CN108192652A - A kind of common liquefaction process of coal and biomass - Google Patents
A kind of common liquefaction process of coal and biomass Download PDFInfo
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- CN108192652A CN108192652A CN201711431460.XA CN201711431460A CN108192652A CN 108192652 A CN108192652 A CN 108192652A CN 201711431460 A CN201711431460 A CN 201711431460A CN 108192652 A CN108192652 A CN 108192652A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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Abstract
The present invention relates to clean energy technology fields, and in particular to a kind of coal and the common sweetening process of biomass.The common liquefaction process of coal provided by the invention and biomass, it is handled by first carrying out " crushing+compression+crush again " to coal and biomass material, slurries are prepared again, the bio-coal slurry oil that solid content is high and can steadily be conveyed with pump is successfully obtained so that the height that cannot function as coal and biomass liquefying solvent in the prior art sticks waste oil and can also be utilized.By the way that be passed through hydrogen into the bio-coal slurry oil and control reaction pressure be 15~25MPa, reaction temperature is 380~480 DEG C, bio oil is finally made；The technique of the present invention causes coal to liquefy under high-pressure high-temperature environment with biomass, and further generation cracking, hydrogenation reaction, so as to fulfill from coal and conversion of the biomass to bio oil.In technique of the present invention, coal is with biomass conversion ratio up to 90~95%, and the yield of bio oil is up to 40~75%, and level of residue is not higher than 3%.
Description
Technical field
The present invention relates to clean energy technology fields, and in particular to a kind of coal and the common sweetening process of biomass.
Background technology
At present, using coal as main energy sources, traditional coal utilization mode is burning in China, but caused by coal burning
Atmosphere polluting problem getting worse；Also, the coal quality in China declines year by year so that raw coal cleaning percent carries year after year
Height, coal washing waste water bring serious water pollution.Severe environmental problem has made energy resource structure be adjusted to as China's energy development
One of vital task.However, the energy resources storage situation in China itself is oil-poor rich coal, need to rely on every year a large amount of
Petroleum import could meet production development demand, if by reducing to coal resources using adjusting the energy knot in China
Structure, the not only vacant energy resources of rich reserves, can also greatly increase the import volume of oil, this will seriously affect China
Energy security.
The Energy restructuring mode for being more suitable for China's national situation is to realize that the clean and effective of coal resources utilizes.Kerosene refines altogether
Technology is the technology that a kind of coal for growing up in the recent period is processed jointly with heavy oil, which overcome the harsh conditions of DCL/Direct coal liquefaction,
And heavy oil can also be utilized simultaneously, has become the research hotspot of coal clean utilization.For example, Chinese patent literature
CN105647578 discloses a kind of technology of kerosene mixed hydrogenation refining, and the technology is first by 50~200 μm of coal dust and slag
Coal is made in oil etc., adds hydrogen, catalyst and vulcanizing agent, is sent into slurry bed system jointly, under the pressure of 17-25MPa into
Row cracking and hydrogenation reacts；Gained hydrogenation products send to hydrofinishing again after being detached, and finally obtain lighter hydrocarbons, naphtha, diesel oil
And wax oil.
However, the technology has two jointly with most kerosene calendering process in the prior art：Liquefaction efficiency
Low and hydrogen-consuming volume is big.
1. liquefaction efficiency is low
The kerosene slurry obtained by coal dust and oil preparation needs to be conveyed into Hydrocracking device by pump, in order to ensure the steady of pump
Operating and conveying, the viscosity of kerosene slurry can not be too high, and as the heavy oil of dispersant, residual oil etc. is more sticky in coal
Liquid, this allows for kerosene, and the content of coal dust can not be excessively high in kerosene slurry in refining technology altogether, so as to cause the concentration of reaction mass
It is limited, cause liquefaction efficiency relatively low.
2. hydrogen-consuming volume is big
Coal to be hydrocracked mechanism as follows：
First stage, coal are cracked to form preasphaltene, asphaltene, and adjoint some gases of generation, liquefaction oil and macromolecular
Condensation polymer.
Second stage, under rich hydrogen condition, a part of preasphaltene is hydrogenated to liquefaction oil, also there is part macromolecular polycondensation
Object again hydrocracking generation low molecule quality liquefaction oil.
When temperature is excessively high or hydrogen supply is insufficient, the insoluble organic matter in part in preasphaltene and asphaltene can generate charcoal or half
It is burnt.The hydrocracking reaction that the high concentration and high partial pressures of hydrogen are conducive to coal carries out, and reduce green coke to forward direction.So kerosene is total to
Often hydrogen-consuming volume is very high for refining technology.
For first problem, in order to improve liquefaction efficiency, researcher is dedicated to improving the content of coal dust in kerosene slurry,
Such as attempt to reduce coal powder size as far as possible, in the hope of improving the ratio of coal dust by increasing dispersibility of the coal dust in kerosene slurry
Example.However, coal dust has a large amount of pore structure, reduce the operation of coal powder size so that these micro-pores further expose,
So as to adsorb a large amount of solvent naphtha.As a result, it is starched by the kerosene that the coal dust of smaller particle size is prepared, in identical coal dust weight proportion
Under, kerosene slurry higher that coal dust that viscosity compares bulky grain instead is prepared can not realize the smooth transport of pump at all.
For Second Problem, in order to reduce the consumption to hydrogen, researcher attempts to be pyrolyzed jointly with coal using biomass
Add hydrogen to realize.The hydrogen source that kerosene reacts in refining technology altogether with the coal dust of cracking mostlys come from：The hydrogen being dissolved in solvent naphtha
Change the reactive hydrogen of generation under catalyst action, solvent naphtha can be supplied to or hydrogen, the coal of transmission crack generated work in itself
Property hydrogen and reaction generation hydrogen.And the H/C higher of biomass, researcher wish just to drop by using hydrogen in biomass
The hydrogen-consuming volume of low coal liquefaction slows down the severity of reaction condition, realizes the mild liquefaction of coal.
