WO2010119973A1

WO2010119973A1 - Hydrocarbon oil production system and method for producing hydrocarbon oil

Info

Publication number: WO2010119973A1
Application number: PCT/JP2010/056898
Authority: WO
Inventors: 直彌吉川; 二郎及川; 浩康中村
Original assignee: Ｇｇｉジャパン株式会社
Priority date: 2009-04-14
Filing date: 2010-04-13
Publication date: 2010-10-21
Also published as: JPWO2010119973A1; WO2010119972A1; JPWO2010119972A1

Abstract

A target hydrocarbon oil is efficiently produced from various starting carbonaceous materials. A system for producing a hydrocarbon oil, which comprises: a heat decomposition device for thermally decomposing a carbonaceous material to give a dry distillation gas; a purification device for purifying the dry distillation gas; and a hydrocarbon-synthesizing device for converting the thus purified gas into a hydrocarbon oil in the presence of a hydrocarbon-synthesizing catalyst. This system is provided with a hydrogen-supply unit for supplying hydrogen gas between the purification device and the hydrocarbon-synthesizing device.

Description

Hydrocarbon oil production system and method for producing hydrocarbon oil

The present invention relates to a hydrocarbon oil production system and a hydrocarbon oil production method.

Various attempts have been made to pyrolyze waste and biomass to generate dry distillation gas and to convert the generated dry distillation gas into a liquid fuel using a Fischer-Tropsch synthesis catalyst.
Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-205135) discloses a methane fermentation tank for methane fermentation treatment of low-calorie waste, a carbonization furnace for burning carbonization by burning high-calorie waste, and the carbonization furnace. A gasification furnace for introducing and burning the generated carbide to gasify, a gas purification device for purifying the gas generated in the gasification furnace, and liquid fuel from the purified gas mainly containing the purified CO and H2 A composite waste treatment system including a liquid fuel synthesizing apparatus that performs FT synthesis (Fischer-Tropsch synthesis) and that supplies biogas generated in a methane fermentation tank to a gasification furnace as a combustor is disclosed.
Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-260832) discloses that solid waste can be efficiently and easily gasified and reformed simultaneously with carbonization in one furnace, and at that time, heat quantity can be easily adjusted. Solid waste can be overheated as a waste recycling method and waste recycling system for small and medium-sized facilities that can be efficiently gasified, and can efficiently recycle carbides, useful gases, and liquid fuel even if the equipment scale is small. It is put into a carbonization / gasification furnace inclined downward from the inlet side to the outlet side together with water vapor, and in this carbonization / gasification furnace, it is heated indirectly in an air shut-off state by an electric heater without burning. Carbonization is performed by pyrolysis, and the amount of sediment in the furnace is increased toward the outlet side, causing water gas shift reaction with the heat, and dry distillation gas mainly composed of hydrogen and carbon monoxide. There is disclosed a waste regeneration treatment method characterized by comprising a pyrolysis carbonization / gasification step for producing a gas and a liquid fuel conversion step for converting the dry distillation gas into a liquid fuel using a Fischer-Tropsch synthesis catalyst. .
Patent Document 3 (Japanese Patent Application Laid-Open No. 2007-204558) includes a gasification unit that holds a certain amount of biomass and heats it with a heating body to gasify it, and particulate matter, tar, A gas refining unit that removes at least one substance selected from sulfur compounds and nitrogen compounds and purifies biomass gas, and a liquid fuel manufacturing unit that liquefies the purified biomass refining gas to produce a biomass liquid fuel stock solution A gas-liquid separator that separates the biomass liquid fuel stock solution into biomass liquid fuel, water, and light hydrocarbons, a vacuum recovery unit that recovers the biomass liquid fuel separated by the gas-liquid separator by reducing the pressure, and Combusting unreacted material that is not gasified in the gasification unit, and supplying the generated heat to the gasification unit, a liquid combustion from biomass Manufacturing apparatus is disclosed.
These technologies are in a design stage or an experimental stage, and a technique for producing hydrocarbon oil with a high yield from a carbonaceous raw material that can be continuously operated on an industrial scale has not been established.
That is, in the prior art, only a small amount of hydrocarbon was obtained as compared with the amount of carbon contained in the carbonaceous raw material as a raw material.

JP 2006-205135 A JP 2008-260832 A JP 2007-204558 A

Another object of the present invention is to provide a hydrocarbon production system and production method capable of obtaining a target industrially valuable hydrocarbon oil in a high yield.

