CN108085041A - A kind of method of biomass liquefying production light oil - Google Patents
A kind of method of biomass liquefying production light oil Download PDFInfo
- Publication number
- CN108085041A CN108085041A CN201711421658.XA CN201711421658A CN108085041A CN 108085041 A CN108085041 A CN 108085041A CN 201711421658 A CN201711421658 A CN 201711421658A CN 108085041 A CN108085041 A CN 108085041A
- Authority
- CN
- China
- Prior art keywords
- reaction
- biomass
- oil
- hydrogenation
- vegetable oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 239000003921 oil Substances 0.000 claims abstract description 111
- 235000019198 oils Nutrition 0.000 claims abstract description 111
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 80
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 41
- 239000008158 vegetable oil Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 239000000470 constituent Substances 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- 229910002588 FeOOH Inorganic materials 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims 2
- 235000014593 oils and fats Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 235000004443 Ricinus communis Nutrition 0.000 description 9
- 239000012075 bio-oil Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- -1 carbon Short chain fatty acids Chemical class 0.000 description 7
- 238000007667 floating Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 5
- 241000931143 Gleditsia sinensis Species 0.000 description 4
- 240000007817 Olea europaea Species 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 235000021391 short chain fatty acids Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 150000004666 short chain fatty acids Chemical class 0.000 description 2
- 239000010913 used oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019752 Wheat Middilings Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to field of biological energy source,More particularly to a kind of method of biomass liquefying production light oil,The specific preparation steps of its biomass slurry are,Vegetable oil residue is dried successively,Just crush,Compression and separating twice,Then with hydrogenation catalyst,Vulcanizing agent is mixed to get mixture,It adds the mixture to and slurrying is ground into solvent naphtha,The biomass slurry that vegetable oil residue concentration is 50 65wt% is made,The present invention it is initiative vegetable oil residue is first compressed after separating twice treatment process,By the way that biomass is compressed processing,Making loose vegetable oil residue, successively experience ranks again,The stages such as mechanically deform,So that density and the proportion increase of vegetable oil residue,It is allowed to be conducive to be dispersed in oil product,And its content in oil product can be improved,Increase the concentration of reaction mass,Pump is improved within the unit interval to the conveying capacity of biomass,It ensure that the steady operating and conveying of pump.
Description
Technical field
The invention belongs to biomass liquefying technical fields, and in particular to a kind of method of biomass liquefying production light oil.
Background technology
All organic matters that can be grown are collectively termed as biomass, in a broad sense, biomass refer to include all plants,
Microorganism and using plant, microorganism as the animal of food and its discarded object of production；In a narrow sense, biomass is primarily referred to as
The lignocellulosics such as the vegetable oil residues such as the Oil Residue in agriculture and forestry production process in addition to grain, fruit, trees are (referred to as wooden
Element), farming industry leftover bits and pieces, the substances such as the fowl and animal excrement during agriculture and forestry organic waste material and Animal husbandry production and discarded object.
Common representative biomass has crops, agricultural waste material, timber, timber waste and animal wastes etc..Various biologies
Exist between matter and interdepend and interaction relationship, biomass can be used as food and the raw material of industry, can also improve environment
With regulate the climate, in addition, biomass also has the characteristics that recyclability, low stain, widely distributed property, become renewable
The important component of the energy, therefore, how Efficient Development using biomass energy, all will to solving the energy, ecological environment problem
Play very positive effect.It is the important component in biomass resource utilization that biomass direct liquefaction, which obtains liquefaction oil,.
The liquefaction mechanism of biomass is as follows：Biomass is cracked into oligomer first, then again through dehydration, dehydroxylation, dehydrogenation, deoxidation and de-
Carboxyl and form micromolecular compound, micromolecular compound is then by being condensed, being cyclized, the reaction such as polymerizeing and generate new chemical combination
Object.Biomass liquefying technology can be divided mainly into two major class of indirect liquefaction and direct liquefaction at present, wherein, biomass direct liquefaction skill
Art refers under the action of solvent or catalyst, using hydrolysis, supercritical liquefaction or hydrogen, inert gas etc. is passed through, appropriate
Temperature, biomass is directly liquefied as liquid from solid under pressure.For example, Chinese patent literature CN103540414A is disclosed
A kind of method of palm dregs of fat and acidification oil refining biodiesel is liquid first by the palm dregs of fat and acidification oil preheating, and
The palm dregs of fat and acidification oil of liquid are sent in electrothermal furnace with high temperature oil pump afterwards and are heated, moisture is completed within 200 DEG C and is steamed
Hair, evaporates oil vapour between 220-380 DEG C, and oil vapour passes through catalyst for cracking pipeline, is transformed into after catalysis below 18 carbon
Short chain fatty acids, then the short chain fatty acids after esterification are finally converted into biodiesel by short chain fatty acids.
