CN106367095B - A kind of processing method that biomass refines product altogether - Google Patents
A kind of processing method that biomass refines product altogether Download PDFInfo
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Abstract
A kind of processing method that biomass refines product altogether, comprising: I) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, after the reaction was completed, product is separated by solid-liquid separation, collects product liquid；II) product liquid is distilled, steaming excess is collected, obtains biomass and refine product altogether；III biomass) is total to refining product to contact with hydrogenation catalyst, makes product hydrogenation deoxidation.By above-mentioned process, grease alcoholysis product adds hydrogen to become the hydro carbons of bigger molecule, and biomass liquefying product adds hydrogen to become the relatively small hydro carbons of molecule, can prepare fuel or purification is chemical products.
Description
Technical field
The invention belongs to the regeneration fields of biomass material, are related to the processing side that a kind of pair of biomass refines product altogether
Method.
Background technique
Biomass is can be uniquely converted to the renewable carbon resource of alternative conventional liquid petroleum fuel and other chemicals,
And heat chemistry Efficient Conversion using technology be biomass energy develop and use main approach, therefore biomass high-pressure liquefy
Concern of the technology by many researchers.High-pressure liquefaction refers to that in solvent medium, reaction temperature is 200-400 DEG C, reaction pressure
Under conditions of power is 5-25MPa, technique that biomass liquefying is produced into product liquid.Catalysis is usually added into during high-pressure liquefaction
The reducibility gas such as agent and H2, CO improve liquefied fraction, improve product liquid property.
Most common high-pressure liquefaction solvent is water, other further include low-carbon alcohols, low-carbon ester, acetone, naphthane, phenol
Or their mixture etc..The characteristics of these solvents is that molecular weight is smaller, to the high-temperature digestion of biomass liquefying macromolecular product
Property it is poor, solid residue is more, and biomass liquefying yield is relatively low, is typically necessary and catalyst is added improves biomass liquefying rate.
For example the patent application of Publication No. CN1952043A proposes biomass liquefied method in water, this method needs to use K2CO3
The liquefied fraction that the equal alkali such as salt or KOH are catalyst to improve biomass；The patent application of Publication No. CN101560416A proposes
The liquifying method of biomass in supercritical methanol, this method are also required to use K2CO3The equal alkali such as salt or KOH are catalyst to mention
The liquefied fraction of high biomass.Although salt or alkali, which is added, as catalyst can improve biomass liquefying rate, production is not only increased
Cost can also generate a large amount of waste pollution environment.
Summary of the invention
Present inventor's discovery, solid biomass and fat compound refine (referred to as biomass altogether in monohydric alcohol
Refining altogether), it can also be improved the liquefied fraction of biomass.But in the liquid product refined altogether, both product containing biomass liquefying, also fatty
Class compound, is unfavorable for following process.
The present invention relates to the processing methods that a kind of biomass refines product altogether, comprising:
I) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, instead
After the completion of answering, product is separated by solid-liquid separation, collects product liquid；
II) product liquid is distilled, steaming excess is collected, obtains biomass and refine product altogether；
III biomass) is total to refining product to contact with hydrogenation catalyst, makes product hydrogenation deoxidation.
By above-mentioned process, grease alcoholysis product adds hydrogen to become the hydro carbons of bigger molecule, and biomass liquefying product
Add hydrogen to become the relatively small hydro carbons of molecule, fuel can be prepared or purification is chemical products.
Step I) in, the solid biomass refer to generated using big gas and water, soil etc. by photosynthesis it is various
The waste and extract that organism and organism generate.The organism includes various plants, animal and microorganism, example
Such as timber, bamboo, algae；The waste include but is not limited to agriculture and forestry organic waste material (such as sawdust, stalk, shell etc.),
Human and animal excreta, domestic waste etc.；The extract includes but is not limited to lignin, cellulose, hemicellulose, animal egg
It is white etc..
The fat compound refers to containing the organic compound of at least one C10-C24 Long carbon chain, refers mainly to
The fatty acid of C10-C24, the fatty alcohol of C10-C24, the fatty aldehyde of C10-C24, the fatty acid amide of C10-C24, C10-C24
Fatty acid C1-C18 alcohol ester, the fatty glyceride of C10-C24 and mixture of above compound composition etc., preferably C10-
C24 fatty glyceride, i.e. animal and plant fat, such as soybean oil, palm oil, lard, butter.
The fat compound can pass through pre-add hydrogen, make part or all of ethylene linkage saturation contained in aliphatic chain, so
Participate in liquefaction reaction again afterwards.
The addition weight of the fat compound is 0.1~10 times of solid biomass weight, preferably 1~8 times, more
It is preferred that 2~6 times.
Solid biomass of the present invention does not include the solid matter rich in fat compound, such as animal tallow.
Described monohydric alcohol refers to the monohydric alcohol of C1-C10, including but not limited to methanol, ethyl alcohol, propyl alcohol, isopropanol etc. or it
Mixture, preferably methanol and ethyl alcohol, more preferable methanol.
The mass ratio of described monohydric alcohol and solid biomass is 1:5-20:1, preferably 1:1-10:1, more preferable 1.5:1-
8:1。
The biological particles size is without restriction, preferably 10~100 mesh, more preferable 30~80 mesh.
The high-pressure bottle type is without restriction, can be reaction kettle or tubular reactor.For example reaction kettle, can be to reaction
Object is stirred, and mixing speed is unlimited；System pressure is determined by reactant dosage, reactant solvents and reaction temperature, is not necessarily to people
Work is adjusted.For example tubular reactor, reaction pressure are 3~25MPa, preferably 8~20MPa, more preferable 10~18MPa.
The reaction temperature is 200~450 DEG C, preferably 280~360 DEG C.
The reaction time is 3min~6h, preferably 10min~2h.
Step II) in, described distillation refers to that refining biomass product liquid altogether distills, with all or part of removing
The light component (i.e. A phase) that the biomass liquefying of monohydric alcohol and boiling point lower than 160 DEG C generates.
Described distillation mode includes air-distillation or vacuum distillation, and different vapo(u)rizing temperatures specifically can be used, or
Person takes to distill at the same temperature, also the mode of fractional condensaion can be used to be separated.
Above-mentioned steps III) in described hydrogenation catalyst can be non-precious metal catalyst, can also be noble metal catalyst,
Active component can be selected from least one of oxide or sulfide of the metals such as Pt, Pd, Ru, Co, Mo, Ni, W, by oxidation
Object poidometer, content are 0.1~50%, preferably 0.5~40%, more preferable the 1~30% of total catalyst weight.Carrier can select
From active carbon, Al2O3、SiO2、TiO2One or more of mixture etc..
The hydrogenation catalyst can be prepared according to existing method, such as can refer to CN1229835A, CN1245204A
Disclosed method preparation.
Described hydrogenation deoxidation reaction condition is that reaction temperature is 150~450 DEG C, and Hydrogen Vapor Pressure is 0.1~10MPa, instead
It should be carried out in intermittently or serially flow reactor.In batch reactor, catalyst amount is the 0.1~10% of oily weight,
Reaction time is 0.5~15h；In continuous flow reactor, standard state hydrogen to oil volume ratio is 100:1~5000:1, oily
Volume space velocity is 0.1~20h‐1。
Described batch reactor preferably has the reaction kettle of gas flowmeter and counterbalance valve, controls kettle with gas flowmeter
Interior gas flow rate, with pressure in counterbalance valve control kettle.
Preferably 220~400 DEG C of described reaction temperature, more preferable 260~380 DEG C.
Described Hydrogen Vapor Pressure preferably 0.5~8MPa, more preferable 1~5MPa.
The preferably oily weight 0.5~8% of described catalyst weight content, more preferable 1~5%.
Preferably 2~10h of described reaction time, more preferable 3~7h.
Described standard state hydrogen to oil volume ratio preferred 300:1~3000:1, more preferable 400:1~2000:1.
Volume space velocity preferably 0.3~10h of described oil‐1, more preferable 0.5~5h‐1。
Above-mentioned steps III) in, if the active component of used catalyst is the oxide of Co, Mo, Ni, W, need to use
CS2Or H2S carries out presulfurization, it is made to be converted into metal sulfide.
Above-mentioned steps III) in, if the catalyst used is metal sulfide, can be refined in product altogether to biomass in advance
Sulfur-containing compound, such as thiophene is added, to improve the service life of catalyst.It is general require the weight content that sulphur is added be 0.05~
0.7%.
Biomass high-pressure liquefaction products complicated composition, and molecular weight is larger, room temperature is solid-state, and direct hydrogenation deoxidation is relatively more tired
Difficulty is mostly used some model compounds on document and is studied, or biomass high-pressure liquefaction products are dissolved in hexamethylene, tetrahydro
In the organic solvents such as naphthalene, hydrogenation deoxidation is then carried out.Method of the invention is that solid biomass and grease is total in monohydric alcohol
Refining, while solid biomass liquefaction, alcoholysis reaction occurs for grease and monohydric alcohol, obtains the solid biomass that room temperature is liquid
Liquefaction products and grease alcoholysis product.Biomass liquefying product is dissolved in grease alcoholysis product, then can add hydrogen together
Deoxidation, grease alcoholysis product add hydrogen to become the hydro carbons of bigger molecule, and to add hydrogen to become molecule relatively small for biomass liquefying product
Hydro carbons, can prepare fuel or purification be chemical products.This process does not need that solvent additionally is added, and can make biomass liquefying
Product has dispersibility well, is conducive to its hydrogenation deoxidation, while grease alcoholysis product can also be made to obtain effectively adding hydrogen.
Specific embodiment
The present invention is further illustrated below by embodiment, but the present invention is not limited thereto.
Embodiment 1
20g dry Poplar Powder (100 mesh) is added in 500ml autoclave, and 80g methanol and 80g soybean oil is added, it is close
It is honored as a queen, 320 DEG C is warming up under conditions of low whipping speed 600RPM, keep the temperature 1h, stop heating, Temperature fall to room temperature.Separation
Solid residue, liquid phase weight 188.0g.Liquid phase is distilled at 100 DEG C, 5000Pa, biomass is obtained and refines product liquid altogether
98.2g, its oxygen content of elemental analysis are 13.0%.(active component is the Hydrobon catalyst produced with Chang Ling catalyst plant
NiO content 2.9wt%, WO3Content 28wt%, carrier Al2O3) product progress hydrogenation deoxidation is refined biomass altogether.Reaction condition
Are as follows: loaded catalyst 10mL, in fixed bed reactors, with containing 5%CS2Hexamethylene at 360 DEG C, 4MPa to catalysis
Agent presulfurization 2h, liquid hourly space velocity (LHSV) 2h‐1, hydrogen-oil ratio is 400 under standard state, oxidizes metal object by presulfurization and is converted into gold
Belong to sulfide；Product liquid is refined biomass altogether under the conditions of same temperature, pressure, liquid hourly space velocity (LHSV), hydrogen-oil ratio again to add
Hydrogen deoxidation is previously added 3000ppm thiophenic sulfur in product.After reaction, elemental analysis shows oxygen content 1.2% in product,
90.7% is reduced compared with reaction raw materials.
Embodiment 2
50g dry Poplar Powder (100 mesh) is added in 500ml autoclave, and 80g methanol and 80g soybean oil is added, it is close
It is honored as a queen, 300 DEG C is warming up under conditions of low whipping speed 600RPM, keep the temperature 1h, stop heating, Temperature fall to room temperature.Separation
Solid residue, liquid phase weight 188.7g.Liquid phase is distilled at 100 DEG C, 5000Pa, biomass is obtained and refines product liquid altogether
98.7g, its oxygen content of elemental analysis are 13.2%.The 5%Pt/Al produced with Xi'an Kai Li chemical company2O3Catalyst is to total refining
Product liquid carries out hydrogenation deoxidation.Reaction condition are as follows: in fixed bed reactors, 320 DEG C of reaction temperature, reaction pressure 4MPa,
Liquid hourly space velocity (LHSV) is 0.2h‐1, hydrogen-oil ratio is 800 under standard state.After reaction, elemental analysis shows oxygen content in product
1.1%, 91.7% is reduced compared with reaction raw materials.
Embodiment 3
30g dry willow powder (100 mesh) is added in 500ml autoclave, and 100g methanol and 80g palm oil is added,
After sealing, it is warming up to 350 DEG C under conditions of low whipping speed 800RPM, keeps the temperature 1.5h, stops heating, Temperature fall to room temperature.
Separating solid residue, liquid phase weight 196.9g.Liquid phase is distilled at 100 DEG C, 5000Pa, biomass is obtained and refines product liquid altogether
88.8g, its oxygen content of elemental analysis are 13.0%.The 10%Pd/C catalyst produced with Xi'an Kai Li chemical company is to total refining liquid
Body product carries out hydrogenation deoxidation.Reaction condition are as follows: in an autoclave with gas flowmeter and counterbalance valve, liquid is added
The Pd/C catalyst of products weight 3%, then in H2Flow velocity 100mL/min, pressure 2MPa, 5h is reacted under the conditions of 300 DEG C of temperature.
After reaction, elemental analysis shows oxygen content 0.7% in product, and 94.6% is reduced compared with reaction raw materials.
Comparative example 1
20g dry Poplar Powder (100 mesh), 160g methanol are added in 500ml autoclave, after sealing, stirred
It is warming up to 320 DEG C under conditions of speed 600RPM, keeps the temperature 1h, stops heating, Temperature fall to room temperature.Isolate solid residue
Afterwards, methanol is distilled out, obtains Poplar Powder liquefaction products (room temperature is solid-state), elemental analysis shows oxygen content 31.2%.Use Chang Ling
(active component is NiO content 2.9wt%, WO to the Hydrobon catalyst of catalyst plant production3Content 28wt%, carrier are
Al2O3) hydrogenation deoxidation is carried out to Poplar Powder liquefaction products.Reaction condition are as follows: liquefaction products are dissolved with hexamethylene, and the two ratio is
1:4,20g liquefaction products, 80g hexamethylene is encased in 500mL reaction kettle, and catalyst 10g, CS is then added2Additional amount
For 1.1g, Hydrogen Vapor Pressure 50bar.After sealing reaction kettle, low whipping speed 500RPM, at 320 DEG C of temperature to the pre- sulphur of catalyst
Change 2h, object is oxidized metal by presulfurization and is converted into metal sulfide；Liquefaction products are carried out under the conditions of 360 DEG C again to add hydrogen
Deoxidation 2h.After reaction, chromatograph reduces 74.3% oxygen-containing 8.0% in product compared with reaction raw materials.
Comparative example 2
30g dry willow powder (100 mesh), 180g methanol are added in 500ml autoclave, after sealing, low whipping speed
It is warming up to 350 DEG C under conditions of 800RPM, keeps the temperature 1.5h, stops heating, Temperature fall to room temperature.After isolating solid residue,
Methanol is distilled out, obtains willow powder liquefaction products (room temperature is solid-state), elemental analysis shows oxygen content 30.8%.It is triumphant with Xi'an
The 10%Pd/C catalyst of vertical chemical company's production is to progress hydrogenation deoxidation.Reaction condition are as follows: dissolve 20g liquid with 80g naphthane
Change product, is then added in the autoclave with gas flowmeter and counterbalance valve, adds the Pd/C of raw material weight 3%
Catalyst, then in H2Flow velocity 100mL/min, pressure 2MPa, it is reacted under the conditions of 300 DEG C of temperature, reaction time 6h.Instead
After answering, chromatograph reduces 70.1% oxygen-containing 9.2% in product compared with reaction raw materials.
Claims (11)
1. the processing method that a kind of biomass refines product altogether, comprising:
I) solid biomass, monohydric alcohol and fat compound are added in high-pressure bottle in 200~450 DEG C of refinings altogether, reacted
Cheng Hou is separated by solid-liquid separation product, collect product liquid, the fat compound be selected from C10-C24 fatty acid,
The fatty alcohol of C10-C24, the fatty aldehyde of C10-C24, the fatty acid amide of C10-C24, C10-C24 fatty acid C1-C18 alcohol ester
And the mixture of above compound composition；
II) product liquid is distilled, steaming excess is collected, obtains biomass and refine product altogether；
III biomass) is total to refining product to contact with hydrogenation catalyst, makes product hydrogenation deoxidation.
2. according to the method for claim 1, wherein the solid biomass includes that various organisms and organism generate
Waste and extract.
3. according to the method for claim 1, wherein the fat compound is selected from the fatty acid glycerine of C10-C24
Ester.
4. according to method described in claim 1 or 3, wherein the addition weight of the fat compound is solid biologic
0.1~10 times of matter weight.
5. according to the method for claim 1, wherein described monohydric alcohol is selected from the monohydric alcohol of C1-C10.
6. according to the method for claim 1, wherein described monohydric alcohol is selected from methanol and/or ethyl alcohol.
7. according to the method for claim 1, wherein the mass ratio of described monohydric alcohol and solid biomass is 1:5-20:
1。
8. according to the method for claim 1, wherein the high-pressure bottle is reaction kettle or tubular reactor, reaction pressure
Power is 3~25MPa.
9. according to the method for claim 1, wherein the reaction temperature is 280~360 DEG C.
10. according to the method for claim 1, wherein the active component of described hydrogenation catalyst be selected from Pt, Pd, Ru, Co,
At least one of oxide or sulfide of Mo, Ni, W metal, based on oxide weight, content is total catalyst weight
0.1~50%, catalyst carrier is selected from active carbon, Al2O3、SiO2、TiO2One of or a variety of mixtures.
11. according to the method for claim 1, wherein described hydrogenation deoxidation reaction condition be reaction temperature be 150~
450 DEG C, Hydrogen Vapor Pressure is 0.1~10MPa, and reaction carries out in intermittently or serially flow reactor；In batch reactor, urge
Agent dosage is the 0.1~10% of oily weight, and the reaction time is 0.5~15h；In continuous flow reactor, standard state hydrogen
Oil volume ratio is 100:1~5000:1, and oily volume space velocity is 0.1~20h‐1。
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| CN101113348B (en) * | 2007-09-06 | 2013-04-10 | 昆明理工大学 | Process for preparing bio-fuel by high-pressure fluid transformation technique |
| CN101906312B (en) * | 2009-06-05 | 2013-07-24 | 北京瑞增兰宇新能源有限公司 | Method for preparing hydrocarbon fuel oil by mixing biomass oil and animal and vegetable oil |
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