The present invention for solving the above-mentioned problems is directed to a pyrolysis device that pyrolyzes a carbonaceous raw material into a dry distillation gas, a purification device that purifies the dry distillation gas, and a hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst. A hydrocarbon oil production system comprising a hydrogen supply device for metering and adding hydrogen to the dry distillation gas, preferably between the purification device and the hydrocarbon synthesis device. It is characterized by having.
Between the said refiner | purifier and the said hydrocarbon synthesizer, it has the gas regulator for mixing the said refined dry distillation gas and the said hydrogen, and adjusting the ratio of the carbon in a gas, and hydrogen. It is preferable. Further, the gas adjusting device further has a gas supply line for mixing unreacted gas from the hydrocarbon synthesizer, and the purified dry distillation gas, hydrogen from the hydrogen supply device, and the hydrocarbon It is particularly preferred to mix the unreacted gas from the synthesizer.
Superheated steam is preferable as the carrier gas heat source of the thermal decomposition apparatus, and more preferably, hydrogen is synthesized by superheated steam.
The refining device is preferably composed of a desulfurization device and an ion exchange scrubber.
As the carbonaceous raw material of the present invention, marine product-derived raw materials, forestry-derived raw materials, agricultural-derived raw materials, livestock-derived raw materials, sludge-derived raw materials, waste-derived raw materials, coal-derived raw materials, general waste-derived raw materials, waste plastics, waste tires, sludge At least one selected from the group consisting of chlorofluorocarbon and asbestos is applicable.
The system of the present invention preferably includes a pretreatment device for pretreating the carbonaceous raw material so as to have a predetermined carbon content and hydrogen content.
The present invention for solving the above-mentioned problems is a method for producing a hydrocarbon oil in which a carbonaceous raw material is pyrolyzed to generate a dry distillation gas, and after purification of the dry distillation gas, a hydrocarbon oil is obtained by a hydrocarbon synthesis catalyst. ) A step of introducing a carbonaceous raw material having a predetermined carbon content and hydrogen content into a thermal decomposition apparatus; (B) a step of converting the input carbonaceous raw material into a dry distillation gas by pyrolysis; and (C) a dry distillation gas A step of refining, (D) a step of preparing a mixed gas for synthesis by adding hydrogen to the purified dry distillation gas so as to have a predetermined carbon: hydrogen molar ratio, and (E) a hydrocarbon prepared from the prepared mixed gas And (F) a method for producing a hydrocarbon oil, comprising the step of separating the mixed gas obtained in step (E) into a hydrocarbon oil and an unreacted component.
The method for producing hydrocarbon oil preferably further includes a step of mixing the unreacted gas generated in step (F) with the mixed gas of step C.

FIG. 1 is a drawing showing a basic configuration of a hydrocarbon oil production system according to an embodiment of the present invention.
FIG. 2 is a drawing showing a basic configuration of a hydrocarbon oil production system according to another embodiment of the present invention.
FIG. 3 is a drawing showing an example of a raw material pretreatment apparatus applicable to the hydrocarbon oil production system of the present invention.
FIG. 4 is a drawing showing an example of a thermal decomposition apparatus in the hydrocarbon oil production system of the present invention.
FIG. 5 is a drawing showing an example of a carrier gas supply system that supplies the thermal decomposition apparatus.
FIG. 6 is a drawing showing an example of a purification apparatus in the hydrocarbon oil production system of the present invention.
FIG. 7 is a drawing showing an example of a hydrogen supply system in the hydrocarbon oil production system of the present invention.
FIG. 8 is a drawing showing an example of an adjusting device in the hydrocarbon oil production system of the present invention.
FIG. 9 is a flowchart showing an example of calculation of the hydrogen addition amount in the hydrocarbon oil production system of the present invention.
FIG. 10 is a flowchart showing a method for producing a hydrocarbon oil of the present invention.
FIG. 11 is a drawing showing an example in which the hydrocarbon oil production system of the present invention is applied to waste treatment.
FIG. 12 is a view showing an example in which the hydrocarbon oil production system of the present invention is mounted on a container.
FIG. 13 is a drawing showing a business model in which the hydrocarbon oil production system of the present invention is applied to waste treatment.
FIG. 14 is a drawing showing an example of a pretreatment device when the hydrocarbon oil production system of the present invention is applied to sludge, sludge, and the like.
FIG. 15 is a diagram showing an example in which the hydrocarbon oil production system of the present invention is applied to treatment of sludge, sludge, and the like.