The liquefaction mechanism of biomass is as follows：Biomass is cracked into oligomer first, then again through dehydration, dehydroxylation, dehydrogenation,
Deoxidation and decarboxylation and form micromolecular compound, micromolecular compound is then by being condensed, being cyclized, the reaction such as polymerizeing and generate
New compound.Studies have reported that, wood powder, which is pyrolyzed the product to be formed, contributes to coal liquefaction intermediate product (preasphaltene and pitch
Alkene) hydrogenation reaction, and then formed liquid oil；The addition of biomass also helps the pyrolysis removing of sulphur and nitrogen in coal, and prevents
Cohering between particle in coal cracking process.
But since kerosene slurry has had very high viscosity in itself, the addition of biological particles can cause viscosity further
It increases and can not be conveyed with pump, so being limited only to utilize in the lab for the common liquefaction of coal and biomass at present
The relatively low naphthane of viscosity carries out the dispersion of coal dust and biological particles as solvent, that is to say that there is no really realize at present
The technology of the mixing production of coal, biomass and oil.
In conclusion how to increase the content of coal dust in kerosene slurry, improve liquefaction efficiency, and further reduce kerosene slurry
Viscosity, mixing liquefaction, reduction hydrogen consumption so as to fulfill coal, biomass and oil, are that current those skilled in the art are still unsolved
Technical barrier.
Invention content
Technical problems to be solved first of the invention are to overcome the coal dust content of coal slurry in the prior art limited and cause
The problem of liquefaction efficiency is relatively low, and further overcome be not carried out the mixed of coal, biomass and oil in the prior art on this basis
The defects of refining production technology, and then provide a kind of hydrogen consumption less, the common liquefaction process of the high coal of liquefaction oil yield and biomass.
For this purpose, technical solution is as follows used by the present invention solves the above problems：
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The preparation of bio-coal slurry oil：
Biomass collection simultaneously controls moisture content to be less than 2wt%, and it is 100~300 μm to be then crushed to median；
Biomass after crushing is subjected to compression forming, compression pressure is 2~5MPa, and compression temperature is 30~60 DEG C；
By the pulverization process again of the biomass after compression forming, it is 30~50 μm to be crushed to median, obtains biomass powder
End；
It collects coal and moisture content is controlled to be less than 2wt%, it is 50~100 μm to be then crushed to median；
Compression forming is carried out to the coal after crushing, compression pressure is 5~15MPa, and compression temperature is 30~60 DEG C；
To the pulverization process again of the coal after compression forming, it is 30-50 μm to be crushed to median, obtains coal dust；
The powdered biomass, the coal dust, catalyst are carried out with oil product to proportioning in proportion to mix, grind slurrying and obtain
Bio-coal slurry oil, the powdered biomass and the coal dust account for 60~70wt% of the bio-coal slurry oil altogether；
Liquefaction reaction：Be passed through hydrogen into the bio-coal slurry oil to react, and control reaction pressure for 15~
25MPa, reaction temperature are 380~480 DEG C, and bio oil is finally made；
In the preparation steps of bio-coal slurry oil, when carrying out the mixing, for first by the powdered biomass and described
Coal dust carries out ash disposal and after being pre-mixed with the catalyst, then gained premix is mixed with the oil product, alternatively, being straight
It connects and mixes the powdered biomass, the coal dust, the catalyst with the oil product.
In the bio-coal slurry oil, a concentration of 20~30wt% of biomass, a concentration of 30~45wt% of coal dust.
Moisture content is controlled using drying and dewatering, the drying and dewatering temperature is 50~70 DEG C, the drying and dewatering time for 3~
5h。
The compression forming is compound stalk forming, compression molding or press strip are molded.
The heap density that the powdered biomass is controlled in the preparation steps of bio-coal slurry oil is 300~500kg/m3, control
The heap density for making the coal dust is 1000~1200kg/m3。
Described crush is broken hammer slice type milling, ball mill grinding, rod milling crushing, ultramicro grinding or air-flow crushing.
The grinding slurrying, which is stirring pulping, dispersion slurrying, emulsify slurrying, shears slurrying, homogeneous slurrying or colloid grinds
Slurry.
The time of the grinding slurrying is 2~8min.
The viscosity of the bio-coal slurry oil is 550~1000mPas (50 DEG C).
The coal is low-order coal；The oil product is hogwash fat, gutter oil, rancid oil, waste lubricating oil, used oil, heavy oil, slag
It is one or more in oil, washing oil, carbolineum, coal tar, oil or bio oil made from this technique.
In the bio-coal slurry oil, the content of the catalyst is 0.1~10wt%, preferably 2wt%；It is described to urge
The grain size of agent is 5 μm~500 μm.
It is described be passed through hydrogen specific method be：
High pressure hydrogen is injected into the bio-coal slurry oil, and controls the high pressure hydrogen and the bio-coal slurry oil
Volume ratio be (600~1000)：1, so as to form reaction raw materials；
The reaction raw materials are sent into paste state bed reactor to occur liquefaction, cracking and hydrogenation reaction, while to described
The injection cold hydrogen of high pressure in paste state bed reactor, it is 0.02~0.2m/s to control total gas velocity in the paste state bed reactor, preferably
For 0.05~0.08m/s；
Wherein, the pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 13~27MPa, and the temperature of the cold hydrogen of the high pressure is 50
~135 DEG C.