Above-mentioned technique realizes the conversion from vegetable oil residue to bio oil.But in above-mentioned technology, on the one hand, by the palm dregs of fat
It needs to be delivered in catalyst for cracking pipeline by pump with the slurry that acidification oil is formed, and the most plants dregs of fat are because with abundant hole
Gap rate causes its proportion relatively low, is allowed to relatively be insoluble in solvent naphtha, and the concentration for causing vegetable oil residue in slurries is relatively low, so as to cause
Pump it is limited to the conveying capacity of vegetable oil residue within the unit interval, cause the production efficiency of above-mentioned technique is relatively low, industrial cost is higher,
Energy consumption is larger；On the other hand, the vegetable oil residue with porosity easily floats on solvent oil meter face, in addition the acid as slurry solvent
Carburetion viscosity is larger so that above-mentioned slurry is not easy to flow, and easily causes the blocking of conveyance conduit so as to be difficult to realize the steady fortune of pump
It is defeated.Although the prior art is attempted to add in dispersant in slurries to improve concentration and dispersiveness of the vegetable oil residue in slurries,
The quality for adding in often bio oil made from influence of dispersant.
For this purpose, how to be improved to increase the dense of vegetable oil residue in slurries to the cracking and catalyzing technique of existing biomass
Degree, improve in the unit interval pump to the conveying capacity of vegetable oil residue, realize the smooth transport of pump, reduce energy consumption this for this field skill
A technical barrier urgently to be resolved hurrily is remained for art personnel.
The content of the invention
Therefore, the technical problem to be solved in the present invention is pumped in existing biomass cracking Catalytic processes are overcome to life
The conveying capacity of substance is few and the defects of transport unstable, high energy consumption, and then provides a kind of side of biomass liquefying production light oil
Method.
Technical solution is as follows used by the present invention solves the above problems：
A kind of method of biomass liquefying production light oil, comprises the following steps：
(1) biomass, hydrogenation catalyst, vulcanizing agent and solvent naphtha are mixed, biomass slurry is made；
(2) biomass slurry and hydrogen are subjected to the first liquefaction reaction, collect the first reaction product；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction, collect the second reaction product；
(4) first time separation is carried out to second reaction product, collects light component and heavy constituent；
(5) heavy constituent is evaporated under reduced pressure, collects light fraction；
(6) light component and the light fraction are mixed and carries out hydrogenation reaction, collect hydrogenation products；
(7) hydrogenation products are fractionated, obtain light oil；
In step (1), the biomass is vegetable oil residue, and the preparation steps of the biomass slurry are, by vegetable oil residue
Be dried successively, just crush, compress and separating twice, be then mixed to get mixture with the hydrogenation catalyst, vulcanizing agent,
The mixture is added in and grinds slurrying into the solvent naphtha, obtains the slurries that vegetable oil residue concentration is 50-65wt%.
Vegetable oil residue in the present invention can be the palm dregs of fat, Oil Residue, the peanut dregs of fat, the gleditsia sinensis dregs of fat, flax dregs of fat,
One or more in castor pomace, the vegetable seeds dregs of fat or the olive dregs of fat etc..
In the preparation steps of the biomass slurry, the pressure that the vegetable oil residue is compressed is 3-5MPa, temperature
For 40-60 DEG C.
In the preparation steps of the slurries, the drying temperature of the vegetable oil residue is 80-110 DEG C, time 2-6h, described
The dried moisture content of vegetable oil residue is less than 2wt%；Median particle size is 100-300 μm after just crushing；The middle position after separating twice
Granularity is 30-50 μm, heap density is 1500-1600kg/m after separating twice3。
The viscosity of the slurries is 300-700mPa ﹒ s (50 DEG C).
The grinding slurrying is stirring pulping, disperses slurrying, emulsifies slurrying, shears slurrying or homogeneous slurrying.
The solvent naphtha is the one or more in waste animal and vegetable oil, waste mineral oil, mineral oil or distillate.
Further, the waste animal and vegetable oil is the one or more in gutter oil, hogwash fat or rancid oil；
The waste mineral oil is one or both of waste lubricating oil or used oil；
The mineral oil is the one or more in heavy oil, residual oil, carbolineum or washing oil.
The biomass and the hydrogenation catalyst, the mass ratio of the vulcanizing agent are 100：(0.5~5)：(0.1~
0.4)。
In the step (2), the reaction condition of first liquefaction reaction is as follows：
Reaction temperature is 380-460 DEG C；
Reaction pressure is 15-25MPa；
Gas liquid ratio is 800-1600L/kg；
The air speed of the biomass slurry is 0.4-2h-1。
In the step (3), the reaction condition of second liquefaction reaction is as follows：
Reaction temperature is 390-490 DEG C；
Reaction pressure is 15-25MPa；
Gas liquid ratio is 700-1600L/kg；
The air speed of the biomass slurry is 0.3-2h-1。
In the step (5), the temperature of the vacuum distillation is 320-400 DEG C, pressure 5-20kPa.
In the step (6), the reaction condition of the hydrogenation reaction is as follows：
Reaction temperature is 400-470 DEG C；
Reaction pressure is 15-20MPa；
Hydrogen to oil volume ratio is 800-1500；
Air speed is 0.4-2h-1。
In the step (8), the temperature of the fractionation is 340-390 DEG C.
It further includes and collects gained distillate and the fractionating step gained heavy end after being evaporated under reduced pressure step, and will
The step of distillate and the heavy end are as the solvent naphtha.
The hydrogenation products further include and the hydrogenation products are carried out with second of separation before being fractionated, respectively
The step of to hydrogen, gas phase lighter hydrocarbons and liquid phase, hydrogen Xun Huan therein are anti-for first liquefaction reaction, second liquefaction
Should in the hydrogenation reaction.
In the step (1), the temperature of the blend step is 25-180 DEG C.
The hydrogenation catalyst is at least one of following catalyst：
1) amorphous Fe oxides and/or unformed FeOOH；
2) the unformed aluminium oxide of carrying active ingredients, the active ingredient is vib metal, Section VII B metals or the
At least one of oxide of group VIII metal, the content of the active ingredient is 10-25wt%.
Compared with prior art, the present invention has the advantages that：
(1) method of biomass liquefying production light oil provided by the invention, the preparation steps of biomass slurry are to incite somebody to action
Vegetable oil residue is dried, just crushes successively, compressing and separating twice, is then mixed to get with hydrogenation catalyst, vulcanizing agent mixed
Object is closed, adds the mixture into solvent naphtha grinding slurrying up to the slurries that vegetable oil residue concentration is 50-65wt%, the present invention
It is initiative vegetable oil residue is first compressed after separating twice treatment process, by the way that vegetable oil residue is compressed place
Reason, make loose vegetable oil residue successively experience cave in, be closed etc. rank again, the stage of mechanically deform so that vegetable oil residue
Volume is greatly lowered, and thus can reduce the porosity of vegetable oil residue, increases its density and proportion, is allowed to be conducive to be dispersed in oil
In product, and its content in oil product can be improved, add the concentration of reaction mass, vegetable oil residue of the present invention containing in slurries
Amount may be up to 50-65wt%, simultaneously because in slurries the increase of biomass concentration will necessarily also improve pump it is right within the unit interval
The conveying capacity of vegetable oil residue, so as to improve the efficiency of entire biomass liquefying process, reduce industrial cost and energy consumption；In addition,
The increase of vegetable oil residue proportion also helps suspension of the vegetable oil residue in slurries with disperseing, and thus can reduce biomass slurry
Viscosity realizes the smooth flow of biomass into the slurries after slurry in the duct, avoids the blocking of pipeline, realizes the flat of pump
Steady operating and conveying, while but also cannot function as the high viscosity waste oil of biomass liquefying solvent in the prior art, such as useless machine
Oil, gutter oil, rancid oil etc., can also be utilized.
Biomass slurry is made by the way that biomass, hydrogenation catalyst, vulcanizing agent and solvent naphtha are mixed in the present invention；Again will
Biomass slurry and hydrogen carry out the first liquefaction reaction and the second liquefaction reaction successively, the second reaction product are collected, by twice
Liquefaction reaction ensures that biomass fully liquefies as liquid phase, raising liquid oil yield；Then the second reaction product is separated,
Collect light component and heavy constituent；Then heavy constituent is evaporated under reduced pressure, collects light fraction；Again by light component and light fraction
Mixing carries out hydrogenation reaction；By three above-mentioned separation, vacuum distillation and hydrogenation reaction continuous steps, realize light component and
The separation of heavy constituent, and by the light fraction being mingled in heavy constituent by vacuum distillation from wherein separating, while by difficulty
The heavy end of hydrogenation liquefaction is separated, in case it influences the conversion of follow-up light oil, then by light fraction and light component
Mixing carries out hydrogenation reaction, and the heavy constituent for a little easy lighting being mingled in light component can be made to be changed into gently by hydrogenation reaction
Component improves the yield of light oil, the yield of low boiling range oil particularly in light oil, such as naphtha, furthermore in advance to life
Substance oil, which is separated and is evaporated under reduced pressure, makes residue therein be enriched with caking as far as possible, is then gone from vacuum distillation apparatus bottom
It removes, reduces residue content in follow-up light oil；Finally hydrogenation products are fractionated, obtain light oil, mink cell focus and the dregs of fat.
Through experimental test, method biomass conversion ratio >=99% of the invention, lightweight biology oil yield of the boiling range below 520 DEG C be
70-80%, residue content is less than 0.1wt% in lightweight bio oil.
(2) method of biomass liquefying production light oil provided by the invention, by controlling compression temperature in 40-60
DEG C, then the rheological characteristic that can significantly increase vegetable oil residue is compressed at a temperature of this to vegetable oil residue, reduce the viscous of biomass slurry
Degree, after tested, the viscosity of the slurries formed in present invention process by vegetable oil residue and oil product is 300-700mPa ﹒ s (50 DEG C), by
This realizes the smooth flow of biomass into the slurries after slurry in the duct, avoids the blocking of pipeline, realizes the steady of pump
Operating and conveying.
(3) method of biomass liquefying production light oil provided by the invention, further includes and collects the vacuum distillation step
Gained distillate and fractionating step gained heavy end afterwards, and using the distillate and the heavy end as described molten
The step of agent oil can effectively be reduced the cost of solvent naphtha by the step, expand the source of solvent naphtha, be not limited to outer solubilization
Agent oil, such as the mode of heavy oil, solvent naphtha supply is flexible, operating flexibility is big.
(4) method for the biomass liquefying production light oil that the embodiment of the present invention is provided, the hydrogenation products are carrying out
It before fractionation, further includes and the hydrogenation products is carried out with second of separation, respectively obtain the step of hydrogen, gas phase lighter hydrocarbons and liquid phase
Suddenly, hydrogen therein can be cycled in the first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution of the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in describing below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the process flow diagram for the method that biomass liquefying of the present invention produces light oil.
Reference numeral：
1- vulcanizing agents；2- biomass；3- hydrogenation catalysts；4- biomass slurry tanks；5- suspended-bed reactors；Xun Huan in 6-
Suspended-bed reactor；7- floating bed hydrogenation products；8- high pressure hot separators；9- light components；10- heavy constituents；11- High Pressure Differences depressurize
Valve；12- vacuum towers；13- overhead oils；14- survey line distillates；15- fixed bed hydrogenation reactors；16- fixed bed hydrogenation products；
17- separators；18- hydrogen；19- gas phase lighter hydrocarbons；20- distillates；21- fractionating columns；22- biomass naphthas；23- biomass firewoods
Oil；24- biomass bottom of towe oil；25- residues；26- hydrogen.
Specific embodiment
In order to which the object, technical solutions and advantages of the present invention are better described, below in conjunction with specific embodiment to this hair
It is bright to be described further.The present invention can be embodied in many different forms, and should not be construed as limited to set forth herein
Embodiment.On the contrary, provide these embodiments so that the disclosure will be thorough and complete, and the design of the present invention will be filled
Divide and be communicated to those skilled in the art, the present invention will only be defined by the appended claims.
As long as in addition, technical characteristic involved in invention described below different embodiments non-structure each other
It can be combined with each other into conflict.
Embodiment 1
A kind of method of biomass liquefying production light oil is present embodiments provided, as shown in Figure 1, comprising the following steps：
(1) the vegetable seeds dregs of fat and the olive dregs of fat are sent into drying machine at 80 DEG C dry 3h to water content less than 2wt%, so
It is sent into micronizer afterwards just crush, the median after just crushing is 100 μm, then by the vegetable seeds dregs of fat after first crush
It is sent into the olive dregs of fat in plodder and is compressed extrusion forming under 50 DEG C of temperature, the pressure of 3MPa, carried out afterwards secondary
Pulverization process obtains median as 30 μm of the vegetable seeds dregs of fat and the hybrid particles 2 of the olive dregs of fat, the mixing after separating twice
The heap density of particle 2 is 1500kg/m3；
By above-mentioned hybrid particles 2, load have the unformed aluminium oxide 3 of Mo oxides and Ni oxides (its grain size for 5 μm-
50 μm, load capacity 10wt%) with sulphur 1 it is 100 in mass ratio：0.5：0.4 is uniformly mixed so as to obtain mixing in biomass slurry tank 4
Object, and the mixing at 100 DEG C is fed the mixture into gutter oil, slurrying is then stirred, forming biomass content is
The biomass slurry of 65wt%, the viscosity of the slurries is 700mPa ﹒ s (50 DEG C), spare；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 380 DEG C, reaction pressure 25MPa, gas-liquid
Than being 2h for the air speed of 800L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 390 DEG C,
Reaction pressure is 25MPa, gas liquid ratio 700L/kg, the air speed of the biomass slurry are 1h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 19MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 320 DEG C, pressure
To be evaporated under reduced pressure under 20kPa, light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12 are collected, is surveyed
Line distillate 14, which is back in step (1), is used as solvent naphtha 1, and recycles residue 25 from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 400 DEG C, reaction pressure 20MPa, hydrogen oil
Volume ratio is 800, air speed 2h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 360 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end, and return it to conduct in step (1) are discharged outside bottom of towe
Solvent naphtha 1.
Through experimental test, the conversion ratio of biomass is 95%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 75%, and residue content is 0.09wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
80wt%, organic hydrogen content 19.5wt%, organic oxygen content are 0.5wt%.
Embodiment 2
A kind of method of biomass liquefying production light oil is present embodiments provided, is comprised the following steps：
(1) the palm dregs of fat and castor pomace are sent into drying machine at 100 DEG C dry 2h to water content less than 2wt%,
It is then fed into micronizer just crush, the median after just crushing is 300 μm, then by the palm oil after first crush
Slag and castor pomace are sent into plodder is compressed extrusion forming under 60 DEG C of temperature, the pressure of 5MPa, carries out two afterwards
Secondary pulverization process obtains median as 50 μm of the palm dregs of fat and the hybrid particles 2 of castor pomace after separating twice, this is mixed
The heap density for closing particle 2 is 1600kg/m3；
By above-mentioned hybrid particles 2, load have the unformed aluminium oxide 3 of W oxides and Pd oxides (its grain size for 100 μm-
150 μm, load capacity 25%) with carbon disulfide 1 it is 100 in mass ratio：5：0.1 be uniformly mixed so as to obtain in biomass slurry tank 4 it is mixed
Object is closed, and feeds the mixture into the miscella of waste lubricating oil and residual oil the mixing at 180 DEG C, then carries out scattered slurrying, shape
Into the biomass slurry that biomass content is 55wt%, the viscosity of the slurries is 300mPa ﹒ s (50 DEG C), spare；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 460 DEG C, reaction pressure 15MPa, gas-liquid
Than being 0.4h for the air speed of 1600L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 490 DEG C,
Reaction pressure is 15MPa, gas liquid ratio 1600L/kg, the air speed of the biomass slurry are 0.3h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 15MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 400 DEG C, pressure
To be evaporated under reduced pressure under 5kPa, light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12 are collected, is surveyed
Line distillate 14, which is back in step (1), is used as solvent naphtha 1, and recycles residue 25 from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 470 DEG C, reaction pressure 15MPa, hydrogen oil
Volume ratio is 1500, air speed 0.4h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 390 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end, and return it to conduct in step (1) are discharged outside bottom of towe
Solvent naphtha 1.
Through experimental test, the conversion ratio of biomass is 100%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 70%, and residue content is 0.08wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
90wt%, organic hydrogen content 9.5wt%, organic oxygen content are 0.5wt%.
Embodiment 3
A kind of method of biomass liquefying production light oil is present embodiments provided, is comprised the following steps：
(1) the gleditsia sinensis dregs of fat are sent into drying machine the dry 6h at 110 DEG C and are less than 2wt% to water content, be then fed into super
Atomizer just crush, and the median after just crushing is 200 μm, and the gleditsia sinensis dregs of fat after first crush then are sent into press strip
Extrusion forming is compressed under 40 DEG C of temperature, the pressure of 4MPa in machine, separating twice processing is carried out afterwards, through separating twice
The gleditsia sinensis dregs of fat particle 2 that median is 40 μm is obtained afterwards, and the heap density of the particle 2 is 1550kg/m3；
Above-mentioned particle 2, load are had the unformed aluminium oxide of Mn oxides, and (its grain size is 100 μm -150 μm, and load capacity is
15%), amorphous Fe oxides and sulphur are 100 in mass ratio：2：2：0.3 is uniformly mixed so as to obtain mixture in biomass slurry tank 4,
And the mixing at 25 DEG C is fed the mixture into the miscella that heavy oil and hogwash fat are formed, emulsification slurrying is then carried out, forms life
Content of material is the biomass slurry of 50wt%, and the viscosity of the slurries is 485mPa ﹒ s (50 DEG C), spare；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 390 DEG C, reaction pressure 17MPa, gas-liquid
Than being 0.7h for the air speed of 1000L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 450 DEG C,
Reaction pressure is 20MPa, gas liquid ratio 1000L/kg, the air speed of the biomass slurry are 2h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 15MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 380 DEG C, pressure
To be evaporated under reduced pressure under 10kPa, light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12 are collected, is surveyed
Line distillate 14, which is back in step (1), is used as solvent naphtha 1, and recycles residue 25 from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 400 DEG C, reaction pressure 18MPa, hydrogen oil
Volume ratio is 1500, air speed 1.5h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 360 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end, and return it to conduct in step (1) are discharged outside bottom of towe
Solvent naphtha 1.
Through experimental test, the conversion ratio of biomass is 98%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 80%, and residue content is 0.09wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
85wt%, organic hydrogen content 13wt%, organic oxygen content are 2wt%.
Embodiment 4
A kind of method of biomass liquefying production light oil is present embodiments provided, is comprised the following steps：
(1) Oil Residue is sent into drying machine the dry 5.0h at 90 DEG C and is less than 2wt% to water content, be then fed into super
Atomizer carries out just pulverization process, and the median after just crushing is 150 μm, is then sent into the Oil Residue after first crush
Extrusion forming is compressed under 45 DEG C of temperature, the pressure of 2.5MPa in plodder, separating twice processing is carried out afterwards, through two
The Oil Residue particle 2 that median is 35 μm is obtained after secondary crushing, the heap density of the particle 2 is 1515kg/m3, it is spare；
By above-mentioned particle 2 and unformed FeOOH 3, dimethyl disulfide 1 in mass ratio 100:4:0.2 in biomass
Mixture is uniformly mixed so as to obtain in serum pot 4, and feeds the mixture into the miscella of washing oil and distillate the mixing at 100 DEG C, so
After carry out shearing slurrying, form the biomass slurry that biomass content is 60wt%, the viscosity of the slurries is 610mPa ﹒ s (50
DEG C), it is spare；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 450 DEG C, reaction pressure 23MPa, gas-liquid
Than being 1.8h for the air speed of 1500L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 475 DEG C,
Reaction pressure is 24MPa, gas liquid ratio 1400L/kg, the air speed of the biomass slurry are 1.5h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 22MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 380 DEG C, pressure
To be evaporated under reduced pressure under 8kPa, collection light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12, and
Residue 25 is recycled from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 460 DEG C, reaction pressure 18MPa, hydrogen oil
Volume ratio is 1300, air speed 1.6h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 390 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end are discharged outside bottom of towe.
Through experimental test, the conversion ratio of biomass is 97%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 76%, and residue content is 0.09wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
80wt%, organic hydrogen content 19.5wt%, organic oxygen content are 0.5wt%.
Embodiment 5
A kind of method of biomass liquefying production light oil is present embodiments provided, is comprised the following steps：
(1) castor pomace is sent into drying machine the dry 4.h at 104 DEG C and is less than 2wt% to water content, be then fed into super
Atomizer just crush, and the median after just crushing is 250 μm, and the castor pomace after first crush then is sent into briquetting
Extrusion forming is compressed under 55 DEG C of temperature, the pressure of 4.5MPa in machine, separating twice processing is carried out afterwards, through two wheat-middlings
The castor pomace particle 2 that median is 45 μm is obtained after broken, the heap density of castor pomace particle 2 is 1582kg/m3, it is spare.
By above-mentioned castor pomace particle 2, amorphous Fe oxides, unformed FeOOH, sulphur 1 in mass ratio 100:2:
1.5:0.1 is uniformly mixed so as to obtain mixture in biomass slurry tank 4, and feed the mixture into the miscella of residual oil and used oil in
Then mixing at 100 DEG C carries out homogeneous slurrying, form the biomass slurry that biomass content is 63wt%, the viscosity of the slurries
It is spare for 386mPa ﹒ s (50 DEG C)；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 420 DEG C, reaction pressure 21MPa, gas-liquid
Than being 1.1h for the air speed of 1300L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 470 DEG C,
Reaction pressure is 24MPa, gas liquid ratio 1500L/kg, the air speed of the biomass slurry are 1.6h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 21MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 330 DEG C, pressure
To be evaporated under reduced pressure under 11kPa, light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12 are collected, is surveyed
Line distillate 14, which is back in step (1), is used as solvent naphtha 1, and recycles residue 25 from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 455 DEG C, reaction pressure 20MPa, hydrogen oil
Volume ratio is 1300, air speed 0.5h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 380 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end, and return it to conduct in step (1) are discharged outside bottom of towe
Solvent naphtha 1.
Through experimental test, the conversion ratio of biomass is 99%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 78%, and residue content is 0.07wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
83wt%, organic hydrogen content 16wt%, organic oxygen content are 1wt%.
Embodiment 6
A kind of method of biomass liquefying production light oil is present embodiments provided, is comprised the following steps：
(1) Oil Residue is sent into drying machine the dry 3.5h at 95 DEG C and is less than 2wt% to water content, be then fed into super
Atomizer just crush, and the median after just crushing is 300 μm, and the Oil Residue after first crush then is sent into press strip
Extrusion forming is compressed under 60 DEG C of temperature, the pressure of 5MPa in machine, separating twice processing is carried out afterwards, through separating twice
The Oil Residue particle 2 that median is 50 μm is obtained afterwards, and the heap density of the Oil Residue particle 2 is 1589kg/m3；
It is 100 in mass ratio by above-mentioned Oil Residue particle 2, amorphous Fe oxides 3 and sulphur 1：4.5：0.1 in biomass
Mixture is uniformly mixed so as to obtain in serum pot 4, and feeds the mixture into carbolineum the mixing at 30 DEG C, then carries out scattered slurrying, shape
Into the biomass slurry that biomass content is 59wt%, the viscosity of the slurries is 301mPa ﹒ s (50 DEG C), spare；
(2) biomass slurry and added hydrogen 26 in suspended-bed reactor 5 are subjected to the first liquefaction reaction, collected
First reaction product, wherein, the parameter of the first liquefaction reaction is as follows：Reaction temperature is 450 DEG C, reaction pressure 21MPa, gas-liquid
Than being 2h for the air speed of 1100L/kg, the biomass slurry-1；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction in internal recycle suspension bed reactor 6, received
Collect the second reaction product, i.e. floating bed hydrogenation product 7, wherein, the parameter of the second liquefaction reaction is as follows：Reaction temperature for 480 DEG C,
Reaction pressure is 16MPa, gas liquid ratio 1600L/kg, the air speed of the biomass slurry are 0.3h-1；
(4) second reaction product is subjected to first time separation in the high pressure hot separator 8 under pressure is 15MPa,
Collect light component 9 and heavy constituent 10；
(5) by heavy constituent 10 after high-pressure-difference pressure reducing valve 11 is depressured into vacuum tower 12, in temperature be 400 DEG C, pressure
To be evaporated under reduced pressure under 5kPa, light fraction, i.e. survey line distillate 14 in overhead oil 13 and vacuum tower 12 are collected, is surveyed
Line distillate 14, which is back in step (1), is used as solvent naphtha 1, and recycles residue 25 from the bottom of towe of vacuum tower 12；
(6) light component 9 and overhead oil 13 are mixed into fixed bed hydrogenation reactor 16 and carry out hydrogenation reaction, collected solid
Fixed bed hydrogenation products 16, the condition of hydrogenation reaction therein are as follows：Reaction temperature is 430 DEG C, reaction pressure 19MPa, hydrogen oil
Volume ratio is 1200, air speed 0.9h-1；
(7) fixed bed hydrogenation product 16 separates for second into progress in separator 17, and isolated hydrogen 18, gas phase are light
Hydrocarbon 19 and liquid phase, i.e. distillate 20, hydrogen 18 can be used for above-mentioned first liquefaction reaction, the second liquefaction reaction and hydrogenation reaction
In, gas phase lighter hydrocarbons 19 recycle；
(8) distillate 20 enters in fractionating column 21, and is fractionated at 390 DEG C, naphtha is isolated from tower top, from tower
Middle and upper part isolate diesel oil, bottom of towe oil 24, i.e. heavy end, and return it to conduct in step (1) are discharged outside bottom of towe
Solvent naphtha 1.
Through experimental test, the conversion ratio of biomass is 96%, wherein, lightweight biomass oil of the boiling range below 520 DEG C is received
Rate is 73%, and residue content is 0.09wt% in lightweight bio oil；
Gained lightweight biomass oil is subjected to elemental analysis, it is known that, organic carbon content is in the lightweight biomass oil
88wt%, organic hydrogen content 10.5wt%, organic oxygen content are 1.5wt%.
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 (14)
1. a kind of method of biomass liquefying production light oil, comprises the following steps：
(1) biomass, hydrogenation catalyst, vulcanizing agent and solvent naphtha are mixed, biomass slurry is made；
(2) biomass slurry and hydrogen are subjected to the first liquefaction reaction, collect the first reaction product；
(3) first reaction product and hydrogen are subjected to the second liquefaction reaction, collect the second reaction product；
(4) first time separation is carried out to second reaction product, collects light component and heavy constituent；
(5) heavy constituent is evaporated under reduced pressure, collects light fraction；
(6) light component and the light fraction are mixed and carries out hydrogenation reaction, collect hydrogenation products；
(7) hydrogenation products are fractionated, obtain light oil；
In step (1), the biomass is vegetable oil residue, and the preparation steps of the biomass slurry are, by vegetable oil residue successively
Be dried, just crush, compress and separating twice, then mixture is mixed to get with the hydrogenation catalyst, vulcanizing agent, by institute
It states mixture and adds in and grind slurrying into the solvent naphtha, obtain the slurries that vegetable oil residue concentration is 50-65wt%.
2. according to the method described in claim 1, it is characterized in that, in the preparation steps of the biomass slurry, by the plant
The pressure that the object dregs of fat are compressed is 3-5MPa, temperature is 40-60 DEG C.
3. method according to claim 1 or 2, which is characterized in that in the preparation steps of the slurries,
The drying temperature of the vegetable oil residue is 80-110 DEG C, time 2-6h, and the dried moisture content of vegetable oil residue is low
In 2wt%；Median particle size is 100-300 μm after just crushing；Median particle size is 30-50 μm, after separating twice after separating twice
Heap density is 1500-1600kg/m3。
4. method according to any one of claim 1-3, which is characterized in that the solvent naphtha is waste oils and fats
One or more in fat, waste mineral oil, mineral oil or distillate.
5. according to the described method of any one of claim 1-4, which is characterized in that in the step (1), the biomass and
The hydrogenation catalyst, the mass ratio of the vulcanizing agent are 100：(0.5~5)：(0.1~0.4).
6. according to the method any one of claim 1-5, which is characterized in that in the step (2), first liquefaction
The reaction condition of reaction is as follows：
Reaction temperature is 380-460 DEG C；
Reaction pressure is 15-25MPa；
Gas liquid ratio is 800-1600L/kg；
The air speed of the biomass slurry is 0.4-2h-1。
7. according to the method any one of claim 1-6, which is characterized in that in the step (3), second liquefaction
The reaction condition of reaction is as follows：
Reaction temperature is 390-490 DEG C；
Reaction pressure is 15-25MPa；
Gas liquid ratio is 700-1600L/kg；
The air speed of the biomass slurry is 0.3-2h-1。
8. according to the described method of any one of claim 1-7, which is characterized in that in the step (5), the vacuum distillation
Temperature for 320-400 DEG C, pressure 5-20kPa.
9. according to the method any one of claim 1-8, which is characterized in that in the step (6), the hydrogenation reaction
Reaction condition it is as follows：
Reaction temperature is 400-470 DEG C；
Reaction pressure is 15-20MPa；
Hydrogen to oil volume ratio is 800-1500；
Air speed is 0.4-2h-1。
10. according to the method any one of claim 1-9, which is characterized in that in the step (8), the fractionation
Temperature is 340-390 DEG C.
11. according to the method any one of claim 1-10, which is characterized in that further include and collect the vacuum distillation step
Gained distillate and fractionating step gained heavy end after rapid, and using the distillate and the heavy end as described in
The step of solvent naphtha.
12. according to the method any one of claim 1-11, which is characterized in that the hydrogenation products are carrying out being fractionated it
Before, the step of further including and the hydrogenation products carried out with second of separation, respectively obtain hydrogen, gas phase lighter hydrocarbons and liquid phase, wherein
Hydrogen cycle in first liquefaction reaction, second liquefaction reaction and the hydrogenation reaction.
13. according to the method any one of claim 1-12, which is characterized in that in the step (1), the mixing step
Rapid temperature is 25-180 DEG C.
14. according to the method any one of claim 1-13, which is characterized in that the hydrogenation catalyst is following catalysis
At least one of agent：
1) amorphous Fe oxides and/or unformed FeOOH；
2) the unformed aluminium oxide of carrying active ingredients, the active ingredient are vib metal, Section VII B metals or group VIII
At least one of oxide of metal, the content of the active ingredient is 10-25wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421658.XA CN108085041B (en) | 2017-12-25 | 2017-12-25 | Method for producing light oil by biomass liquefaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711421658.XA CN108085041B (en) | 2017-12-25 | 2017-12-25 | Method for producing light oil by biomass liquefaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108085041A true CN108085041A (en) | 2018-05-29 |
| CN108085041B CN108085041B (en) | 2020-07-17 |
Family
ID=62179046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711421658.XA Active CN108085041B (en) | 2017-12-25 | 2017-12-25 | Method for producing light oil by biomass liquefaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108085041B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN104927948A (en) * | 2015-06-16 | 2015-09-23 | 神华集团有限责任公司 | Water coal slurry preparing method |
| CN105733693A (en) * | 2016-03-21 | 2016-07-06 | 江苏大学 | Method for preparing biological oil by co-liquefaction of algae and lignocellulosic biomass |
-
2017
- 2017-12-25 CN CN201711421658.XA patent/CN108085041B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN104927948A (en) * | 2015-06-16 | 2015-09-23 | 神华集团有限责任公司 | Water coal slurry preparing method |
| CN105733693A (en) * | 2016-03-21 | 2016-07-06 | 江苏大学 | Method for preparing biological oil by co-liquefaction of algae and lignocellulosic biomass |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108085041B (en) | 2020-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Hydrothermal liquefaction of Chlorella vulgaris and Nannochloropsis gaditana in a continuous stirred tank reactor and hydrotreating of biocrude by nickel catalysts | |
| CN102127462A (en) | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps | |
| CN103265971A (en) | Heterogeneous coal tar suspension bed hydrogenation method | |
| CN110028985A (en) | A kind of method that biomass pyrolysis liquid prepares high-quality fuel oil and/or industrial chemicals | |
| CN108085037B (en) | Method for producing light oil by biomass liquefaction | |
| CN108085038B (en) | Method for directly liquefying biomass | |
| CN108117882B (en) | A method of processing waste plastics and cellulose | |
| CN108285806B (en) | Method for directly liquefying biomass | |
| CN108085041A (en) | A kind of method of biomass liquefying production light oil | |
| CN108277037A (en) | A kind of method of coal and biomass liquefying production light oil | |
| CN108315039A (en) | A kind of method of biomass liquefying production light oil | |
| CN108273558B (en) | Catalytic cracking catalyst and its preparation method and application | |
| CN108355711B (en) | A kind of catalytic cracking catalyst and its preparation method and application | |
| CN108085042A (en) | A kind of one kettle way liquefaction process of biomass | |
| CN108085040B (en) | Method for directly liquefying biomass | |
| CN108329514B (en) | Method for processing waste plastic and cellulose | |
| CN108219818A (en) | A kind of one kettle way liquefaction process of biomass | |
| CN108264919B (en) | Process for producing fuel oil and chemical raw materials by using biomass | |
| CN108264917B (en) | Hydrolysis hydrogenation process of biomass | |
| CN106635195B (en) | A kind of processing method that biomass refines product altogether | |
| CN108251146B (en) | A kind of method of waste plastics and cellulose coprocessing | |
| CN108203590B (en) | A kind of method of coal and biomass direct liquefaction | |
| CN108219815B (en) | The method for the treatment of of waste plastics and cellulose | |
| CN108239552B (en) | A kind of method for the treatment of of waste plastics and cellulose | |
| CN213506760U (en) | Suspension bed enhanced reaction system for direct coal liquefaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100044 Beijing Haidian District Xizhimen North Street a 43 Jinyun building A block 9. Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |