pass through this inert liq bubbling.

In another embodiment of carbonylation reaction, catalyzer is a homogeneous catalyst, and it is made up of one or more VIII family metal complexess of dissolved in the solution.In this embodiment, gaseous reactant is dissolved in the solution that comprises catalyzer, and reacts under appropriate condition.In this embodiment, reaction soln is distilled one or many, thereby from carbonylation product, separate the solution that comprises catalyzer.

In this embodiment, many VIII family title complex is suitable for the homogeneous catalysis of carbonylation.These catalyzer comprise IrCl ₃, IrI ₃, IrBr ₃, [Ir (CO) ₂I] ₂, [Ir (CO) ₂Cl] ₂, [Ir (CO) ₂Br] ₂, [Ir (CO) ₂I ₂] ^-, [Ir (CO) ₂Br ₂] ^-, [Ir (CO) ₂I ₂] ^-, [Ir (CH ₃) I ₃(CO) ₂]--, Ir ₄(CO) ₁₂, IrCl ₃4H ₂O, IrBr ₃4H ₂O, Ir ₃(CO) ₁₂, iridium metals, Ir ₂O ₃, IrO ₂, Ir (acac) (CO) ₂, Ir (acac) ₃, [Ir ₃O (OAc) ₆(H ₂O) ₃] [OAc] and six chloro-iridic acid [H ₂IrCl ₆], [Rh (CO) ₂Cl] ₂, [Rh (CO) ₂I] ₂, [Rh (Cod) Cl] ₂, rhodium chloride (III), three hydration rhodium chlorides (III), bromination rhodium (III), iodate rhodium (III), rhodium acetate (III), dicarbapentaborane acetylacetonate rhodium, RhCl ₃(PPh ₃) ₃And RhCl (CO) (PPh ₃) ₂With U.S. Patent number 5,773,642,5,883,289,5,877,348,5,917,089,5,750,007,5,874,610,5,883,295,5,663,430,5,625,094 and 7,115,774 are incorporated herein as a reference, and it discloses, and to be used for alcohol be the method for ester such as the methyl alcohol homogeneous carbonylation.

In another embodiment, carbonylation reaction can carry out in reactive distil container.With the reactant in this situation cooling and be fed in the reaction vessel that comprises catalyzer.Reactor heats this container, removes lighter boiling product, such as methyl acetate, carries out towards the direction of described product thereby promote this reaction.

In other embodiments, use alternative catalyzer promotor, such as the halogenation alkane except that methyl-iodide, such as monobromoethane or iodoethane.

Get back to Fig. 1 C, the mixture of discharging from methyl acetate reactor 120a must separate with promotor.At first in single flash device equipment 123 or other suitable separator, the mixture of discharging is carried out single flash from the methyl acetate reactor, wherein from the residuum of mixture, remove hydrogen.Hydrogen 123a is fed directly into ethanol synthesis device 127.With mixture resistates 123b, it comprises methyl acetate, methyl alcohol, water and acetate, is fed in the distillation column 124, wherein separates methyl-iodide, methyl acetate, hydrogen and methanol mixture 124a from the mixture 124b of acetate and water.Methyl-iodide, methyl acetate and methanol mixture 124a are sent in the distillation column 125, wherein methyl-iodide 125a are reclaimed and is separated into the azeotropic mixture in the vapor phase.Then, recirculation methyl-iodide promotor 125a, thus participate in the gas that enters methyl acetate reactor 122.Methyl acetate and carbinol mixture 125b are sent to ethanol synthesis device 127.

In another embodiment, the mixture that will discharge from the methyl acetate reactor is fed in the distillation column, and this distillation column divides the liquid portion of dried up and acetate and the steam part of methyl acetate, methyl-iodide, hydrogen and methyl alcohol.Methyl acetate, methyl-iodide and methanol mixture are sent in the after-fractionating device, in vapor phase, separate methyl-iodide, and the methyl acetate reactor is got back in its recirculation.Remaining methyl acetate, methyl alcohol and hydrogen are sent to ethanol synthesis device 127.

In preferred embodiments, acetate and water are sent to another distillation column 126, this removes most of water from acetate 126b.Then, with acetate 126b vaporization feeding to ethanol synthesis device 127.Remove water 126a, thereby use in the method or discharge.

Ethanol synthesis device 127 is pressure range (4000kPa) packed bed reactors of work best, of temperature range (about 260 degrees centigrade best) at 160-300 degree centigrade and 3500-4500kPa.Catalyzer is commercial known hydrogenation catalyst, and it is made up of chromium, nickel and copper, can be available from goldschmidt chemical corporation (Degussa).Catalyzer is loaded in the packed bed with inert substance.Container in this embodiment is one or more vertical tubes, internal diameter about 0.5 inch-2 inches and 20 feet (scope 15-30 foot) length.In this reaction, used excessive hydrogen, in preferred embodiments the hydrogen of 10:1: excessive (this can change) of methyl acetate in the never excessive scope excessive to 15:1.Hydrogen is Already in the mixture of reactant.If there is hydrogen in shortage, then can use outside source.Reaction in the ethanol synthesis device is heat release, and utilizes via in the pipe of this container or as the heat exchange medium that the chuck around container tube moves, and cools off this reactor vessel indirectly such as dowtherm.

In other embodiments, can use multiple hydrogenation catalyst.The hydrogenation catalyst that can use in this hydrogenation comprises copper bearing those compounds, for example, and Cu--Co--Zn, Cu--Zn--Fe, Cu--Co--Zn--Fe, Cu--Co--Zn--Fe--Ca, Cu--Co--Zn--Mo--Na and Cu--Co--Zn--Fe.This catalyzer can be made through the following steps: will be dissolved in (the NH in the distilled water ₄) ₂CO ₃Solution adds at least a metal compound solution that is selected from by the following group of forming: Zn (OAc) ₂2H ₂O, Co (OAc) ₃H ₂O, Cu (OAc) ₂H ₂O, Fe (NO ₃) ₃9H ₂O, (NH ₄) ₆Mo ₇O ₂₄4H ₂O, Ca (NO ₃) ₂4H ₂O, NaOH, K ₂PtCl ₄, PdCl ₂, RhCl ₃, RuCl ₃, NiCl ₂, CrCl ₃, WCl ₃, OsCl ₃And AlCl ₃,, and calcined this exsiccant material about 16 hours in about 450 degrees centigrade temperature at the dry consequent mixture of about 120 degrees centigrade temperature overnight.This metallic compound can be with 0.01-95 weight %, more preferably 0.1-80 weight % and the most preferably interior amount use of 1-50 weight % scope.Being used for such ester can obtain and characterize to many other catalyzer of acid-respons.With U.S. Patent number 5,414,161,5,233,099,5,233,100 and 6,002,054 conduct is with reference to combination.

Get back to Fig. 1 C, form by methyl alcohol, ethanol, hydrogen and water from the outflow logistics 127a of hydrogenation reactor.In distillation column 128,,, and hydrogen 128a recirculation is got back to the import of methanol reactor 120 from this mixture separation hydrogen 128a by single flash or other distillation.In water distilling apparatus 129, distill the mixture 128b of remaining ethanol, first alcohol and water, and the methyl alcohol 129a in the vapor fraction is recycled to the import of methanol reactor.

Then,, and be less than 20% water, be sent to pervaporation (pervaporation) equipment 130, such as by in those of Sulzer design, thereby divide dried up 130b and produce the ethanol of regulation grade remaining ethanol fraction 129b.Then, will be directed in the hold-up vessel from the absolute alcohol 130a of ethanol pervaporation equipment.For alcoholic acid stores, two hold-up vessels of 000 liter (1.2MM US gallon) (operation in about 21 days) are provided to have total volume 4,700.Before storage, injection is used for the gasoline of sex change.The gasoline denaturation agent mixes with straight alcohol with 5.263% volume reference.The gasoline hold-up vessel has the capacity of 235,000 liters (62,500 US gallon), and this enough carries out about 16 days operation.

In another embodiment of the invention, can use by four reactor carbonylations and form the alcoholic acid route, as shown in Figure 6.In this embodiment, as preceding general introduction ground, in methanol reactor 120, change synthetic air 115.With these gas transfer to Liquid-phase reactor 601, they and catalyzer therein, for example contact of the iridium on the carbon.Rhodium, and other VIII family metal on the solid carrier also can be used for this reaction effectively.Some known effective catalysts that can use in this carbonylation are Ir ₄(CO) ₁₂, IrCl3, dicarbapentaborane two iodate rhodiums, RhCl3, RhI3, RhI2 (CO) 2.In this embodiment, reactant is under the pressure of 140-160psi and 215-250 degree centigrade temperature, at promotor, such as reacting in the alkylogen solution.Methyl-iodide can be such promotor, although also have other, such as CH ₃Br, CH ₃Cl, I ₂, Br ₂, Cl ₂, HI, HBr, HCl.

The product of this reaction is acetate, hydrogen, He Shui.Must from solution, remove hydrogen by distillation in distiller 602.Hydrogen 602a is sent to ethanol synthesis device 127.In next step, acetate and water are sent in the reactor 603, wherein in the presence of oxide catalyst such as sulfur oxide, add ethanol.This temperature that is reflected at about normal atmosphere (15-25psi) and 90-110 degree centigrade (preferably, 100 degrees centigrade) takes place in liquid phase.It is that ethyl acetate and water are warming up to 250-270 degree centigrade and be compressed to after the pressure of 580-610psi in well heater 604 in compressor 605 that final step can occur in product, and this is the condition of ethanol synthesis device 606.Add hydrogen 602a to reactant ethyl acetate and water, thereby produce the second alcohol and water.Can use and those similar hydrogenation catalysts that are used for the methyl acetate method at this, such as the Cu-Cr-Ni in the packed bed catalyzer.

The flow point of consequent second alcohol and water is two streams, and wherein 606a is passed in the acetic acid ethyl reaction device 603, and remaining 606b pervaporation in Sulzer pervaporation equipment 130, thereby separates remainder water from ethanol.In this mode, form ethanol by synthetic gas.

Noticed before that the ethanol synthesis device 127 of Fig. 1 C, methyl acetate reactor 122 and methanol reactor 120 were heat releases, and methyl acetate and ethanol synthesis device use liquid transfer medium, reactant cooled off such as dowtherm.Therefore the liquid heat-exchange medium can be used for this heat passage other process to needs heat.Therefore, may design the liquid heat-exchange medium loop that can around equipment, conduct heat.This scheme is illustrated among Fig. 8.Liquid heat-exchange medium flow 801 around this diagram display equipment.Will be along the various processing equipment of this loop, be to have the heat exchange surface of can the contact liq reaction medium and transferring heat to described medium or conducting heat from described medium such as distiller or reactor design.In a step, this liquid medium is applied to heat in the moisture eliminator 102 of Figure 1A.This moisture eliminator by cooling off the steam of its discharge, also can contact with this liquid medium by making expellant gas, and provides heat to liquid medium.Simultaneously, this moisture eliminator needs heat to produce and is used for the steam of dried biomass, and can use liquid medium for this purpose.

In this embodiment, described loop, it can produce by the pipeline of transport liquid medium between equipment unit, can be directed to the inter-stage gas booster compressor 116 and 118 of Figure 1B, and this generation can be passed to the heat of medium.Along identical route, medium 801 conducts heat by heat exchanger 116a and the 118a of contact Figure 1B.This medium can also be removed system 119 to CO2 and conduct heat.

In a further detailed description, the liquid transfer medium can receive heat by the thermo-contact of carrying out with the stack gas of discharging from the ethanol synthesis device 127 of steam gasification device 106, methanol reactor 120, methyl acetate reactor 122 and Fig. 1 C.In a similar fashion, this medium can conduct heat to the water distilling apparatus 124,125,126,129 and 130 of Fig. 1 C.

In other embodiments, for the use in the process externally, this liquid medium can be used in interchanger 802 heating steams.This example only is illustrative, and does not get rid of the possibility of using liquid heat-transfer medium.This distillating method uses the cold quenching step to make response composite liquid, and this cold quenching step can be used for conducting heat to this medium.The use of this medium should highly depend on specified equipment certainly, and must calibrate it, thereby balance is through the hot-fluid of this system best.

In this mode,, can see that biomass have utilized obtainable heat to carry out to alcoholic acid processing most, and the amount of the external fuel of this method of operation is minimized together with recovery of heat from stack gas and synthetic gas.

In whole described equipment, need some application systems.These comprise high pressure steam (HighPressure Steam), middle pressure steam (Medium Pressure Steam), low-pressure steam (LowPressure Steam), water coolant (Cooling Water), instrument air (Instrument Air), Controlling System (Control System), electricity (Electrical), fuel gas (Fuel Gas) and fill-in light (Auxiliary Flare), product water is regulated (Product Water Conditioning), regulate (Boiler Feed Water Conditioning) with boiler feed water.In the ethanol distillation system, need water coolant.Dowtherm is used to distillation column that heat is provided, and removes heat from methyl alcohol, methyl acetate and ethanol synthesis device.Two 100% screw air compressors in 760kPag work provide the instrument air.Should provide the instrument air when-50 ℃ of dew points (at 700kPag) based on the instrument instrument air dryer of silica gel dehydration technique.In the dry air receptor, 60-minute instrument air of accumulation is supplied with between normal and minimum pressure.Process control by based on be fixed on dcs on the processing units (Distributed Control System, DCS) instrument (transmitter/umformer) is realized, described instrument is arranged in canyon everywhere.Alarm and closing control should be passed through to arrive in the watch-keeping cubicle and realize from the field signal (field signal) that DCS transmits, and should pass through sequence event data recorder (Sequence Event Data Recorder) and follow the trail of, and are used for subsequent analysis.Flow measurement device should be sent to PLC with information, is used for the local display electric current and adds up to stream.By PLC monitoring that is arranged in the PCO plant control office and control P﹠amp; The input and output from the process instrument and equipment of the last demonstration of ID.All processes point from the watch-keeping cubicle, field with I/O is suitable for this zone.By use current limiting device in local watch-keeping cubicle, all field wiring should be safe in essence.Arrive or should be safe I/O in essence from the analog and digital signal of described field device.Controlling System should be used the 24V DC control loop that is used for field device.The battery backup of this Controlling System can be interrupted power system by real online (load is connected with transverter all the time) to be provided, and this energy system can be kept system works one hour.Procedure quality should realize that described analyzer provides the online indication of required process data by the analyzer of installing.The data that acquisition subsequently is used to analyze.Complete Controlling System and process variable can also pass through operator's remote monitoring, thereby guarantee to keep machinery and method efficient.

Should be appreciated that more than description only relates to the present invention by example.Many should be obvious about variation of the present invention for those skilled in the art, and no matter whether described obvious variation recorded and narrated clearly, belongs to scope of the present invention as herein described.

Claims (140)

1. produce the alcoholic acid method from synthetic gas, described method comprises:

Synthetic gas is provided;

In the presence of catalyzer, change described synthetic gas, thereby produce the mixture that comprises methyl alcohol and carbon monoxide and hydrogen;

By in the presence of promotor and metal catalyst, make the reaction of described methyl alcohol, carbon monoxide and hydrogen and described promotor, generation comprises the mixture of methyl acetate, hydrogen, methyl alcohol, acetate and water, and described metal catalyst comprises a kind of metal that is selected from the group of being made up of iridium, iron, cobalt, nickel, ruthenium, palladium, osmium and platinum;

Separate the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water, thereby produce methyl acetate and methanol mixture and a kind of fraction that is selected from the group that is grouped into by hydrogen fraction, promotor fraction, acetate fraction and water level;

By in the presence of hydrogenation catalyst, make described methyl acetate and carbinol mixture and H-H reaction, generation comprises the alcoholic acid mixture.

2. the production alcoholic acid method described in claim 1 wherein saidly comprises that the catalyzer of metal is an iridium catalyst.

3. the production alcoholic acid method described in claim 1 or 2 wherein saidly comprises that the catalyzer of metal is an iridium acetate.

4. as each described production alcoholic acid method among the claim 1-3, wherein said promotor is an alkylogen.

5. the production alcoholic acid method described in claim 4, wherein said promotor is a methyl-iodide.

6. as each described production alcoholic acid method among the claim 1-5, wherein change described synthetic gas and also comprise:

Compress described synthetic gas, thereby produce the synthetic gas of compression;

Heat the synthetic gas of described compression, thereby produce the compressed synthesis gas of heating;

The compressed synthesis gas of the described heating of steam reforming, thus the synthetic gas that transforms produced;

Recompress the synthetic gas of described conversion, thereby produce the conversion synthetic gas of compression; With

Change the conversion synthetic gas of described compression into comprise methyl alcohol, carbon monoxide, carbonic acid gas and hydrogen mixture.

7. as each described production alcoholic acid method among the claim 1-6, wherein change described synthetic gas and also comprise the described carbonic acid gas of removal from described mixture.

8. as each described production alcoholic acid method among the claim 1-7, wherein from described mixture, remove described carbonic acid gas and be at least and be used to from the heat of heat exchange medium and the part heating, wherein said medium receives the mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water from generation, or comprises the heat that produces the alcoholic acid mixture from generation.

9. as each described production alcoholic acid method among the claim 6-8, the pressure of the compressed synthesis gas of wherein said heating is 2400-3500kPa, and the temperature of the compressed synthesis gas of wherein said heating is 220-450 degree centigrade.

10. as each described production alcoholic acid method among the claim 6-9, wherein the synthetic gas of the described compression of steam reforming is to carry out at the pressure of 2400-3500kPa with 220-300 degree centigrade temperature.

11. as each described production alcoholic acid method among the claim 6-10, the pressure of the conversion synthetic gas of wherein said compression is 4700-5500kPa, and the temperature of the conversion synthetic gas of described compression is 220-300 degree centigrade.

12., wherein the conversion synthetic gas of described compression is changed into and comprises methanol mixture and also comprise as each described production alcoholic acid method among the claim 6-11:

The conversion synthetic gas that makes described compression is by the slurry bubbling, thus generation methyl alcohol, and wherein said slurry comprises the metal catalyst that is suspended in the inert liq.

13. the production alcoholic acid method described in claim 12 wherein changes the conversion synthetic gas of described compression into and comprises methanol mixture and also comprise:

Conversion synthetic gas to described compression adds steam, thereby produces hydrogen, and described hydrogen is added to the conversion synthetic gas of described compression.

14. the production alcoholic acid method described in claim 13 wherein changes the conversion synthetic gas of described compression into and comprises methanol mixture and also comprise the removal carbonic acid gas.

15. as each described production alcoholic acid method among the claim 6-14, wherein changing the conversion synthetic gas of described compression into methyl alcohol is to carry out at the pressure of 4700-5500kPa with 220-300 degree centigrade temperature.

16. as each described production alcoholic acid method among the claim 1-15, described method also comprises the promotor fraction, described promotor fraction is recycled to the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water.

17. as each described production alcoholic acid method among the claim 1-16, described method also comprises the acetate fraction, described acetate fraction is recycled to the described alcoholic acid mixture that comprises.

18. as each described production alcoholic acid method among the claim 1-17, wherein packed bed reactor is used to produce the described alcoholic acid mixture that comprises.

19. the production alcoholic acid method described in claim 18, wherein said packed bed reactor contain by a kind of catalyzer that is adsorbed on copper on the inert substance, nickel, chromium or combinations thereof.

20. as each described production alcoholic acid method among the claim 1-19, wherein producing the described alcoholic acid mixture that comprises is to carry out in 160-300 degree centigrade temperature and the gas phase at the pressure of 3500-4500kPa.

21. as each described production alcoholic acid method among the claim 1-19, wherein producing the described alcoholic acid mixture that comprises is to carry out with the hydrogen of 0:1-15:1 and the ratio of methyl acetate.

22. as each described production alcoholic acid method among the claim 1-20, wherein generation comprises that the alcoholic acid mixture is to carry out with the hydrogen of about 10:1 and the ratio of methyl acetate.

23., wherein produce the described mixture of methyl acetate, hydrogen, methyl alcohol, acetate and water that comprises and in the packed bed carbonylation reactor, carry out as each described production alcoholic acid method among the claim 1-22.

24. the production alcoholic acid method described in claim 23, wherein said packed bed carbonylation reactor are to fill with the absorbent charcoal material of the described metal catalyst of absorption on it.

25. as each described production alcoholic acid method among the claim 1-24, wherein produce the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water and be in the pressure of 1000-1500kPa and gas phase and carry out 200-300 degree centigrade temperature.

26. as each described production alcoholic acid method among the claim 1-25, wherein said separation comprises:

Distill the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water, thereby separate and unreacted component of recirculation and promotor.

27. according to the method for claim 26, wherein distillation also comprises the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water of distillation, thereby produces hydrogen fraction and the mixture that comprises acetate, methyl acetate, methyl-iodide, first alcohol and water.

28. according to the method for claim 27, described method also comprises the described mixture that comprises acetate, methyl acetate, methyl-iodide, first alcohol and water of distillation, comprises the mixture of methyl acetate and methyl-iodide and comprises acetate and the mixture of water thereby produce.

29. according to the method for claim 28, described method also comprises the described mixture that comprises methyl acetate and methyl-iodide of distillation, thereby produces methyl acetate fraction and methyl-iodide fraction; With

Remove water from the described mixture of acetate and water that comprises, thereby produce the acetate fraction.

30. according to each method among the claim 1-29, wherein separating the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water and be to small part is used to from the heat heating of heat exchange medium, wherein said medium receives the mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water from generation, or comprises the heat that the alcoholic acid mixture is produced from generation.

31. as each described production alcoholic acid method among the claim 1-30, described method also comprises

Separate the described alcoholic acid mixture that comprises, thereby produce ethanol fraction, methyl alcohol fraction and the second hydrogen fraction;

Described methanol steam and the described second hydrogen fraction be recycled to change described synthetic gas into the described step that comprises methanol mixture.

32. the production alcoholic acid method described in claim 31, wherein separating the described alcoholic acid mixture that comprises is to be used to heat from the heat of heat exchange medium to small part, wherein said medium receives the mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water from generation, or comprises the heat that the alcoholic acid mixture is produced from generation.

33., wherein provide synthetic gas also to comprise as each described production alcoholic acid method among the claim 1-32:

Gasified bio-matter in having the steam gasification device of fluidized-bed, thus synthetic gas steam produced.

34. the production alcoholic acid method described in claim 33 wherein provides synthetic gas also to comprise:

Before the described biomass of gasification, dry described biomass are to the water capacity of 1%-30% in steam-heated oven.

35. the production alcoholic acid method described in claim 34, wherein dry described biomass are to be used to heat from the heat of heat exchange medium to small part in steam-heated oven, wherein said medium receives the mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water from generation, or comprises the heat that the alcoholic acid mixture is produced from generation.

36. as each described production alcoholic acid method among the claim 33-35, wherein gasified bio-matter is to carry out 750-900 degree centigrade temperature with at the pressure of 100-175kPa in the steam gasification device.

37., wherein provide synthetic gas also to comprise from described synthetic gas steam and remove particulate matter as each described production alcoholic acid method among the claim 33-36.

38. the production alcoholic acid method described in claim 37 wherein provides synthetic gas also to be included in the described synthetic gas of cooling in the synthetic gas heat recovery steam generator, thereby generates steam.

39., wherein provide synthetic gas also to comprise the described synthetic gas steam of cleaning, thereby remove the compound that contains nitrogen or sulphur as each described production alcoholic acid method among the claim 33-38.

40. as each described production alcoholic acid method among the claim 33-39, wherein gasified bio-matter also comprises in the steam gasification device:

Generate hot flue gases by combustion fuel;

Described hot flue gases is delivered to a series of pipes embedding in the fluidized-bed of described steam gasification device, thereby heats described fluidized-bed.

41. the production alcoholic acid method described in claim 40, wherein said fuel are the low-BTU synthetic gas by gasified bio-matter produced in the air blowing gasifier.

42. the production alcoholic acid method described in claim 33 or 41, wherein said pipe have one or more at each metal inset of managing inside and extending on each length of tube.

43. as each described production alcoholic acid method among the claim 33-42, wherein gasified bio-matter also comprises in the steam gasification device:

Described hot flue gases is discharged in the stack gas heat recovery steam generator;

To change the steam in the described stack gas heat recovery steam generator from the steam of described synthetic gas heat recovery steam generator into; With

Described steam is delivered to gasified bio-matter in the steam gasification device.

44. the production alcoholic acid method described in claim 43 wherein provides synthetic gas also to comprise:

Before the described biomass of gasification, dried biomass is 1%-30% or lower to water capacity in steam-heated oven in the steam gasification device;

To be delivered to from the condensation product in the described steam-heated oven in the described stack gas heat recovery steam generator, thereby produce steam;

To be delivered to the dried biomass in the steam-heated oven by the steam that described stack gas heat recovery steam generator generates.

45. as each described production alcoholic acid method among the claim 33-44, wherein said fuel is selected from the group of the gas composition that obtains by methane, Sweet natural gas, landfill gas or by anaerobic digestion fertilizer or biosolids.

46. according to the production alcoholic acid method of claim 1, described method also comprises:

At the pressure of 4700-5500kPa with 220-300 degree centigrade temperature, by with synthetic gas through the inert liq bubbling, change described synthetic gas into methyl alcohol;

In the presence of promotor, in packed bed reactor, generate the mixture of described methyl acetate, hydrogen, methyl alcohol, acetate and water, wherein said metal catalyst is the iridium acetate that is adsorbed on the gac, and wherein said reaction is to carry out in the temperature of the pressure of 900-1500kPa and 200-300 degree centigrade;

In packed bed reactor, generate the described alcoholic acid mixture that comprises, wherein said hydrogenation catalyst is made up of the copper, nickel and the chromium that are adsorbed on the inert substance, wherein producing the described alcoholic acid mixture that comprises is to carry out 160-300 degree centigrade temperature with at the pressure of 3500-4500kPa;

Separate the described mixture that comprises methyl acetate, hydrogen, methyl alcohol, acetate and water, thereby produce the acetate fraction;

Add described acetate fraction to described reactor, thereby produce ethanol;

Wherein provide synthetic gas also to comprise:

Dried biomass is 1%-30% to water capacity in steam-heated oven; The described biomass of gasification in the steam gasification device, thus synthetic gas produced, wherein said gasifier is a box describe device, it has vertical wall and top board; The fluidized-bed that comprises silica sand, rhombspar or peridotites or its combination; The bottom of forming by dispenser panel with internal surface and many through holes, right cylinder with lid has been installed in described through hole, the wherein said right cylinder of adding a cover is hollow, thereby has the passage that transports steam that the plemum below described dispenser panel extends, and wherein said passage extension also narrows to one or more outlet openings that bore in described lid, the described cylindrical longitudinal axis of described outlet opening crosscut, thus steam is expelled to the described bed via described through hole from described plemum, thereby by described outlet opening, with with the parallel plane direction that limits by described dispenser panel internal surface, the described bed of fluidisation equably; And wherein said container has a plurality of pipes that are embedded in the described bed, described pipe transmission hot flue gases, thereby heat described bed, and the plane parallel of wherein said pipe and described dispenser panel, and be arranged complete, wherein the pipe in described cover is parallel to each other, and has triangular orientation each other, and wherein said pneumatolysis is to carry out 750-900 degree centigrade temperature with at the pressure of 100-175kPa; And wherein said hot flue gases produces by gasified bio-matter in the air blowing gasifier, thereby produces the synthetic gas and the described low BTU synthetic gas that burns of low BTU.

47. be used for producing the alcoholic acid method from synthetic gas, described method comprises:

Synthetic gas is provided;

In the presence of catalyzer, change described synthetic gas, thereby produce the mixture that comprises methyl alcohol, carbon monoxide and hydrogen;

By in the presence of one or more catalyzer, make methyl alcohol, carbon monoxide and H-H reaction, produce the mixture that comprises acetate, carbon monoxide and hydrogen;

By in the presence of one or more catalyzer, make acetate, ethanol and reaction of carbon monoxide, produce the mixture that comprises ethyl acetate; With

By in the presence of hydrogenation catalyst, make ethyl acetate and H-H reaction, generation comprises the alcoholic acid mixture.

48. according to claim 47 produce the alcoholic acid method from synthetic gas, wherein produce the mixture that comprises acetate, carbon monoxide and hydrogen and be in the gas phase of the pressure of 215-250 degree centigrade temperature and 140-160psi and carry out.

49. according to claim 47 or 48 produce the alcoholic acid method from synthetic gas, wherein producing the mixture that comprises acetate, carbon monoxide and hydrogen is to utilize to comprise that the catalyzer of VIII family metal carries out.

50. according to claim 49 produce the alcoholic acid method from synthetic gas, wherein said catalyzer is an iridium, and wherein said catalyzer is adsorbed on the solid carbon matrix.

51. according among the claim 47-50 each produce the alcoholic acid method from synthetic gas, wherein produce the mixture that comprises ethyl acetate and be in the liquid phase of 90-110 degree centigrade temperature and 15-25psi and carry out.

52. according among the claim 47-51 each produce the alcoholic acid method from synthetic gas, wherein producing the mixture that comprises ethyl acetate is to utilize to comprise that the catalyzer of sulfur oxide carries out.

53. according among the claim 47-52 each produce the alcoholic acid method from synthetic gas, be in the gas phase of the pressure of 250-270 degree centigrade temperature and 580-610psi, to carry out wherein by ethyl acetate and H-H reaction being produced comprise the alcoholic acid mixture.

54. according among the claim 47-53 each produce the alcoholic acid method from synthetic gas, be to carry out comprising in the presence of a kind of catalyzer of copper, nickel, chromium or its arbitrary combination wherein by making ethyl acetate and H-H reaction produce ethanol.

55. according among the claim 47-54 each produce the alcoholic acid method from synthetic gas, described method also comprises a part of ethanol that charging is produced by ethyl acetate and H-H reaction, thereby produces the mixture that comprises ethyl acetate.

56. according among the claim 47-55 each produce the alcoholic acid method from synthetic gas, described method also is included in and produces separation of hydrogen behind the mixture comprise acetate, carbon monoxide and hydrogen, with the described hydrogen of interpolation, thereby produce ethanol by the reaction of ethyl acetate and hydrogen.

57. be used for producing the alcoholic acid method from biomass, described method comprises:

In the steam gasification device, there is steam and do not having under the conditions of air, gasified bio-matter, thus producing synthetic gas, wherein said steam gasification device is the box describe device that comprises a plurality of pipes and bottom, described bottom is a dispenser panel;

In the presence of one or more catalyzer, make described synthesis gas reaction, thereby produce ethanol; Wherein gasified bio-matter comprises:

Transmit hot gas via described pipe;

Biomass are placed described steam gasification device; With

By via described dispenser panel with vapor injection in described bed, come the described bed of fluidisation.

58. according to claim 57 produce the alcoholic acid method from biomass, described synthesis gas reaction is comprised:

By in the presence of one or more catalyzer, make described synthesis gas reaction, produce the mixture of methyl alcohol, carbon monoxide and hydrogen;

By in the presence of one or more catalyzer, make described methyl alcohol, carbon monoxide and H-H reaction, produce the mixture that comprises acetate hydrogen and carbon monoxide;

From comprising the mixture separation hydrogen of acetate, hydrogen and water;

By in the presence of one or more catalyzer, make described acetate and ethanol synthesis, produce the mixture that comprises ethyl acetate and water;

By in the presence of one or more catalyzer, make described ethyl acetate and H-H reaction, generation comprises the alcoholic acid mixture.

59. according to claim 57 produce the alcoholic acid method from biomass, described synthesis gas reaction is comprised:

By in the presence of one or more catalyzer, make described synthesis gas reaction, produce the mixture that comprises methyl alcohol, carbon monoxide and hydrogen;

By in the presence of one or more catalyzer, make described methyl alcohol, carbon monoxide and H-H reaction, produce the mixture that comprises acetate and hydrogen;

By in the presence of one or more catalyzer, make described acetate and H-H reaction, generation comprises the alcoholic acid mixture.

60. according to claim 57 produce the alcoholic acid method from biomass, described synthesis gas reaction is comprised:

By in the presence of catalyzer, make described synthesis gas reaction become methyl alcohol, produce the mixture that comprises methyl alcohol, carbon monoxide and hydrogen;

By in the presence of catalyzer, make described methyl alcohol and reaction of carbon monoxide, produce the mixture that comprises methyl acetate and hydrogen;

By in the presence of one or more catalyzer, make described methyl acetate and H-H reaction, generation comprises ethanol and methanol mixture.

61. according to claim 57 produce the alcoholic acid method from biomass, described synthesis gas reaction is comprised:

By in the presence of catalyzer, make described synthesis gas reaction become methyl alcohol, produce the mixture that comprises methyl alcohol, carbon monoxide and hydrogen;

By in the presence of one or more catalyzer, make described methyl alcohol, carbon monoxide and H-H reaction, generation comprises the alcoholic acid mixture.

62. according to claim 57 produce the alcoholic acid method from biomass, wherein said described synthesis gas reaction is comprised:

By in the presence of one or more Fischer-Tropsch catalyzer, make described synthesis gas reaction, generation comprises the alcoholic acid mixture.

63. according to claim 57 produce the alcoholic acid method from biomass, wherein said described synthesis gas reaction is comprised:

By in the presence of catalyzer, make described synthesis gas reaction, produce the mixture that comprises acetaldehyde; With

By in the presence of hydrogenation catalyst, make acetaldehyde and H-H reaction, generation comprises the alcoholic acid mixture.

64. as each describedly produces the alcoholic acid method from biomass among the claim 57-63, wherein gasified bio-matter is to carry out at the pressure of 100-175kPa and 750-900 degree centigrade temperature in the steam gasification device.

65. as each describedly produces the alcoholic acid method from biomass among the claim 57-64, thereby wherein said hot flue gases is to produce low BTU synthetic gas by gasified bio-matter in the air blowing gasifier, and the described low BTU synthetic gas that burns, provide thereby produce hot flue gases.

66. as each describedly produces the alcoholic acid method from biomass among the claim 57-66, wherein gasified bio-matter is to carry out at the pressure of 100-175kPa and 750-900 degree centigrade temperature in the air blowing gasifier.

67. as each describedly produces the alcoholic acid method from biomass among the claim 57-66, wherein said steam gasification device comprises wall and crooked top board, described top board is for described eluting gas steam, in described top board or in the top of wall, has outlet, and described fluidized-bed is remained on the height that fully is lower than described top board, so that described fluidized-bed can leak via described outlet without any part, and so that stop the 1-5 period of second in the space of synthetic gas under described top board that produces.

68., wherein described pipe is arranged in the tube bank that extends in parallel with described board plane as each describedly produces the alcoholic acid method from biomass among the claim 57-67.

69. produce the alcoholic acid method from biomass described in claim 68, wherein when observing endways, described intrafascicular pipe relative to each other forms triangle pattern.

70. as each describedly produces the alcoholic acid method from biomass among the claim 57-69, wherein said dispenser panel has the right cylinder of adding a cover in a plurality of holes that are installed in the described dispenser panel, and each adds a cover right cylinder is hollow, thereby form the passage that the plemum below described dispenser panel is drawn, described passage transports steam, and enters described bed via the outlet opening of one or more and described dispenser panel plane parallel orientation.

71. as each describedly produces the alcoholic acid method from biomass among the claim 57-70, wherein said internal diameter of adding a cover the cylindrical hollow 0.25-1.0 of having inch, and describedly add a cover right cylinder extends upward the 1-4 inch from described dispenser panel distance.

72., wherein saidly add a cover the diameter that cylindrical outlet opening has the 1/16-1/4 inch as each describedly produces the alcoholic acid method from biomass among the claim 57-71.

73. as each describedly produces the alcoholic acid method from biomass among the claim 57-72, wherein said pipe has the internal diameter of 0.5-4 inch.

74. as each describedly produces the alcoholic acid method from biomass among the claim 57-73, wherein said hot flue gases enters pipe in the described steam gasification device with 1000-1200 degree centigrade temperature, and leaves described steam gasification device with 750-900 degree centigrade temperature.

75. from the method for biomass generation synthetic gas, described method comprises the following steps:

The bed that has a plurality of pipes and comprise mineral material is provided, and wherein said bed is contained in the box describe device with base plate, and described base plate is a dispenser panel;

By steam is expelled in the described bed via described dispenser panel, with the described bed of the mode fluidisation of the described bed of even fluidisation;

By heating described bed via described pipe transmission hot gas, wherein said hot flue gases produces by combustion fuel;

Biomass are expelled in the described bed, thereby the described biomass that gasify produce synthetic gas.

76. the method from biomass generation synthetic gas described in claim 75, wherein said container has vertical wall, top board and is arranged in the described top board or the outlet in the top of described wall.

77. the method described in claim 75 or 76 from biomass generation synthetic gas, wherein inject biomass by this way, described mode is the height that the fluidized-bed that will have biomass remains on does not have a material to leak via described outlet, and stops the 1-5 period of second in the space of wherein said gas between described bed and described top board.

78. as each described method that produces synthetic gas from biomass among the claim 75-77, wherein carry out described by heat the step of described bed via described pipe transmission hot gas, so that described hot gas enters described pipe with 900-1200 degree centigrade temperature, and described hot gas leaves described pipe with 750-900 degree centigrade temperature.

79. as each described method from biomass generation synthetic gas among the claim 75-78, wherein said pipe has one or more metal insets in each pipe, and wherein said inset extends on the length of pipe.

80., wherein described pipe is arranged in the tube bank of extending with the plane parallel of described plate as each described method among the claim 75-79 from biomass generation synthetic gas.

81. the method from biomass generation synthetic gas described in claim 80, wherein when observing endways, described intrafascicular pipe relative to each other forms triangle pattern.

82. the method from biomass generation synthetic gas described in claim 80 or 81, wherein said bed comprises 1-4 tube bank, has the interval of 2-4 foot between described tube bank, and wherein minimum tube bank 2-4 foot on described dispenser panel.

83. as each described method from biomass generation synthetic gas among the claim 75-82, the described biomass that wherein gasify are to carry out at the pressure of 100-175kPa with 750-900 degree centigrade temperature.

84. as each described method that produces synthetic gas from biomass among the claim 75-83, wherein said dispenser panel has a plurality of holes and a plurality of right cylinder of adding a cover that is installed in the described hole, and the wherein said right cylinder of adding a cover is hollow, thereby has the passage that transports steam that the plemum below described dispenser panel extends, and wherein said passage extends to one or more outlet openings that bore in described lid, the described cylindrical longitudinal axis of described lid crosscut, thus steam is expelled to the described bed from described plemum, thereby via described outlet opening, to be parallel to the planar direction of described dispenser panel, the described bed of fluidisation.

85. according to claim 84 produce the device of synthetic gas from biomass, wherein the described right cylinder of adding a cover is arranged on the described dispenser panel, thus described of fluidisation equably.

86. the device from biomass generation synthetic gas according to claim 84 or 85 wherein is arranged in the described right cylinder of adding a cover on the described dispenser panel, thereby forms multiple rectilinearity or triangle pattern.

87. according among the claim 84-86 each produce the device of synthetic gas from biomass, wherein saidly add a cover right cylinder extends upward the 1-4 inch from described dispenser panel distance, and wherein said outlet opening has the diameter of 1/16-1/4 inch, and wherein saidly adds a cover cylindrical passage and have 1/4 inch-1 inch diameter.

88. as each described method that produces synthetic gas from biomass among the claim 75-87, wherein utilize the conical screw feeder that is arranged on the described wall of container to carry out biomass are expelled in the described bed, during with the described bed of convenient fluidisation, described biomass are expelled to the middle part of described bed, and when described bed is non-fluidizing, be expelled on the top of described bed, and so that enter in described biomass near the site of described container, to be used to prevent the mode of the described bed of air admission, form the biomass plug.

89. as each described method from biomass generation synthetic gas among the claim 75-88, wherein said pipe has 0.5 inch-4 inches internal diameter.

90. as each described method from biomass generation synthetic gas among the claim 75-89, wherein said bed comprises the mineral material of the size of particles with 300-400 micron.

91. as each described method from biomass generation synthetic gas among the claim 75-90, wherein said bed comprises silica sand, rhombspar or peridotites or their combination.

92. as each described method from biomass generation synthetic gas among the claim 71-85, described method also comprises:

Before gasified bio-matter, dried biomass to 30% or lower water capacity in the steam under pressure moisture eliminator.

93. the method described in claim 92 from biomass generation synthetic gas, described method also comprises described hot flue gases is discharged to heat recovery steam generator from described pipe, to be discharged to described heat recovery steam generator by condensation product and the steam that described moisture eliminator produces, in described heat recovery steam generator, generate steam and in drying or in the described bed of fluidisation, use described steam.

94. as each described method that produces synthetic gas from biomass among the claim 75-93, described method also comprises described hot flue gases is discharged to the heat recovery steam generator from described pipe, generate steam and in the described bed of fluidisation, use the steam that generates by described heat recovery steam generator from vapour source.

95. the method from biomass generation synthetic gas described in claim 94, wherein generating steam is to utilize by the synthetic gas that is produced by gasification is carried out through the steam that the synthetic gas heat recovery steam generator produces.

96. according among the claim 75-95 each produce the method for synthetic gas from biomass, wherein said hot gas is the heating flue gas that produces by combustion fuel.

97. according to claim 96 produce the method for synthetic gas from biomass, wherein said fuel is selected from by by the following group of forming: landfill gas, Sweet natural gas, methane, the liquid fuel that is derived from oil, oil fuel, diesel oil, biomass-derived fuel, biofuel, fischer-tropsch liquid (Fischer-Tropschliquids) or the gas that is produced by the anaerobic digestion of fertilizer or biosolids.

98. the method from biomass generation synthetic gas described in claim 96, wherein said fuel is the low BTU synthetic gas by gasified bio-matter produced in the air blowing gasifier.

99. the method from biomass generation synthetic gas described in claim 98, wherein gasified bio-matter comprises in the air blowing gasifier:

The container that contains the silica sand bed is provided;

By injecting air in the described bed the described bed of fluidisation;

Biomass are placed described bed;

The described biomass that gasify, thus low BTU synthetic gas produced.

100. the method from biomass generation synthetic gas described in claim 93, wherein said silica sand has the size of particles of 300-400 micron.

101. the method from biomass generation synthetic gas described in claim 99 or 100 is wherein injected the described bed of air admission and is comprised:

Provide dispenser panel as container floor with a plurality of holes, each hole has the right cylinder of adding a cover that is installed in wherein, each adds a cover right cylinder is hollow, thereby passage with the plemum extension below described dispenser panel of transporting air, extend to one or more outlet openings that in described lid, bore, the described cylindrical longitudinal axis of described lid crosscut;

To be parallel to the direction of described dispenser panel, transport air is through described right cylinder and enter described bed, thus the described bed of fluidisation.

102. the method from biomass generation synthetic gas according to claim 101 wherein is arranged in the described right cylinder of adding a cover on the described dispenser panel with multiple rectilinearity or triangle pattern.

103. method from biomass generation synthetic gas according to claim 101 or 102, the wherein said right cylinder of adding a cover extends upward 1/4 inch-1 inch distance from described dispenser panel, and wherein said outlet opening has the diameter of 1/16-1/4 inch, and wherein saidly adds a cover the diameter that cylindrical passage has the 0.5-1 inch.

104. as each described method from biomass generation synthetic gas among the claim 99-103, the described biomass that wherein gasify produce low BTU synthetic gas and also comprise:

Utilize the startup burner that described bed is heated to operating temperature; With

Keep described temperature by injection air and biomass in described bed.

105. be used to produce the alcoholic acid device, such equipment comprises:

Methanol reactor, described methanol reactor have synthetic gas input thing, and have the output that comprises methyl alcohol, carbon monoxide and hydrogen;

The methyl acetate reactor, described methyl acetate reactor has the catalyzer that comprises a kind of metal that is selected from the group of being made up of iridium, iron, cobalt, nickel, ruthenium, palladium, osmium and platinum, and utilize promotor, and have the methyl acetate of comprising, acetate, hydrogen, water and methanol mixture as output;

Distiller, described distiller separates the described component that comprises methyl acetate, acetate, hydrogen, water and methanol mixture; With

The ethanol synthesis device, described ethanol synthesis utensil has the input thing that comprises hydrogen, methyl acetate and methyl alcohol, and has the alcoholic acid of comprising output.

106. according to the production alcoholic acid device of claim 105, wherein said distiller separates hydrogen with comprising methyl acetate, acetate, water and methanol mixture, wherein described hydrogen fraction is fed to described ethanol synthesis device; And has the after-fractionating device that separates the composition that comprises methyl acetate, acetate, water and methanol mixture.

107. according to the production alcoholic acid device of claim 106, wherein said after-fractionating device with methyl acetate and methanol mixture from comprising the mixture separation of acetate and water; And has the 3rd distiller that separates the ingredients of a mixture comprise methyl acetate, methyl alcohol and described promotor.

108. production alcoholic acid device according to claim 107, wherein said the 3rd distiller separates from comprising methyl acetate the promotor fraction with methanol mixture, and wherein described methyl acetate and methanol mixture are fed to described ethanol synthesis device, and wherein described promotor are fed to described methyl acetate reactor.

109. as each described production alcoholic acid device among the claim 105-108, wherein said methyl acetate reactor has the catalyzer that comprises iridium.

110. according to the production alcoholic acid device of claim 109, wherein said methyl acetate reactor has the catalyzer that comprises iridium acetate.

111. according to each production alcoholic acid device among the claim 105-110, wherein said promotor is an alkylogen.

112. according to each production alcoholic acid device among the claim 105-111, wherein said methyl acetate reactor is worked in the gas phase of the pressure of 200-300 degree centigrade temperature and 1000-1500kPa.

113. according to each production alcoholic acid device among the claim 105-112, wherein said methyl acetate reactor is a packed bed reactor, wherein said packed bed contains the catalyzer that is adsorbed on the gac.

114. according to each production alcoholic acid device among the claim 105-113, wherein said ethanol synthesis device uses catalyzer, described catalyzer comprises copper, nickel and chromium or its combination that is adsorbed on the inert substance.

115. according to each production alcoholic acid device among the claim 105-114, wherein said ethanol synthesis device is worked in the gas phase of the pressure of 225-300 degree centigrade temperature and 3500-4500kPa.

116. according to each production alcoholic acid device among the claim 105-115, wherein said ethanol synthesis device is with the ratio work to methyl acetate of the hydrogen of 0:1-15:1.

117. according to each production alcoholic acid device among the claim 105-116, described device has the total evaporator that is used for separating acetic acid and water, wherein described acetate is added to described ethanol synthesis device, thereby produces ethanol.

118. according to each production alcoholic acid device among the claim 105-117, wherein said ethanol synthesis device is the packed bed reactor with heterogeneous catalyst.

119. according to each production alcoholic acid device among the claim 105-118, wherein said methanol reactor comprises the catalyzer of being made up of metallic compound that is suspended in the inert liq, and wherein said carbon monoxide, hydrogen and methyl alcohol are in gas phase.

120. according to each production alcoholic acid device among the claim 105-119, wherein said methanol reactor is at 200-300 degree centigrade temperature and the pressure of 4700-5500kPa, in gas phase with described reactant and product work.

121. according to each production alcoholic acid device among the claim 105-120, wherein said methanol reactor can receive steam, and described methanol reactor can make carbon monoxide and steam reaction, thereby produces dioxide and hydrogen.

122. according to each production alcoholic acid device among the claim 105-121, described device also comprise with synthetic gas be compressed to 2400-3500kPa pressure compressor and described synthetic gas is heated to the well heater of 220-450 degree centigrade temperature, and described synthetic gas is delivered to the steam converter that comprises base metal catalysts, and wherein said steam converter changes the hydrocarbon that contains in the described synthetic gas into carbon monoxide and hydrogen.

123. according to each production alcoholic acid device among the claim 105-122, described device also comprises the compressor that synthetic gas is compressed to the pressure of 4700-5500kPa, with the well heater that described synthetic gas is heated to 220-300 degree centigrade temperature, and wherein the synthetic gas of the described compressor of described process is delivered to described methanol reactor.

124. according to each production alcoholic acid device among the claim 105-123, described device also comprises the output that receives described ethanol synthesis device and the single flash device of separation of hydrogen, wherein said methanol reactor can receive the hydrogen from described single flash device, and comprise reception from the methyl alcohol of described ethanol synthesis device and the methyl alcohol distiller of ethanol and separation of methanol, wherein said methanol reactor can receive the methyl alcohol from described methyl alcohol distiller.

125. according to each production alcoholic acid device among the claim 105-124, described device also comprises:

Steam gasification device with fluidized-bed, described fluidized-bed receives biomass and steam and exports synthetic gas,

Wherein said steam gasification utensil has the pipe that is embedded in the bed that receives hot gas, and in addition, the described bed of wherein said pipe heating.

126. production alcoholic acid device according to claim 125, wherein said steam gasification device is the container with vertical wall, wherein said wall forms rectangle, has dispenser panel as base plate, and wherein said dispenser panel has a plurality of holes, each hole occupies by adding a cover right cylinder, the wherein said right cylinder of adding a cover is hollow, thereby has the passage that transports steam that the plemum below described dispenser panel extends, and wherein said passage extends to one or more outlet openings that bore in described lid, the described cylindrical longitudinal axis of described lid crosscut wherein to be parallel to the in-plane of described dispenser panel, is expelled to steam the described bed from described plemum.

127., wherein the described right cylinder of adding a cover is arranged on the described dispenser panel with multiple trilateral or rectangular pattern according to the production alcoholic acid device of claim 126.

128. according to each production alcoholic acid device among the claim 125-127, wherein said steam gasification device is in 750-900 degree centigrade temperature and the pressure work of 100-175kPa.

129. according to each production alcoholic acid device among the claim 125-128, wherein said steam gasification utensil has the bed that comprises silica sand, rhombspar, peridotites or their combination.

130., produce the burner of described hot gas thereby described device also comprises combustion fuel according to each production alcoholic acid device among the claim 128-129.

131. according to the production alcoholic acid device of claim 130, wherein said fuel is selected from by by the following group of forming: methane, Sweet natural gas, landfill gas, the liquid fuel that is derived from oil, oil fuel, diesel oil, biomass-derived fuel, biofuel, fischer-tropsch liquid or the gas that produces by the anaerobic digestion of fertilizer or biosolids.

132. according to the production alcoholic acid device of claim 130, described device also comprises the air blowing gasifier that receives biomass and produce low BTU synthetic gas, and wherein said low BTU synthetic gas is a burnt fuel in described burner.

133. according to each production alcoholic acid device among the claim 130-132, described device comprises that also reception is from the hot gas of described steam gasification device and produce the heat recovery steam generator of steam.

134. production alcoholic acid device according to claim 133, described device also comprises the steam under pressure moisture eliminator, described steam under pressure moisture eliminator receives steam and the humidogene material from described heat recovery steam generator, and output exsiccant biomass, refrigerative steam and water condensate, wherein described exsiccant biomass are added to described steam gasification device and described air blowing gasifier, and wherein described condensate feed is arrived described heat recovery steam generator.

135. according to each production alcoholic acid device among the claim 125-134, wherein described pipe is provided with bunchy, wherein described bundle is arranged to make described pipe to be parallel to described dispenser panel plane and extends.

136. according to each production alcoholic acid device among the claim 125-135, wherein when observing endways, described intrafascicular tubular triangulation pattern.

137. according to each production alcoholic acid device among the claim 125-136, wherein said pipe has one or more metal insets in described pipe inside, wherein said inset extends along the length of described pipe.

138. according to the production alcoholic acid device of claim 105, wherein

Described methanol reactor is in the pressure of 4700-5500kPa and 220-300 degree centigrade temperature work;

Wherein said methyl acetate reactor is a packed bed reactor, and described packed bed reactor has the catalyzer of being made up of the iridium acetate that is adsorbed on the gac, and wherein said reactor is in the pressure of 900-1500kPa and 200-300 degree centigrade temperature work;

Wherein said ethanol synthesis device is a packed bed reactor, described packed bed reactor has the catalyzer that comprises the copper, nickel and the chromium that are adsorbed on the inert substance, and wherein said reactor is in 160-300 degree centigrade temperature and the pressure work of 3500-4500kPa, and can make acetic acidreaction, thereby produce ethanol from described methyl acetate reactor; And comprise:

Biomass moisture eliminator, described biomass moisture eliminator are dried to biomass and are lower than 30% humidity level;

The steam gasification device, described steam gasification device turns to synthetic gas with biogas, wherein said gasifier is the box describe device with bed, described bed comprises silica sand, rhombspar or peridotites, or their combination, described container has the bottom, described bottom is the dispenser panel with a plurality of holes, right cylinder with lid has been installed in described hole, the wherein said right cylinder of adding a cover is hollow, thereby has the passage that transports steam that the plemum below described dispenser panel extends, and wherein said passage extends to one or more outlet openings that bore in described lid, the described cylindrical longitudinal axis of described lid crosscut, so that steam is expelled to the described bed from described plemum, thereby via described outlet opening, with with parallel plane direction by described dispenser panel, the described bed of fluidisation; And wherein said container has a plurality of pipes that are embedded in the described bed, described pipe transports hot flue gases, thereby heat described bed, and wherein said pipe is parallel to the plane of described dispenser panel and extends, and wherein described pipe is arranged bunchy, wherein when observing endways, described pipe has triangular orientation mutually, and described steam gasification device is in 750-900 degree centigrade temperature and the pressure work of 100-175kPa;

The air blowing gasifier, described air blowing gasifier turns to low BTU synthetic gas with biogas; With

Burner, its described low BTU synthetic gas that burns, thus described hot flue gases is provided to described steam gasification device.

139. be used to produce the alcoholic acid method, described method comprises:

Gasified bio-matter, thus the synthetic gas that contains carbon monoxide and hydrogen produced;

In the presence of metal catalyst, make synthesis gas reaction, thereby produce the mixture that comprises methyl alcohol and carbon monoxide;

In the presence of second metal catalyst, make methyl alcohol and reaction of carbon monoxide, thereby produce the mixture that comprises methyl acetate; With

In the presence of hydrogenation catalyst, make methyl acetate and H-H reaction, comprise the alcoholic acid mixture thereby produce.

140. be used to produce the alcoholic acid method, described method comprises:

Adding steam and not having under the situation of air, at the indoor gasified bio-matter of fluidized-bed gasification, wherein utilize the described chamber of hot gas indirect heating that forms from combustion fuel, thereby produce synthetic gas;

Synthetic gas is progressively being reacted in the catalyzed reaction, thereby produce ethanol.

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