The high pressure hydrogen is injected into two times in the bio-coal slurry oil, specially：
It is changed after high pressure medium temperature hydrogen is injected for the first time into the bio-coal slurry oil, and by the bio-coal slurry oil
Heat is warming up to 300~400 DEG C, then injects high pressure-temperature hydrogen for the second time into the bio-coal slurry oil again；
Wherein, the temperature of the high pressure medium temperature hydrogen is 300~400 DEG C, the temperature of the high pressure-temperature hydrogen for 410~
510℃。
The cold hydrogen is injected via 3~5 inlets on the paste state bed reactor side wall.
Storage of the catalyst in the paste state bed reactor controls the liquid phase quality in the paste state bed reactor
5~30wt%.
The time of the reaction is 30~90min.
In the preparation steps of the bio-coal slurry oil, further include and the powdered biomass and the coal dust are screened
Operation, and will more than limit granularity the solid material send back to it is described compression or it is described crushing link in operate again；Institute
It states and limits granularity as 80 μm~100 μm.
Biomass carbon of the catalyst for the active component of load through vulcanizing treatment, the active component is oxidation
It is one or more in iron, FeOOH or iron hydroxide；
Or the catalyst is the unformed FeOOH through vulcanizing treatment.
Biomass used in the present invention can be solid, such as straw of the crops such as wheat, rice, corn, cotton
The industrial crops such as stalk or reed, tabasheer grass, trees, leaf, gourd, fruit and vegetable, can also be algae, industrial wood
Matter, papery waste etc.；Or liquid, such as liquid excrement, when using liquid biological matter, then in biomass kerosene
Compression and the crushing process to biomass material are saved in the step of slurry is prepared；Can also can also be a variety of for a kind of biomass
The biomass material that biomass collectively constitutes.
The preparation method that the biomass carbon of active component is loaded in the present invention includes：
(1) it is biomass high-area carbon to choose biomass carbon；
(2) active component is carried on the biomass carbon carrier, the catalyst is made.
It is by the specific method that active component is carried on the biomass carbon carrier：
The biomass carbon carrier, the active component aqueous solution are hybridly prepared into suspension, adding in precipitating reagent will be living
Property components precipitate on biomass carbon carrier, it is washed, dry that the catalyst is made；Wherein, the precipitating reagent for ammonium hydroxide or
The aqueous solution of at least one of the carbonate of alkali metal, bicarbonate, hydroxide, the control of precipitation process temperature are 30 DEG C~90
DEG C, pH value is 7~9.
Or the catalyst is the unformed FeOOH through vulcanizing treatment.
The above-mentioned technical proposal of the present invention has the following advantages that：
1st, the mixing for realizing coal, the biomass and oil for the first time liquefaction of the invention, provides a kind of coal and biology
The common liquefaction process of matter.The present invention by biomass, coal is dehydrated, crushed, compressed, crushed again, first slurry, grinding
This technological process of slurrying, and pass through to the preferred of the grain size of crushing and contractive condition, biomass and coal content has successfully been made
Reach 60-70wt%, and viscosity is only the bio-coal slurry oil of 550-1000mPas (50 DEG C).
Compression processing coal is enabled to cave in, be closed with the pore structure inside biological material, occur plastic flow with
Plastic deformation, so as to substantially increase the density of coal and biomass material, good can be scattered in solvent naphtha；Together
When, caving in and being closed for pore structure avoids coal and absorption of the biomass to solvent naphtha so that solvent naphtha can give full play to
Its effect as dispersant；It was found that compression temperature has a significant impact for the degree of plastic flow and plastic deformation, temperature
Degree is higher, and obtained density is bigger, however temperature is excessively high, and material can be caused to decompose or bring other problems, so using
30~60 DEG C as temperature when compressing.Compressed crushing operation again increases the accessible area of raw material so that raw material
It can preferably be contacted with catalyst and solvent naphtha, the transmission of hydrogen can be strengthened, greatly reduce raw material because in hole shape structure
It is interior and can not be contacted with hydrogen and catalyst so as to reaction situation.
" crushing+compression+crush again " provided by the invention, which can be suitable for all inside, has the coal material of pore structure
Material and biological material, the especially biomass material to the porosity and looseness such as the low-order coals such as lignite raw material and stalk, rice husk；
The paste-forming properties of high-concentration raw substance kerosene slurry obtained are good, and mobility is high, can not only can effectively be carried directly with the steady conveying of pump
High transport system running stability, liquefying plant utilization ratio and liquefaction efficiency meet the feed needs of subsequent treatment process, also
The clean and effective for realizing colm and biomass utilizes；Coal and biomass it is close adjacent so that caused by biomass pyrolytic
Hydrogen can add the part hydrogen source of hydrogen as pyrolysis of coal, reduce the consumption to hydrogen.Made by common liquefaction process provided by the invention
The height that must cannot function as coal and biomass liquefying solvent in the prior art sticks waste oil, such as used oil, gutter oil, rancid oil etc.,
Also it can be utilized.
By being passed through hydrogen into the bio-coal slurry oil to react, and control reaction pressure for 15~25MPa,
Reaction temperature is 380~480 DEG C, and bio oil is finally made；The technique of the present invention causes coal with biomass in high pressure-temperature condition
Lower liquefaction, and under the action of hydrogen and catalyst is faced, cracking, hydrogenation reaction further occurs, so as to fulfill by coal and biomass
Conversion to bio oil.In technique of the present invention, coal and biomass conversion ratio are up to 90~95%, the yield of bio oil
Up to 40~75%, and level of residue is not higher than 3%.
2nd, coal provided by the invention and the common liquefaction process of biomass, coordinate the process screened to solid material, can
Guarantee is uniform for preparing the solid grain size of bio-oil coal slurry, makes gained bio-coal slurry oil stability more preferable, is not easy
It is settled in transportational process, avoids the blocking to transport pipeline and the damage to liquefaction device.By first being given birth to solid
Substance is dried, crushes and the pretreatments such as ash disposal, is then mixed again with catalyst, preferably to utilize coal and biomass powder
Surface can so that catalyst is attached to its surface, such catalyst can provide hydrogen for coal and biomass liquefying product in time
Transfer so that it is guaranteed that will not generate coke polycondensation in entire technical process, achievees the purpose that reduce level of residue.
3rd, coal provided by the invention and the common liquefaction process of biomass, first will reaction by using paste state bed reactor
Raw material is sent into paste state bed reactor by reactor bottom to react, while injects cold hydrogen into reactor again, is so existed
It can be drawn in reactor by the yield of biological oil product after gas, liquid, the different specific weight of each material of solid and complex reaction
The otherness control of each phase flow velocity is realized in the difference in specific gravity variation risen so that coal and biomass material in reactor by down toward
It is upper generation liquefaction, cracking, hydrogenation reaction, even if in the process the larger coal of proportion, biomass and catalyst solid particle with
Gas and biological oil product rise, but it is again return under the cold hydrogen effect on top participate in reacting again to bottom, according to reactor
The material density in upper, middle and lower portion is suitably adjusted into hydrogen content and cold hydrogen injection rate in the bio-coal slurry oil of reactor,
It is discharged so as to fulfill unconverted coal and biomass in the cycle of inside reactor and the balance of catalyst, thus can ensure that liquid
The abundant progress of the reactions such as change, cracking plus hydrogen, so as to be conducive to improve the conversion ratio of coal and biomass and biological oil yield.
4th, coal provided by the invention and the common liquefaction process of biomass, by the way that high pressure hydrogen is injected into biology in two times
In matter kerosene slurry, i.e., respectively inject a high pressure hydrogen, the injection of previous sub-high pressure hydrogen before and after heating up to bio-coal slurry oil
The disturbance of heat exchanger endogenous substance kerosene slurry can be increased, so as to avoid coal, biomass and the deposition of catalyst.
Specific embodiment
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
All other embodiments obtained under the premise of creative work are made, shall fall within the protection scope of the present invention.In addition, below
Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention
With reference to.
Coal described in following each embodiment and comparative examples and the conversion ratio of biomass, biological oil yield and residue content
Calculation formula is as follows：
Coal and the conversion ratio of biomass=(quality of quality-solvent naphtha of liquefaction reaction product quality-catalyst)/(coal
With the quality of biomass and)
The quality of obtained oil phase of the biological oil yield=liquefaction reaction product after the separation/(quality of coal and biomass
With)
Residue content=mass of residue/(quality of coal and biomass and).
Embodiment 1
The common liquefaction process of a kind of coal and biomass, includes the following steps：
Lignite is taken, is baked to be dehydrated, and it is 50 μm to be crushed to median, and extrusion forming is then carried out at 30 DEG C,
Briquetting pressure is 15MPa, obtains lignite compression material.Lignite compression material is crushed, the lignite that grain size is 30 μm is obtained and crushes
Material.Above-mentioned lignite crushed material is added in jointly with the unformed FeOOH in reactor after vulcanizing treatment to liquid excrement
Just it is anti-to occur with, to form bio-coal slurry oil, into the bio-coal slurry oil hydrogen is passed through in the mixture of used oil
Should, and to control reaction pressure be 16MPa, reaction temperature is 480 DEG C, and bio oil is finally made.
Embodiment 2
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of stalk：
(1) stalk is taken, is baked to be dehydrated, it is 300 μm to be crushed to median, is then fed into cuber or plodder exists
Extrusion forming is carried out at 60 DEG C, briquetting pressure 2MPa obtains straw compression material.
(2) straw compression material is sent into hammer crusher, crushes, obtain stalk crushed material, for use.
The pretreatment of coal raw material：
(1) take lignite, be baked to be dehydrated, be crushed to median as 100 μm, be then fed into cuber at 30 DEG C into
Row extrusion forming, briquetting pressure 5MPa obtain lignite compression material.
(2) lignite is compressed into material and is sent into ball mill, crushed, obtained the lignite crushed material that median is 50 μm, treat
With.
The preparation of bio-coal slurry oil and liquefaction reaction：
There to be iron oxide with the load after vulcanizing treatment after above-mentioned stalk crushed material and the progress ash disposal of lignite crushed material
Biomass carbon is mixed to get mixture, and the mixture is added in into rancid oil, so as to form the bio-coal slurry oil, to
Hydrogen is passed through to react in the bio-coal slurry oil, and to control reaction pressure be 15MPa, reaction temperature is 440 DEG C, most
Obtained bio oil eventually.
In the present embodiment, the biomass carbon for having iron oxide that loads is to be prepared by the following method：
(1) it is biomass high-area carbon to choose biomass carbon；
(2) iron oxide through vulcanizing treatment is carried on the biomass carbon carrier, the catalyst is made.
It is by the specific method that the iron oxide through vulcanizing treatment is carried on the biomass carbon carrier：
The biomass carbon carrier, the oxidation water solution through vulcanizing treatment are hybridly prepared into suspension, added in
Iron oxide through vulcanizing treatment is deposited on biomass carbon carrier by precipitating reagent, washed, dry that the catalyst is made；Its
In, the precipitating reagent is ammonium hydroxide and sodium carbonate liquor, and the control of precipitation process temperature is 30 DEG C, pH value 7.
In terms of the gross mass of iron oxide and biomass carbon, the content of iron oxide is 10wt%；
Embodiment 3
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of biomass material：
(1) reed is taken, is baked to be dehydrated, airslide disintegrating mill is then fed into and crushes processing, obtains one wheat-middlings of reed
Particle, grain size D50It is 200 μm.
(2) crushed material of reed is sent into cuber or plodder carries out extrusion forming at 50 DEG C, briquetting pressure is
3MPa obtains reed compression material.
(3) reed is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain reed separating twice material, grain size D50
It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 80 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming at 55 DEG C, be molded
Pressure is 12MPa, obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 40 μm, for use.
The preparation of bio-coal slurry oil and liquefaction reaction：
Load of the separating twice material of reed and coal after ash disposal and in reactor after vulcanizing treatment has hydroxyl oxidation
The biomass carbon of iron is mixed to get mixture, and the mixture is added in into used oil, so as to form the biomass kerosene
Slurry.As a preferred mode, above-mentioned bio-coal slurry oil can continue through milling treatment of colloid, can continue to described in raising
The paste-forming properties of bio-coal slurry oil.
Hydrogen is passed through to react into the bio-coal slurry oil, and controls reaction pressure as 17MPa, reaction temperature
It is 400 DEG C, bio oil is finally made.In the bio-coal slurry oil, the content of the reed is 30wt%, and the coal contains
It measures as 40wt%, the content of the catalyst is 0.1wt%, and the grain size of the catalyst is 500 μm.
Embodiment 4
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of biomass material：
(1) leaf is taken, is baked to be dehydrated, airslide disintegrating mill is then fed into and crushes processing, obtains one wheat-middlings of leaf
Particle, grain size D50It is 100 μm.
(2) crushed material of leaf is sent into cuber or plodder carries out extrusion forming at 40 DEG C, briquetting pressure is
2MPa obtains leaf compression material.
(3) leaf is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain leaf separating twice material, grain size D50
It it is 50 μm, for use.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 60 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming at 45 DEG C, be molded
Pressure is 12MPa, obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 50 μm, for use.
The preparation of bio-coal slurry oil and liquefaction reaction：
Load of the leaf after drying, crushing and ash disposal and in reactor after vulcanizing treatment has the biology of iron hydroxide
Matter charcoal is mixed to get mixture, and the mixture is added in into heavy oil, so as to form the bio-coal slurry oil, makes above-mentioned life
Substance kerosene slurry is by milling treatment of colloid, so as to continue to improve the paste-forming properties of the bio-coal slurry oil.
Hydrogen is passed through into the bio-coal slurry oil by colloid mill to react, and control reaction pressure for 19MPa,
Reaction temperature is 380 DEG C, and bio oil is finally made.In the bio-coal slurry oil, the content of the leaf is 20wt%, institute
The content for stating coal is 45wt%, and the content of the catalyst is 2wt%, and the grain size of the catalyst is 400 μm.
Embodiment 5
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of biomass material：
(1) algae is taken, is baked to be dehydrated, airslide disintegrating mill is then fed into and crushes processing, obtains one wheat-middlings of algae
Particle, grain size D50It is 200 μm.
(2) crushed material of algae is sent into cuber or plodder carries out extrusion forming at 45 DEG C, briquetting pressure is
2MPa obtains algae compression material.
(3) algae is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain algae separating twice material, grain size D50
It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) lignite is taken, is baked to be dehydrated, ball mill is then fed into and crushes processing, obtains crushed material of lignite,
Grain size D50It is 80 μm.
(2) crushed material of lignite is sent into cuber or plodder carries out extrusion forming at 60 DEG C, briquetting pressure is
15MPa obtains lignite compression material.
(3) lignite is compressed into material and is sent into ball mill, carried out separating twice, obtain lignite separating twice material, grain size D50For 30 μ
M, for use.
The separating twice material of above-mentioned algae and lignite is screened, 100 μm of algae of ＞ is separated with lignite, so
It is handled again with follow-up charging in input compression link or second of crushing link afterwards, to obtain more uniform grain size,
So as to obtain more stable bio-coal slurry oil.
The preparation of bio-coal slurry oil and liquefaction reaction：
Algae is determined with separating twice material of the lignite by screening after ash disposal with the nothing in reactor after vulcanizing treatment
Type FeOOH is mixed to get mixture, the mixture is added in into bio oil made from this technique, so as to be formed
State bio-coal slurry oil, hydrogen be passed through to react into the bio-coal slurry oil, and control reaction pressure for 20MPa,
Reaction temperature is 390 DEG C, and bio oil is finally made.Wherein, sulphur and unformed FeOOH are using mass ratio as 0.4：1 mixing
Preparation obtains catalyst.In the bio-coal slurry oil, the content of the algae is 20wt%, and the content of the coal is
40wt%, the content of the catalyst is 4wt%, and the grain size of the catalyst is 300 μm.
It is described be passed through hydrogen specific method be：High pressure hydrogen is injected into the bio-coal slurry oil, and described in control
The volume ratio of high pressure hydrogen and the bio-coal slurry oil is 600：1, so as to form reaction raw materials；The reaction raw materials are sent into
Liquefaction, cracking and hydrogenation reaction occurs in paste state bed reactor, while the cold hydrogen of high pressure is injected into the paste state bed reactor,
It is 0.2m/s to control total gas velocity in the paste state bed reactor；Wherein, the pressure of the high pressure hydrogen and the cold hydrogen of high pressure is
13MPa, the temperature of the cold hydrogen of high pressure is 135 DEG C.
Embodiment 6
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of biomass material：
(1) the soybean oil dregs of fat are taken, are baked to be dehydrated, micronizer is then fed into and crushes processing, obtain soybean
Crushed material of the dregs of fat, grain size D50It is 200 μm.
(2) crushed material of the soybean oil dregs of fat is sent into cuber or plodder carries out extrusion forming at 550 DEG C, be molded
Pressure is 4MPa, obtains soybean oil dregs of fat compression material.
(3) the soybean oil dregs of fat are compressed into material and is sent into micronizer, carried out separating twice, obtain two wheat-middlings of the soybean oil dregs of fat
Particle, grain size D50It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 80 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming at 55 DEG C, be molded
Pressure is 10MPa, obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 50 μm, for use.
The preparation of bio-coal slurry oil and liquefaction reaction：
By the separating twice material of refreshing eastern jet coal and the soybean oil dregs of fat with it is unformed after vulcanizing treatment in reactor
FeOOH is added in waste lubricating oil jointly, so as to form the bio-coal slurry oil, mode as a further preference, on
Milling treatment of colloid can be continued through by stating bio-coal slurry oil, can continue to improve the paste-forming properties of the bio-coal slurry oil.
Hydrogen is passed through to react into the bio-coal slurry oil, and controls reaction pressure as 22MPa, reaction temperature
It it is 410 DEG C, the time of reaction is 30min, and bio oil is finally made.Wherein, sulphur and unformed FeOOH are with mass ratio
It is 0.8：1 mixed preparing obtains catalyst.In the bio-coal slurry oil, the content of the soybean oil dregs of fat is 30wt%,
The content of the coal is 30wt%, and the content of the catalyst is 6wt%, and the grain size of the catalyst is 200 μm.
It is described be passed through hydrogen specific method be：Injected for the first time into the bio-coal slurry oil pressure for 18MPa,
After temperature is 350 DEG C of high pressure medium temperature hydrogen, and bio-coal slurry oil heat exchange is warming up to 200 DEG C, then again to described
In bio-coal slurry oil second injection pressure be 18MPa, the high pressure-temperature hydrogen that temperature is 510 DEG C, and control and inject twice
The volume ratio of high pressure hydrogen and the bio-coal slurry oil be 700：1, so as to form reaction raw materials；The reaction raw materials are sent
Enter liquefaction, cracking and hydrogenation reaction occurs in paste state bed reactor, while inject pressure into the paste state bed reactor and be
18MPa, the cold hydrogen of high pressure that temperature is 100 DEG C, the cold hydrogen are noted via 5 inlets on the paste state bed reactor side wall
Enter, it is 0.08m/s to control total gas velocity in the paste state bed reactor.
Embodiment 7
The common liquefaction process of a kind of coal and biomass, includes the following steps：
Biomass and the processing of coal raw material：
Water intaking rice straw, the palm oil dregs of fat and lignite, are baked to be dehydrated, and it is 100 μm to be crushed to median, then
It is common to be sent into cuber or plodder carries out extrusion forming, briquetting pressure 5MPa, obtain rice straw, the palm oil dregs of fat and
The compression material of lignite.Above-mentioned compression material is sent into ball mill, is crushed, obtains the rice straw and palm fibre that median is 30 μm
The crushed material of the palmitic acid oil dregs of fat and lignite, for use.
The preparation of bio-coal slurry oil and liquefaction reaction：
It will be mixed to get in reactor with the unformed FeOOH after vulcanizing treatment after above-mentioned crushed material ash disposal
Mixture adds in the mixture into mixed coal tar and oil, so as to form the bio-coal slurry oil, to institute
It states and hydrogen is passed through in bio-coal slurry oil to react, and to control reaction pressure be 23MPa, reaction temperature is 450 DEG C, reaction
Time for 60min, bio oil is finally made.Wherein, sulphur and unformed FeOOH are using mass ratio as 0.6：1 mixing is matched
Catalyst is made.In the bio-coal slurry oil, the content of the palm oil dregs of fat is 20wt%, the rice straw
Content is 10wt%, and the content of the coal is 40wt%, and the content of the catalyst is 8wt%, and the grain size of the catalyst is
100μm。
It is described be passed through hydrogen specific method be：
Injecting the high pressure medium temperature hydrogen that pressure is 23MPa, temperature is 350 DEG C for the first time into the bio-coal slurry oil
Afterwards, and by bio-coal slurry oil heat exchange 400 DEG C are warming up to, then second of injection is pressed into the bio-coal slurry oil again
The high pressure-temperature hydrogen that power is 23MPa, temperature is 510 DEG C, and control the high pressure hydrogen injected twice and the biomass kerosene
The volume ratio of slurry is 800：1, so as to form reaction raw materials；The reaction raw materials are sent into paste state bed reactor liquid occurs
Change, cracking and hydrogenation reaction, while the high pressure that injection pressure is 23MPa into the paste state bed reactor, temperature is 80 DEG C is cold
Hydrogen, the cold hydrogen are injected via 4 inlets on the paste state bed reactor side wall, are controlled in the paste state bed reactor
Total gas velocity is 0.05m/s.Storage of the catalyst in the paste state bed reactor is controlled in the paste state bed reactor
The 30wt% of liquid phase quality.
Embodiment 8
The common liquefaction process of a kind of coal and biomass, includes the following steps：
The pretreatment of biomass material：
(1) reed is taken, is baked to be dehydrated, airslide disintegrating mill is then fed into and crushes processing, obtains one wheat-middlings of reed
Particle, grain size D50It is 200 μm.
(2) crushed material of reed is sent into cuber or plodder carries out extrusion forming, briquetting pressure 3MPa is obtained
Reed compression material.
(3) reed is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain reed separating twice material, grain size D50
It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) lignite is taken, is baked to be dehydrated, ball mill is then fed into and crushes processing, obtains crushed material of lignite,
Grain size D50It is 80 μm.
(2) crushed material of lignite is sent into cuber or plodder carries out extrusion forming, briquetting pressure 12MPa is obtained
It compresses and expects to lignite.
(3) lignite is compressed into material and is sent into ball mill, carried out separating twice, obtain lignite separating twice material, grain size D50For 35 μ
M, for use.
The preparation of bio-coal slurry oil and liquefaction process：
Reed after separating twice and lignite are added in washing oil, so as to form the bio-coal slurry oil.As one kind
Preferred embodiment, above-mentioned bio-coal slurry oil can also continue to through milling treatment of colloid, can continue to improve the biomass kerosene
The paste-forming properties of slurry.
Hydrogen is passed through to react into the bio-coal slurry oil, and controls reaction pressure as 25MPa, reaction temperature
It it is 380 DEG C, the time of reaction is 90min, and bio oil is finally made.Wherein, sulphur and unformed FeOOH are with mass ratio
It is 1：1 mixed preparing obtains catalyst.In the bio-coal slurry oil, the content of the reed is 25wt%, the coal
Content is 40wt%, and the content of the catalyst is 10wt%, and the grain size of the catalyst is 5 μm.The tool for being passed through hydrogen
Body method is：
Injecting the high pressure medium temperature hydrogen that pressure is 27MPa, temperature is 360 DEG C for the first time into the bio-coal slurry oil
Afterwards, and by bio-coal slurry oil heat exchange 420 DEG C are warming up to, then second of injection is pressed into the bio-coal slurry oil again
The high pressure-temperature hydrogen that power is 27MPa, temperature is 440 DEG C, and control the body of the high pressure hydrogen and the bio-coal slurry oil
Product is than being 1000：1, so as to form reaction raw materials；The reaction raw materials are sent into paste state bed reactor liquefaction, cracking occurs
And hydrogenation reaction, while into the paste state bed reactor inject pressure be 27MPa, the cold hydrogen of high pressure that temperature is 50 DEG C, it is described
Cold hydrogen is injected via 3 inlets on the paste state bed reactor side wall, controls total gas velocity in the paste state bed reactor
For 0.02m/s.Storage of the catalyst in the paste state bed reactor controls the liquid phase matter in the paste state bed reactor
The 5wt% of amount.
Comparative example 1
The common liquefaction process of a kind of coal and biomass, includes the following steps：
Lignite is taken, is baked to be dehydrated, and it is 50 μm to be crushed to median, cuber is then fed into or plodder carries out
Extrusion forming, briquetting pressure 15MPa obtain lignite compression material.Lignite is compressed into material and is sent into hammer crusher, is crushed,
Obtain the lignite crushed material that grain size is 30 μm.By above-mentioned lignite crushed material and the unformed hydroxyl in reactor after vulcanizing treatment
Base iron oxide is added in into the mixture of liquid excrement and used oil to form bio-coal slurry oil jointly, to the bio-coal
Hydrogen is passed through in slurry oil to react, and to control reaction pressure be 4MPa, reaction temperature is 430 DEG C, bio oil is finally made.
Comparative example 2
The common liquefaction process of a kind of coal and biomass, includes the following steps：
Lignite is taken, is baked to be dehydrated, and it is 50 μm to be crushed to median, cuber is then fed into or plodder carries out
Extrusion forming, briquetting pressure 15MPa obtain lignite compression material.Lignite is compressed into material and is sent into hammer crusher, is crushed,
Obtain the lignite crushed material that grain size is 30 μm.By above-mentioned lignite crushed material and the oil-soluble point in reactor after vulcanizing treatment
It dissipates type hydrogenation catalyst to add in into the mixture of liquid excrement and used oil to form bio-coal slurry oil jointly, to the life
Hydrogen is passed through to react in substance kerosene slurry, and to control reaction pressure be 16MPa, reaction temperature is 480 DEG C, it is final to be made
Bio oil.
The technological effect of the embodiment of the present invention and comparative example is compared, result is as shown in table 1 below.
The technological effect of 1 each embodiment and comparative example of table compares
As it can be seen from table 1 relative to comparative example 1-2, biomass that technique using the present invention obtains and coal it is common
Conversion ratio and the yield of bio oil are higher, and level of residue then significantly reduces, so as to which the method for learning the present invention can be carried significantly
The yield of high biomass conversion ratio and bio oil reduces level of residue.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (12)
1. the common liquefaction process of a kind of coal and biomass, which is characterized in that include the following steps：
The preparation of bio-coal slurry oil：
Biomass collection simultaneously controls moisture content to be less than 2wt%, and it is 100~300 μm to be then crushed to median；
Biomass after crushing is subjected to compression forming, compression pressure is 2~5MPa, and compression temperature is 30~60 DEG C；
By the pulverization process again of the biomass after compression forming, it is 30~50 μm to be crushed to median, obtains powdered biomass；
Collect coal and simultaneously control moisture content less than 2wt%, it is 50~100 μm to be then crushed to median, compression temperature for 30~
60℃；
Compression forming is carried out to the coal after crushing, compression pressure is 5~15MPa；
To the pulverization process again of the coal after compression forming, it is 30~50 μm to be crushed to median, obtains coal dust；
By the powdered biomass, the coal dust, catalyst mixed with oil product, grind slurrying and obtain bio-coal slurry oil, it is described
Powdered biomass and the coal dust account for 60~70wt% of the bio-coal slurry oil altogether；
Liquefaction reaction：Be passed through hydrogen into the bio-coal slurry oil to react, and control reaction pressure for 15~
25MPa, reaction temperature are 380~480 DEG C, and bio oil is finally made；
In the preparation steps of the bio-coal slurry oil, when carrying out the mixing, for first by the powdered biomass and described
Coal dust carries out ash disposal and after being pre-mixed with the catalyst, then gained premix is mixed with the oil product, alternatively, being straight
It connects and mixes the powdered biomass, the coal dust, the catalyst with the oil product.
2. the common liquefaction process of coal according to claim 1 and biomass, which is characterized in that the bio-coal slurry oil
In, a concentration of 20~30wt% of biomass, a concentration of 30~45wt% of coal dust.
3. the common liquefaction process of coal according to claim 1 or 2 and biomass, which is characterized in that using drying and dewatering
Moisture content is controlled, the drying and dewatering temperature is 50~70 DEG C, and the drying and dewatering time is 3~5h.
4. according to claim 1-3 any one of them coal and the common liquefaction process of biomass, which is characterized in that bio-coal
The heap density that the powdered biomass is controlled in the preparation steps of slurry oil is 300~500kg/m3, the heap for controlling the coal dust is close
It spends for 1000~1200kg/m3。
5. according to claim 1-4 any one of them coal and the common liquefaction process of biomass, which is characterized in that the grinding
The time of slurrying is 2~8min.
6. according to claim 1-5 any one of them coal and the common liquefaction process of biomass, which is characterized in that the coal is
Low-order coal；The oil product is hogwash fat, gutter oil, rancid oil, waste lubricating oil, used oil, heavy oil, residual oil, washing oil, carbolineum, coal
It is one or more in tar, oil or bio oil made from this technique.
7. according to claim 1-6 any one of them coal and the common liquefaction process of biomass, which is characterized in that in the life
In substance kerosene slurry, the content of the catalyst is 0.1~10wt%, preferably 2wt%；The grain size of the catalyst is 5 μm
~500 μm.
8. according to claim 1-7 any one of them coal and the common liquefaction process of biomass, which is characterized in that described to be passed through
The specific method of hydrogen is：
High pressure hydrogen is injected into the bio-coal slurry oil, and controls the body of the high pressure hydrogen and the bio-coal slurry oil
Product is than being (600~1000)：1, so as to form reaction raw materials；
The reaction raw materials are sent into paste state bed reactor to occur liquefaction, cracking and hydrogenation reaction, while to the slurry
The injection cold hydrogen of high pressure in bed reactor, it is 0.02~0.2m/s to control total gas velocity in the paste state bed reactor, preferably
0.05~0.08m/s；
Wherein, the pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 13~27MPa, the temperature of the cold hydrogen of the high pressure for 50~
135℃。
9. the common liquefaction process of coal according to claim 8 and biomass, which is characterized in that by the High Pressure Hydrogen qi leel
It is injected into twice in the bio-coal slurry oil, specially：
After high pressure medium temperature hydrogen is injected for the first time into the bio-coal slurry oil, and the bio-coal slurry oil is exchanged heat and is risen
Temperature then injects high pressure-temperature hydrogen for the second time into the bio-coal slurry oil again to 300~400 DEG C；
Wherein, the temperature of the high pressure medium temperature hydrogen is 300~400 DEG C, and the temperature of the high pressure-temperature hydrogen is 410~510
℃。
10. coal and the common liquefaction process of biomass according to claim 8 or claim 9, which is characterized in that the catalyst exists
Storage in the paste state bed reactor controls 5~30wt% of the liquid phase quality in the paste state bed reactor.
11. according to claim 1-10 any one of them coal and the common liquefaction process of biomass, which is characterized in that described anti-
The time answered is 30~90min.
12. according to claim 1-11 any one of them coal and the common liquefaction process of biomass, which is characterized in that described to urge
Biomass carbon of the agent for the active component of load through vulcanizing treatment, the active component is iron oxide, FeOOH or
It is one or more in iron hydroxide；
Or the catalyst is the unformed FeOOH through vulcanizing treatment.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128867A1 (en) * | 2017-12-25 | 2019-07-04 | 北京三聚环保新材料股份有限公司 | Hydrolysis hydrogenation process for biomass |
| CN110218573A (en) * | 2019-06-18 | 2019-09-10 | 太原理工大学 | A kind of no catalyst coal base heavy component method for upgrading |
| RU2737888C1 (en) * | 2020-05-12 | 2020-12-04 | Евгений Петрович Яковенко | Method of producing hydrocarbon fuel from coal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109131A (en) * | 1984-11-22 | 1986-10-01 | 莱茵褐煤动力燃料联合股份公司 | The process for subsequent treatment of carbonaceous wastes and biomass |
| US20090299112A1 (en) * | 2008-05-30 | 2009-12-03 | Bauer Lorenz J | Slurry Hydroconversion of Biorenewable Feedstocks |
| CN101899314A (en) * | 2009-05-27 | 2010-12-01 | 新奥科技发展有限公司 | Method for preparing light oil by from coal and/or biomass |
| CN103242882A (en) * | 2013-04-15 | 2013-08-14 | 新疆大学 | Method for producing oil by using co-liquefaction of cotton stalks and coal without adding catalyst |
| CN104927948A (en) * | 2015-06-16 | 2015-09-23 | 神华集团有限责任公司 | Water coal slurry preparing method |
-
2017
- 2017-12-26 CN CN201711431460.XA patent/CN108192652B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109131A (en) * | 1984-11-22 | 1986-10-01 | 莱茵褐煤动力燃料联合股份公司 | The process for subsequent treatment of carbonaceous wastes and biomass |
| US20090299112A1 (en) * | 2008-05-30 | 2009-12-03 | Bauer Lorenz J | Slurry Hydroconversion of Biorenewable Feedstocks |
| CN101899314A (en) * | 2009-05-27 | 2010-12-01 | 新奥科技发展有限公司 | Method for preparing light oil by from coal and/or biomass |
| CN103242882A (en) * | 2013-04-15 | 2013-08-14 | 新疆大学 | Method for producing oil by using co-liquefaction of cotton stalks and coal without adding catalyst |
| CN104927948A (en) * | 2015-06-16 | 2015-09-23 | 神华集团有限责任公司 | Water coal slurry preparing method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128867A1 (en) * | 2017-12-25 | 2019-07-04 | 北京三聚环保新材料股份有限公司 | Hydrolysis hydrogenation process for biomass |
| CN110218573A (en) * | 2019-06-18 | 2019-09-10 | 太原理工大学 | A kind of no catalyst coal base heavy component method for upgrading |
| RU2737888C1 (en) * | 2020-05-12 | 2020-12-04 | Евгений Петрович Яковенко | Method of producing hydrocarbon fuel from coal |
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