(Basic configuration)
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. First, the basic structure of the hydrocarbon oil production system of the present invention will be described with reference to FIG.
As shown in FIG. 1, the hydrocarbon production system of the present invention includes a pyrolysis device 10 that pyrolyzes a carbonaceous raw material into a dry distillation gas, a purification device 20 that purifies the dry distillation gas, and a hydrocarbon synthesized from the purified gas. The FT synthesis tower 70, which is a hydrocarbon synthesis device that uses hydrocarbon oil in the presence of a catalyst, and a hydrogen supply device 50 that supplies hydrogen to the dry distillation gas in a shortage for hydrocarbon synthesis, are mainly constituted. This hydrocarbon production system has an adjustment device 40 that mixes purified dry distillation gas and hydrogen. More preferably, in the hydrocarbon production system of the present invention, the adjusting device 40 has a configuration in which unreacted gas in the FT synthesis tower is returned to the adjusting device 40 via the unreacted gas tank 100 as desired.
As will be described later, the pyrolysis apparatus 10 replaces the inlet 11 for charging a carbonaceous raw material, which is a raw material or a processed product, and the atmosphere in the pyrolysis apparatus 10, and the generated dry distillation gas is purified later. A carrier gas supply system 20 for sending to the apparatus 30 is provided.
The hydrocarbon oil production apparatus of the present invention purifies a dry distillation gas generated by pyrolyzing a predetermined carbonaceous raw material with a thermal decomposition apparatus 10 with a purification apparatus 30 and adds hydrogen to the purified dry distillation gas to form a mixed gas. The mixed gas is converted into hydrocarbon oil by the FT synthesis tower. At this time, since the shortage of hydrogen is supplied from the hydrogen supply system 50 based on the carbon content and hydrogen content of the carbonaceous raw material, the yield of the hydrocarbon oil in the hydrocarbon oil production apparatus of the present invention is increased.
In a preferred embodiment of the present invention, since the unreacted gas is circulated and mixed in the FT synthesis tower, the yield of the hydrocarbon oil is further increased.
As shown in FIG. 2, it is also within the scope of the present invention to add a predetermined amount of hydrogen directly from the hydrogen supply system to the dry distillation gas from the purification device 30 without providing the adjusting device 40. Further, a predetermined amount of hydrogen may be added to the pyrolysis furnace simultaneously with the carrier gas from the carrier gas supply system 20.
(material)
The carbonaceous raw material that can be used in the present invention is not particularly limited as long as it has a carbon source that generates dry distillation gas by thermal decomposition treatment, and can be appropriately used from a wide range of carbon-containing materials. .
As a carbonaceous raw material applicable in the present invention, as shown in FIG. 3, marine product-derived raw materials, forestry-derived raw materials, agricultural-derived raw materials, livestock-derived raw materials, sludge-derived raw materials, waste-derived raw materials, coal-derived raw materials, general waste-derived raw materials , Waste plastics, waste tires, sludge, chlorofluorocarbons and asbestos and mixtures thereof, but are not limited thereto.
The hydrocarbon oil production system of the present invention includes two concepts of a waste treatment system for producing hydrocarbon oil as a valuable material from waste and a hydrocarbon oil production system from a predetermined raw material such as biomass. Those skilled in the art will readily understand that.
These carbonaceous materials have different carbon contents and hydrogen contents depending on the origin. For example, in the case of wood chips, about 50 to 60% by mass of carbon on a dry basis, 4 to 8% by mass of hydrogen, about 20 to 30% by mass of carbon in the case of waste plus chips, 50 to 70% by mass of hydrogen, and about carbon in the case of sludge. 40 to 50% by mass, 10 to 20% by mass of hydrogen, and in the case of general waste, about 40 to 60% by mass of carbon and 15 to 30% by mass of hydrogen are contained. Thus, many carbonaceous raw materials have an excessive carbon content relative to the hydrogen content.
In the present invention, hydrogen is added based on such carbon content and hydrogen content so as to obtain an optimal carbon: hydrogen molar ratio (C: H). Generally, C: H = 1: 1. The hydrogen content is adjusted to be from 5 to 1: 6, preferably from 1: 2 to 1: 5, more preferably from 1: 2 to 1: 4.
At this time, the carbonaceous raw material is provided in various forms as a crude raw material. Therefore, in the present invention, two viewpoints are used for pretreatment for using such a crude material as a production material.
In the pretreatment in the present invention, (1) sufficient moisture adjustment to be within a predetermined carbon hydrogen molar ratio range (moisture adjustment is important from the viewpoint of energy reduction in thermal decomposition); (2) It is important to pulverize to a predetermined size in advance so as to efficiently thermally decompose.
However, pretreatment of these carbonaceous raw materials is appropriately selected from the viewpoints of introduction of pretreatment devices, energy required for moisture adjustment, introduction of pulverizers, efficiency of pulverizers, and the like. What is important in the present invention is that the carbonaceous raw material satisfies predetermined raw material standards (carbon and hydrogen content, water content, and size).
In addition, for carbonaceous raw materials, for example, when the moisture content is sufficiently low, such as wood chips, moisture adjustment may be omitted, and when pulverization after drying is not required, such as sludge, grinding is omitted. May be.
The pretreatment in the present invention is appropriately selected according to the carbon source (carbonaceous raw material) to be used and its situation. What is important in the pretreatment is removal of impurities as much as possible, moisture adjustment, and size adjustment.
The target moisture content is less than 60%, preferably less than 30%, more preferably less than 10%. If the water content is too high, energy consumption due to excessive evaporation in the thermal decomposition apparatus becomes too large.
The size of the carbonaceous raw material is preferably as fine as possible from the viewpoint of efficiently performing thermal decomposition. For example, when the carbonaceous raw material is derived from waste, impurities are clearly removed by sorting, dewatering, crushing, pulverizing, and drying, so that the raw material has a predetermined size and moisture content.
By pretreating in this way, the carbon content and hydrogen content per unit weight can be assumed. In other words, in the present invention, the carbonaceous raw material thus pretreated is used as a raw material reference for the starting material, and is used as a calculation reference for the amount of hydrogen to be described later based on the carbon and hydrogen content per unit weight. .
In the specific embodiment of the present invention, it is preferable to crush and pulverize the carbonaceous raw material while adjusting the water content.
(Thermal decomposition)
The carbonaceous raw material pretreated in the present invention is then thermally decomposed into crude dry distillation gas by the thermal decomposition apparatus 10. The pyrolysis apparatus 10 applicable in the present invention includes, for example, an inlet 11 for charging a pretreated carbonaceous raw material as shown in FIG. 4, a function of replacing the atmosphere in the pyrolysis apparatus 10, and generated dry distillation gas. It has a carrier gas introduction port 13 having a carrier gas function to be transferred to the next process, and a discharge port 12 for discharging the generated dry distillation gas (crude dry distillation gas). It is a device having a heat source (not shown) that performs thermal decomposition, and is not particularly limited as long as it has such a function, and can be applied to a continuous type such as a rotary kiln type or a batch type. It is.
The pyrolysis apparatus 10 shown in FIG. 4 has a configuration in which a carbonaceous raw material charged from the charging port 11 is pushed in by a raw material pushing device 11a. At this time, the air contained in the raw material is removed from below the inlet, and a substantial amount of oxygen is removed when entering the inside of the thermal decomposition apparatus 10.
Therefore, a considerable amount of air is replaced by the introduction of the carrier gas. The introduced carbonaceous raw material is heated to a pyrolysis temperature in a carrier gas atmosphere by a heating means (not shown) and pyrolyzed to become a dry distillation gas containing impurities and a remaining solid component.
The heat source of the thermal decomposition apparatus can be oil as in the past, but those using electric energy or a hybrid with an oil type are preferred from the viewpoint of easy temperature control in the heat separator.
When electric energy is used, the hydrocarbon (gas and / or oil) obtained by the present invention is used as a heat source, or the mixture of hydrogen and hydrocarbons generated by the present invention is used as an energy source. It is preferable to do. The thermal decomposition apparatus using electric energy may be a conventional electric furnace, but may be a heating method using microwaves or a heating method using a ceramic heating element.
In a preferred embodiment of the present invention, the pyrolysis apparatus includes an input amount measuring device (for example, a weight sensor) for measuring the input amount of the carbonaceous raw material, a flow rate sensor for measuring the flow rate of the carrier gas, and a furnace It is preferable to provide a known sensor such as a temperature sensor for measuring the internal temperature, a pressure sensor for measuring the internal pressure of the apparatus, and a flow rate sensor for measuring the discharge amount and discharge pressure of the dry distillation gas.
In particular, the pyrolysis apparatus 10 includes a weight sensor for measuring the input amount of the carbonaceous raw material, a flow sensor for measuring the flow rate of the carrier gas, and a flow rate sensor and temperature for measuring the discharge amount and discharge temperature of the dry distillation gas. Information from the sensor is important for calculating the carbon content and the hydrogen content (and hence the molar ratio of carbon to hydrogen).
The electric heating method is easy to control based on information from these sensors, and is preferable in terms of energy cost reduction, quick start-up, and ease of maintenance and operation. In particular, in the case of the micro-wave type, the energy cost is about 1/10 compared to an electric furnace (an additional half by inserting an inverter circuit), the start-up is faster (about 5 minutes), and higher-temperature pyrolysis is possible. There is an advantage that downsizing is possible and maintenance and operation are easy.
In this manner, the predetermined carbonaceous raw material is generally thermally decomposed at a high temperature of 700 ° C. or higher, so that the water gas can be obtained at a predetermined thermal decomposition rate depending on the type of carbonaceous raw material to be thermally decomposed and the degree of pretreatment A carbonization gas mainly composed of is produced (crude carbonization gas).
For example, according to experiments by the present inventors, for example, when waste is used as a starting material, the crude dry distillation gas is composed of carbon monoxide + hydrogen (water gas) 50 to 60%, low molecular weight hydrocarbons (methane, ethane, butane). Propane, etc.) about 20%, other gases (nitrogen oxide, sulfur oxide, hydrochloric acid, VOC, etc.) about 10%, and the balance was solids (char, inorganic, etc.). Subsequently, the crude dry distillation gas generated by the thermal decomposition is sent to the next purification apparatus.
The carrier gas supply system 20 is mainly composed of a water tank 21 for storing water for generating water vapor and an induction heating line 22 for overheating the generated water vapor. Since the superheated steam can be heated to a temperature of about 600 ° C. to 900 ° C., it can also be used as a heat source for the thermal decomposition apparatus 10.
In the embodiment shown in FIG. 5, superheated steam can be sent to a hydrogen supply system 50 to be described later and used for generating hydrogen by catalytic reaction, and water from a purification device 40 such as an ion exchange scrubber can be used. It is also possible to adopt a configuration in which the water is sent to the hot water tank 21.
This configuration has an advantage that the apparatus configuration is simplified and energy consumption is reduced.
(Purification equipment)
The purification device 30 is a device that removes impurities from the generated crude dry distillation gas, and can be configured by combining devices well known in the art. In a preferred embodiment of the present invention, as shown in FIG. 6, the combination of the desulfurization / detarring device 31 and the ion exchange scrubber 33 or the combination of the desulfurization / detarging device 31, the ion exchange scrubber 33 and the cyclone 32 is purified. It is preferable in that the dry distillation gas is purer and the hydrocarbon oil as the final product does not contain chlorine or the like.
In other words, the ion exchange scrubber is a scrubber having both an anion exchange resin layer and a cation exchange resin layer, and is removed at an efficiency of 98% or more during gas treatment of HCl, HCN, Cl ₂ , NO ₂ , SO _2, etc. Is possible. Further, it is possible to simultaneously perform the adsorption treatment of the contaminated gas and the regeneration of the ion exchange fiber in one chamber.
Conventionally, the gas generated by this type of pyrolysis has been treated with a normal scrubber. However, depending on the origin of the carbonaceous raw material, normal scrubbers may not sufficiently remove halogens and metal ions such as chlorine and iodine, and may remain in the purified gas, adversely affecting the hydrocarbon oil that is the final product. There was a case. Therefore, in the present invention, it is preferable to employ an ion exchange scrubber.
In addition, the crude water gas often contains a sulfur component, a tar component, and the like, which may adversely affect the hydrocarbon oil that is the final product. Therefore, in the present invention, these components are removed by a desulfurization / detar apparatus. Such an apparatus is not particularly limited as long as it achieves the object of the present invention, but can be composed of activated carbon that becomes denser from upstream to downstream, and is configured to switch a plurality of activated carbon layers in terms of maintenance. It is also possible to do.
The desulfurization / detarging apparatus 31 is a known apparatus as described in Patent Document 3, for example, and the cyclone 32 is also a known apparatus.
By comprising in this way, the refinement | purification recirculation | reflux gas which has a fixed property irrespective of the origin of a carbonaceous raw material can be obtained combining with the pretreatment of this invention. That is, it is preferable to use a reflux gas substantially free of ionic components, particularly halogen components and sulfur components. Such purified carbonization gas is extremely advantageous for providing the desired hydrocarbon oil containing no chlorine or the like.
(Hydrogen supply system)
In the present invention, purified water gas is mixed with hydrogen in order to make up for the lack of hydrogen compared to carbon. That is, the hydrogen required to produce hydrocarbon oils according to the present invention is deficient compared to carbon from purified water gas. Therefore, in order to produce hydrocarbon oil with a good yield (yield) by the system and method of the present invention, hydrogen is supplied from the hydrogen supply system to the purified water gas. In the present invention, it is preferable to synthesize hydrogen on-site and use the synthesized hydrogen according to the required amount, more preferably to use superheated steam used as a carrier gas and hydrogen generated by a hydrogen generation catalyst. .
More specifically, as shown in FIG. 7, by bringing the CaBr / FeO catalyst into contact with the superheated steam shown in FIG. 5, the steam is decomposed into oxygen and hydrogen. The resulting hydrogen is taken into a hydrogen tank and used to mix with purified water gas as necessary.
In this way, hydrogen can be produced in the system. By arranging a hydrogen supply system 50 capable of producing hydrogen in the system, a large amount of hydrogen can be supplied to the purified water gas. This makes it possible to obtain hydrocarbons with a good yield in the system of the present invention. It is also possible to use the obtained hydrogen for power generation.
(Hydrogen addition to dry distillation gas)
In the present invention, hydrogen from such a hydrogen supply system is added to the purified dry distillation gas. Hydrogen may be added in advance to the carrier gas or added to the water source of superheated steam as microbubbles. However, it is preferable to provide an adjusting device as shown in FIG.
(Adjustment device)
The adjusting device 40 mixes the dry distillation gas purified by the purifying device 30, hydrogen from the hydrogen supply system 50, and preferably unreacted gas from the FT synthesis tower 70 described later, into a predetermined amount, and sends it to the FT synthesis tower. A buffer tank that is a device for adjusting a mixed gas to be sent and temporarily stores a gas mixed with a gas mixer 41 including control valves 42a, 42b, and 42c such as electromagnetic valves for adjusting a gas pressure of each gas. 43.
The amount of hydrogen added at this time is determined, for example, as shown in FIG.
That is, in the present invention, as described with reference to FIG. 3, the raw material standards are determined in advance by the starting raw material and its pretreatment (hydrogen content and carbon content), and the hydrogen content and carbon of the dry distillation gas are determined by this raw material standard. The content rate is determined.
The amount of dry distillation gas generated per unit time is calculated by measuring the amount of gas generated by the actual operation of the thermal decomposition apparatus 10 and discharged from the thermal decomposition apparatus 10. The gas generation amount of the dry distillation gas can be approximately obtained as a value obtained by subtracting the flow rate of the carrier gas introduced per unit time from the flow rate of gas discharged from the discharge port 11 per unit time.
Then, the amount of hydrogen shortage is calculated from the composition of carbonized gas (carbon and hydrogen content) and the flow rate.
Further, in the specific embodiment of the present invention, when the unreacted gas from the FT synthesis tower 70 is mixed, since the component of the unreacted gas is generally a lower hydrocarbon, the required hydrogen amount is calculated from the composition and the flow rate thereof. The amount of hydrogen to be actually introduced is calculated by correcting the above.
The adjusting device 40 supplies a predetermined amount of hydrogen gas from the hydrogen supply system 50 based on the hydrogen addition amount calculated in this way via the control valve 42c and the dry distillation gas purified from the purification device 30 via the control valve 42a. If necessary, the flow rate of the off-gas is controlled through the control valve 42 b and sent to the gas mixer 41, and the mixed gas of these gases is temporarily stored in the buffer tank 43.
In this way, it is possible to prepare a mixed gas in which the carbon: hydrogen molar ratio is optimized in the adjusting device 40.
In this way, the mixed gas in which the ratio of carbon and hydrogen is optimized is sent to the subsequent FT synthesis tower.
(FT synthesis)
In the present invention, a mixed gas in which the ratio of carbon and hydrogen is optimized is sent to the FT synthesis tower 70 and subjected to the FT synthesis reaction until it becomes a hydrocarbon having a predetermined molecular weight range. The FT synthesis tower itself is composed of an FT synthesis tower in which a Fischer-Tropsch catalyst known in the art is packed by a known method.
In the FT synthesis tower 70, the mixed gas having an optimized ratio of carbon and hydrogen is compressed by, for example, the compressor 60 and brought into contact with the Fischer-Tropsch catalyst at a predetermined temperature, typically 200 to 250 ° C. To convert to the desired hydrocarbon.
The gas containing hydrocarbons thus synthesized is a separation device 80, generally a device that separates hydrocarbon oil 90 and off-gas (unreacted gas) mainly composed of lower hydrocarbons by a condenser. .
In a preferred embodiment of the present invention, the separated unreacted gas is temporarily stored in the unreacted gas tank 100 if desired, and then returned to the adjusting device 40 again to be mixed with purified dry distillation gas and hydrogen. The FT synthesis tower 70 is again used for the hydrocarbon synthesis reaction. In the present invention, the unreacted gas means a gas that has not been converted to a desired molecular weight, and generally means an unreacted water gas and a lower hydrocarbon (methane, ethane, butane, propane, etc.).
Thus, the yield of hydrocarbon oil is increased by circulating the unreacted gas.
In the hydrocarbon oil production system of the present invention configured as described above, the carbonized raw material that has been pretreated is thermally decomposed as a starting material, and the dry distillation gas generated by the thermal decomposition is purified and purified. At this time, impurities contained in the carbonaceous raw material are within an assumed range in advance, and substantially all impurities can be removed by a purification apparatus including a desulfurization / detarring apparatus and an ion exchange scrubber. Therefore, a dry distillation gas having a carbon: hydrogen content within a predetermined range is stably generated. By adding a predetermined amount of hydrogen to such dry distillation gas, it becomes possible to produce hydrocarbon oil with high yield. Also. Since the separated unreacted gas is circulated to the adjusting device and FT synthesis is performed together with a predetermined amount of hydrogen and dry distillation gas, the yield can be further improved.
(Production method)
Next, the manufacturing method of the hydrocarbon oil of this invention is demonstrated based on FIG.
The method for producing a hydrocarbon oil of the present invention is a method for producing a hydrocarbon oil in which a carbonaceous raw material is pyrolyzed to generate a dry distillation gas, and after the dry distillation gas is purified, a hydrocarbon oil is obtained by a hydrocarbon synthesis catalyst, The following steps (A) to (F) are included.
(A) introducing a carbonaceous raw material having a predetermined carbon content and hydrogen content into a thermal decomposition apparatus;
(B) a step of converting the input carbonaceous raw material into a dry distillation gas by pyrolysis,
(C) refining the dry distillation gas;
(D) preparing a mixed gas for synthesis by adding hydrogen to the purified dry distillation gas so as to have a predetermined carbon: hydrogen molar ratio;
(E) The step of converting the prepared mixed gas into hydrocarbon and (F) The step of separating the mixed gas obtained in step (E) into hydrocarbon oil and unreacted components First, in step A, for example, FIG. As shown in FIG. 3, a carbonaceous raw material pretreated so as to have a known carbon content and hydrogen content is put into a thermal decomposition apparatus. At this time, it is important to pre-treat the carbon content and the hydrogen content within a predetermined range in advance.
Next, the known amount of the carbonaceous raw material charged in Step B is pyrolyzed, and the impurities are purified in Step C.
The carbon content and hydrogen content in the carbonized gas purified in this way are within a known range, and the amount of hydrogen necessary to obtain the optimum carbon to hydrogen molar ratio is, for example, as shown in FIG. Can be obtained by calculation. In step D, the amount of hydrogen calculated in this way is added to the refined dry distillation gas to optimize the amount of carbon and hydrogen components in the mixed gas.
The molar ratio at this time is C: H = 1: 1.5 to 1: 6, preferably 1: 2 to 1: 5, more preferably 1: 2 to 1: 4, as described above.
In this way, the mixed gas in which the molar ratio of carbon and hydrogen is adjusted is converted into a hydrocarbon by FT synthesis in Step E.
And the component obtained at the process E in the process F is isolate | separated into a hydrocarbon oil and an unreacted part, and hydrocarbon oil is collect | recovered.
The unreacted component can be returned to step D and re-synthesised as desired.
As described above, in the method of the present invention, hydrogen is added to a large number of carbonaceous raw materials that are excessive in carbon content and insufficient in hydrogen content, so that they can be converted into hydrocarbon oil without leaving the carbon content. Further, the yield can be further increased by returning the unreacted component to the adjustment step and performing FT synthesis again.
(Application example)
The following specific embodiments of the invention are shown. Note that the system shown in the following embodiment is preferably the one shown in FIG. 1, for example.
(Waste treatment)
11 to 12 show examples in which the system of the present invention is applied to waste treatment.
The embodiment shown in FIG. 11 is an example in which the hydrocarbon oil production system of the present invention is applied to waste treatment such as garbage, general waste, and waste plastic.
As shown in FIG. 11, waste can be treated as a carbonaceous raw material satisfying a predetermined raw material standard by dehydrating, selecting, pulverizing (primary / secondary), and drying.
Since the molar ratio of carbon: hydrogen fluctuates depending on the content of waste, sampling of component analysis of waste (carbonaceous raw material) that has been pretreated appropriately may be performed to correct the raw material standards. preferable.
In addition, as shown in FIG. 12, the system of the present invention can be mounted on a container or the like to constitute a mobile waste treatment system or a temporarily installed waste treatment system. These mobile waste disposal systems and temporarily installed waste disposal systems are suitable for small-scale waste disposal in terms of installation of the system building and application for permission.
In addition, the waste treatment system based on the hydrocarbon oil production system of the present invention adds hydrogen under a preset raw material standard to optimize the molar ratio of carbon and hydrogen. The amount of hydrocarbon oil obtained can be assumed to some extent. Therefore, since it is possible to calculate the introduction cost, profits obtained by selling hydrocarbon oil, etc., it is possible to easily introduce the system.
In FIG. 12, the hydrocarbon production system of the present invention is separately introduced into two containers, container 1 and container 2, but all the components may be mounted in one container, or, for example, a pretreatment device Etc. can be changed as appropriate, for example, fixedly installed on site.
In addition, as shown in FIG. 13, from a waste disposal contractor (raw material supplier) that collects waste, an operation site of a waste disposal system based on the hydrocarbon oil production system of the present invention, and a manufactured hydrocarbon oil distributor It is possible to build a series of new businesses.
(Sludge treatment, household waste treatment, animal manure treatment, etc.)
The hydrocarbon oil production system of the present invention appropriately pretreats sludge, sludge, household waste, animals (especially livestock, poultry manure) and the like to satisfy the raw material standards required by the present invention. It can be used as a quality raw material.
At this time, for example, as shown in FIG. 14, the slurry-like sludge is agitated and cut as desired, and dried by hot air after dehydration by mesh and / or dehydration by centrifugation and suction, thereby requiring the raw material required by the present invention. It is possible to make the carbonaceous raw material satisfy the standards, and it is possible to reduce the volume of sludge and the like. Production of hydrocarbon oil from the carbonaceous raw material thus obtained is as described above.
In addition, as shown in FIG. 15, it is also possible to manufacture hydrocarbon oil by stocking garbage and manure discharged from a home.
(BTL)
In the embodiment shown in FIG. 11, for example, algae, wood chips, agricultural product residues (corn cores, unnecessary parts of agricultural products (parts that do not become edible, such as stems and branches), and waste agricultural products are appropriately pretreated as biomass. By carrying out the method of the present invention, it is possible to obtain a predetermined hydrocarbon oil, in particular, such a biomass feedstock has a clear origin, so that hydrocarbon oil for jet fuel after appropriate pretreatment, etc. It can be applied to products that meet the prescribed requirements.
Similarly to the business model shown in FIG. 13, the cultivation of biomass production and the conservation of biomass resources in the biomass manufacturer that is the raw material supplier, the production of hydrocarbons at the hydrocarbon oil production site, and the produced hydrocarbons It is possible to implement a series of new businesses that consist of a hydrocarbon oil sales business that sells oil.
Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments and can be widely applied. For example, the production system and the production method of the present invention can be applied to any raw material containing a predetermined amount of carbon such as a carbonaceous raw material such as coal and waste plastic shown in FIG. 3 or a gaseous raw material such as chlorofluorocarbon gas.

The present invention relates to a pyrolysis apparatus for pyrolyzing a carbonaceous raw material to obtain a dry distillation gas, a purification apparatus for purifying the dry distillation gas, and a hydrocarbon synthesis using the purified gas as a hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst. In a hydrocarbon oil production system composed of an apparatus, hydrocarbon oil is produced by FT synthesis after adding hydrogen so as to have a predetermined molar ratio according to the carbon: hydrogen molar ratio of the carbonaceous raw material. It is possible to produce the desired hydrocarbon oil with a good yield.
for that reason. It is applicable not only for the introduction of a new hydrocarbon oil production system, but also in a wide range of fields such as waste treatment and biomass energy production.

DESCRIPTION OF SYMBOLS 10 Thermal decomposition apparatus 20 Carrier gas supply system 30 Purification apparatus 40 Adjustment apparatus 50 Hydrogen supply system 70 FT synthesis tower 80 Hydrocarbon oil

Claims

A pyrolysis device that pyrolyzes the carbonaceous raw material into a dry distillation gas;
A refining device for refining dry distillation gas;
A hydrocarbon synthesizer that converts the purified gas into hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst;
A hydrocarbon oil production system comprising:
A hydrocarbon oil production system comprising a hydrogen supply device for metering and adding hydrogen to the dry distillation gas according to the amount of dry distillation gas generated.
Between the said refiner | purifier and the said hydrocarbon synthesizer, it has the gas regulator for mixing the said refined dry distillation gas and the said hydrogen, and adjusting the ratio of the carbon in a gas, and hydrogen. The hydrocarbon oil production system according to claim 1.
The pyrolysis apparatus includes a weight sensor for measuring the input amount of the carbonaceous raw material, a flow sensor for measuring the flow rate of the carrier gas, a flow sensor and a temperature sensor for measuring the discharge amount and discharge temperature of the dry distillation gas. With
The system is equipped with an electronic computer for measuring the carbon content and hydrogen content in dry distillation gas per unit time using these sensors, and adding hydrogen based on the measurement results and the type of carbonaceous raw material The hydrocarbon oil production system according to claim 2, wherein an amount is calculated, and hydrogen is supplied from the hydrogen supply system based on the calculated hydrogen addition amount.
The gas regulator further includes a gas supply line for mixing unreacted gas from the hydrocarbon synthesizer, and the purified dry distillation gas, hydrogen from the hydrogen supplier, and the hydrocarbon synthesis The hydrocarbon oil production system according to claim 2, wherein unreacted gas from the apparatus is mixed.
The gas adjusting device includes a gas mixing section having a purified dry distillation gas inlet, a hydrogen gas inlet and an unreacted gas inlet each having a flow rate adjustment bubble, and at least one for temporarily storing the mixed gas. The hydrocarbon oil production system according to claim 4, comprising a buffer tank.
The hydrocarbon oil production system according to claim 1, wherein superheated steam is introduced into the thermal decomposition apparatus as a carrier gas or a carrier gas and a heat source of the thermal decomposition apparatus.
6. The hydrocarbon oil production system according to claim 5, wherein the hydrogen supply device includes a hydrogen generation device that generates hydrogen by contact between superheated steam and a hydrogen generation catalyst.
3. The hydrocarbon oil production system according to claim 2, wherein the hydrogen supply device includes a hydrogen generation device that generates hydrogen by electrolysis of water.
The hydrocarbon oil production system according to claim 2, wherein the refining device comprises a desulfurization device and an ion exchange scrubber.
The hydrocarbon oil production system according to claim 2, further comprising at least one crushing device for crushing the carbonaceous raw material into a predetermined size.
The carbonaceous raw materials are marine product-derived raw materials, forestry-derived raw materials, agricultural-derived raw materials, livestock-derived raw materials, sludge-derived raw materials, waste-derived raw materials, coal-derived raw materials, general waste-derived raw materials, waste plastics, waste tires, sludge, chlorofluorocarbons. 2. The hydrocarbon oil production system according to claim 1, wherein the system is at least one selected from the group consisting of asbestos and asbestos.
10. The hydrocarbon oil production system according to claim 9, further comprising a pretreatment device for pretreating the carbonaceous raw material to have a predetermined carbon content and hydrogen content.
The hydrocarbon oil production system according to claim 1, wherein the carbonaceous raw material is a biomass raw material.
The hydrocarbon oil production system according to claim 2, further comprising a pretreatment device for pretreating the carbonaceous raw material to have a predetermined carbon content and hydrogen content.
The hydrocarbon oil production system according to claim 11, wherein the hydrocarbon oil to be produced is for jet fuel.
A method for producing a hydrocarbon oil in which a carbonaceous raw material is pyrolyzed to generate a dry distillation gas, and after purification of the dry distillation gas, a hydrocarbon oil is obtained by a hydrocarbon synthesis catalyst,
(A) introducing a carbonaceous raw material having a predetermined carbon content and hydrogen content into a thermal decomposition apparatus;
(B) a step of converting the input carbonaceous raw material into a dry distillation gas by pyrolysis,
(C) refining the dry distillation gas;
(D) preparing a mixed gas for synthesis by adding hydrogen to the purified dry distillation gas so as to have a predetermined carbon: hydrogen molar ratio;
(E) a step of converting the prepared mixed gas into hydrocarbon, and (F) a step of separating the mixed gas obtained in step (E) into hydrocarbon oil and unreacted components. A method for producing hydrocarbon oil.
Furthermore, the manufacturing method of the hydrocarbon oil of Claim 16 which has the process of mixing the unreacted part which arose in the process (F) with the mixed gas of the process D.
Based on the ratio of carbon to hydrogen contained in the carbonaceous raw material to be introduced, hydrogen is added so that the ratio of carbon to hydrogen in the mixed gas is 1: 2 to 1: 4 in molar ratio. The method for producing a hydrocarbon oil according to claim 16, wherein the hydrocarbon oil is produced.
Adjusting the moisture of the carbonaceous raw material so that the carbon content and the hydrogen content are within a predetermined range;
Crushing the carbonaceous raw material;
The method for producing a hydrocarbon oil according to claim 15, further comprising: