CN116286067B - Long-period stable operation method and device for producing gasoline and diesel oil by biomass - Google Patents
Long-period stable operation method and device for producing gasoline and diesel oil by biomass Download PDFInfo
- Publication number
- CN116286067B CN116286067B CN202310049602.5A CN202310049602A CN116286067B CN 116286067 B CN116286067 B CN 116286067B CN 202310049602 A CN202310049602 A CN 202310049602A CN 116286067 B CN116286067 B CN 116286067B
- Authority
- CN
- China
- Prior art keywords
- oil
- gas
- hydrogen
- reactor
- pyrolysis
- 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.)
- Active
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 116
- 239000003502 gasoline Substances 0.000 title claims abstract description 94
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000000197 pyrolysis Methods 0.000 claims abstract description 167
- 239000007788 liquid Substances 0.000 claims abstract description 160
- 239000003054 catalyst Substances 0.000 claims abstract description 143
- 239000003921 oil Substances 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000012075 bio-oil Substances 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 38
- 239000002101 nanobubble Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000006872 improvement Effects 0.000 claims abstract description 16
- 230000009471 action Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims description 200
- 229910052739 hydrogen Inorganic materials 0.000 claims description 200
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 193
- 239000007789 gas Substances 0.000 claims description 142
- 239000002296 pyrolytic carbon Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 38
- 230000004913 activation Effects 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 30
- 230000008929 regeneration Effects 0.000 claims description 26
- 238000011069 regeneration method Methods 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 19
- 238000011065 in-situ storage Methods 0.000 claims description 16
- 230000000171 quenching effect Effects 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000004087 circulation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 8
- 239000013520 petroleum-based product Substances 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000004939 coking Methods 0.000 description 12
- 238000012546 transfer Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000010724 circulating oil Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- ZWRLWJAFBLTMSQ-UHFFFAOYSA-N Docosa-7,10,14-triensaeure Natural products C1C(C)=C2CC(C)(C)CC2C(O)C2=COC=C21 ZWRLWJAFBLTMSQ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- YKASHPSKFYVZRC-UHFFFAOYSA-M furan-2-ylmethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CO1 YKASHPSKFYVZRC-UHFFFAOYSA-M 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- -1 oxygen furanol Chemical compound 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
Abstract
The invention discloses a long-period stable operation method and a device for producing gasoline and diesel by biomass, wherein the device comprises a biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I), a bio-oil hydrodeoxygenation deoxidization liquid production system (II) and a deoxidization liquid hydrogenation quality improvement gasoline and diesel production system (III); the biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) is used for carrying out low-temperature, micro-positive pressure and second-level non-phase-change drying pretreatment on biomass, and is coupled with rapid pyrolysis reaction conversion to obtain bio-oil with low water content and oxygen content; the biological oil hydrodeoxygenation deoxidization liquid system (II) is used for carrying out hydrodeoxygenation reaction on the biological oil under the action of micro-nano bubbles and a catalyst to obtain deoxidization liquid; the deoxidization liquid hydrogenation quality-improving gasoline and diesel oil preparing system (III) is used for carrying out hydrogenation quality-improving reaction on the deoxidization liquid to obtain gasoline and diesel oil components. The invention can reduce the energy consumption of the whole process by 30%, improve the total yield of gasoline and diesel by 50%, and continuously and stably operate the device; directly converts the biomass into high-quality gasoline and diesel oil which can be directly used to replace petroleum-based products, thereby realizing carbon emission reduction.
Description
Technical Field
The invention belongs to the technical field of resource carbon neutralization, relates to the emerging field of biomass zero-carbon fuel, and particularly relates to a long-period stable operation method and device for producing gasoline and diesel from biomass.
Background
Biomass is a medium for storing solar energy, has zero carbon property, and can replace petroleum to produce gasoline and diesel oil, and the carbon emission reduction in heavy carbon fields such as booster agriculture, petrochemical industry, traffic and the like. The waste biomass yield in China is about 35 hundred million tons/year, the development potential is large, the recycling utilization rate is low, and the conventional incineration, stacking and other disposal modes are accompanied by serious secondary pollution and large carbon dioxide emission, and the dual pressure of pollution reduction and carbon reduction is faced.
Biomass can be converted into bio-oil with higher energy density by a fast pyrolysis technology. The biomass fast pyrolysis technology is to take lignocellulose biomass as a raw material to be rapidly heated and decomposed under anaerobic or anaerobic conditions, and convert the biomass with low energy density into liquid fuel with high energy density, so that the biomass is easy to collect, transport and store. The fast pyrolysis reactor comprises an ablative pyrolysis reactor, a rotary cone reactor, a fluidized bed pyrolysis reactor and the like. The fluidized bed pyrolysis reactor has the advantages of small carrier gas demand, high yield, low operation cost, extremely short gas-solid or solid-solid residence time, quick reaction, flexible adjustment of solid-gas ratio or solid-solid ratio and the like in a fast pyrolysis system, however, biomass which is not subjected to drying pretreatment (the water content is about 30% -40%) enters the fast pyrolysis reaction, and the excessive water content and oxygen content of the product can cause coking to block a pipeline. Therefore, the fast pyrolysis reactor has high requirements for biomass pretreatment. Most of biomass in China adopts high-temperature hot gas as a heating medium for conventional drying pretreatment, but the conventional drying method relies on phase change evaporation of water for treatment, and has the advantages of long time, high energy consumption, high heat dissipation loss, large occupied area and poor economic benefit, so that the development scale of biomass drying-pyrolysis technology is restricted.
The bio-oil obtained by the rapid pyrolysis conversion of biomass contains a large amount of substances such as acid, aldehyde, alcohol, ketone and phenol, and has the problems of high water content (about 25-60 wt%), high oxygen content (30-55 wt%), low heat value (17 MJ/kg), strong polarity, high viscosity, strong corrosiveness, poor stability and the like, is difficult to mix with petroleum-based products, is difficult to directly replace fossil-based gasoline and diesel oil, and needs further deoxidization and quality improvement. Bio-oil hydrodeoxygenation technology is considered as one of the effective methods for achieving bio-oil quality enhancement: the biological oil is subjected to hydrogenolysis reaction in the presence of a catalyst and hydrogen, oxygen can be removed in the form of water, carbon dioxide and the like, so that the biological oil with high oxygen content is converted into hydrocarbon fuel with low oxygen content, but the technology still has a plurality of problems in hydrogenation reaction devices and treatment systems. Biological oil hydrodeoxygenation studies have been conducted primarily around fluidized bed hydrodeoxygenation reactors and fixed bed hydrodeoxygenation reactors. The national laboratory in the northwest of the Pacific of the United states developed more work on hydrodeoxygenation device research, research results suggest that the fixed bed hydrogenation upgrading reactor has extremely high deoxidation efficiency, easily controlled reaction conditions and great application potential, however, the fixed bed cannot strengthen the mass transfer rate of biological oil, so that the easily coked components are condensed and coked to block the bed layer, and the device cannot realize long-period operation (Biomass and Bioenergy,2019,125,151-168.). Therefore, the Chinese patent No. 110028985A discloses a method for preparing high-quality fuel oil and/or chemical raw materials from biomass biological oil, which uses a fluidized bed hydrodeoxygenation reactor, and the biological oil and a catalyst are in a fully mixed flow state in the reactor, so that condensation and coking of the biological oil can be alleviated to a certain extent. However, bio-oil has poor hydrogen-dissolving capacity, so that the demand of hydrogen supply agent and circulating oil is increased, the bio-oil is difficult to be rapidly dispersed to generate catalytic hydrogenation reaction after entering the reactor, and the inlet of the reactor is blocked. Therefore, it is highly desirable to provide a micro-nano bubble generating device which is helpful for dispersing biological oil, avoiding coking of the biological oil at the inlet of the reactor, and reducing the use amount of hydrogen donor and circulating oil. On the other hand, the core of the hydrodeoxygenation of biological oil is to construct a high-activity catalyst, and the main operation cost also comprises the preparation cost and the operation loss of the catalyst, so that the on-line activation and regeneration of the catalyst are important in the industrial production process. Aiming at the bottleneck of the biological oil hydrodeoxygenation technology, a fluidized bed hydrodeoxygenation reactor with high biological oil dispersion degree and high mass transfer rate and capable of realizing on-line activation of a catalyst is needed.
The oxygen content of the biological oil is reduced to about 10% after the hydrodeoxygenation reaction of the fluidized bed, so that deoxidized liquid with stable properties is obtained, but the deoxidized liquid is still difficult to directly replace gasoline and diesel oil with extremely low oxygen content, and the complete conversion from the biological oil to the gasoline and diesel oil is realized. Therefore, a two-step or multi-step reaction system is required to be constructed for producing gasoline and diesel oil by using the biological oil, and a biological oil fluidized bed hydrodeoxygenation reaction-deoxidization liquid fixed bed hydrogenation upgrading reaction system is constructed by utilizing the technical characteristic of high deoxidization efficiency of a fixed bed reactor, so that the problem of incomplete deoxidization caused by independently using the fluidized bed hydrodeoxygenation reactor is solved, and the gasoline and diesel oil with extremely low oxygen content is obtained. However, the deoxidizing liquid has strong heat release in the deep hydrogenation process in the fixed bed hydrogenation upgrading reactor, the temperature of the device is easy to run away, the phenomenon of 'flying temperature' occurs, the phenomena of sintering, structural collapse, inactivation and the like of the active components of the catalyst metal are caused, and even the serious safety risk is caused. Chinese patent No. CN113840654a discloses a method for preparing biofuel from biomass by hydrodeoxygenation catalyst and fixed bed series catalytic reactor. The invention relates to a fixed bed series catalytic modification method and a reactor, wherein the upstream of a fixed bed comprises a carbon-carbon coupling catalyst, and the downstream comprises a hydrodeoxygenation catalyst, so that the conversion of light oxygen-containing organic matters and the generation of high aromatic hydrocarbon components are realized, and the method has the potential of partially replacing aviation fuel. In the invention, the bio-oil directly enters a fixed bed device to generate series catalytic reaction, and compared with the single-stage reaction, the catalyst has more serious coking deactivation phenomenon and the possibility of 'flying temperature' of the device, so that the industrial application is difficult to realize. The invention discloses a process for producing biodiesel by using biological raw oil, which adopts a suspension bed reactor to carry out primary cracking on the biological oil, reduces the oxygen content of the biological raw oil, and then enters a fixed bed device to carry out deep hydrogenation, thereby effectively inhibiting the fly temperature. However, the system is a combination of two devices, has higher cost and more complex operation, and does not solve the technical problem that the deoxidized liquid with high oxygen content enters a fixed bed and is easy to fly. Therefore, it is necessary to invent a fixed bed hydrogenation quality-improving reactor for inhibiting the fly temperature to realize the safe, stable and deep hydrogenation quality improvement of the deoxidized liquid. The Chinese patent No. 114958399A discloses a pressurized biomass drying-pyrolysis and energy recovery device, which takes biomass as a raw material to carry out drying-pyrolysis conversion to obtain bio-oil, wherein the temperature of a heating medium is higher than 100 ℃, and the pressure is between 0.1 and 10Mpa, and belongs to phase-change drying pretreatment, the pretreatment energy consumption is higher, and the economical efficiency is poor. The Chinese patent No. 112442404A adopts different biomass raw materials to prepare pyrolysis solid and liquid after being dried, mixed and pyrolyzed independently, and biomass semicoke is prepared by mixing, pressing and forming. The method needs to carry out zoned hot air drying aiming at different biomass, has high manual sorting cost, large occupied area, long time period and high energy consumption, and the economic benefit of biomass semicoke is far lower than that of gasoline and diesel. Chinese patent No. 104498065A discloses a high-efficiency biomass pyrolysis and purification process, which is characterized by long time (> 10 min), high temperature (> 100 ℃) and high energy consumption by heating in a drying oven.
The Chinese patent No. 104845667A discloses a deoxidized biomass oil hydrogenation device, which adopts a pre-hydrogenation reactor, a heating furnace and a main hydrogenation reactor for high-temperature hydrogenation, and has stable operation, but does not consider the problems of raw material dispersion and catalyst on-line activation at the inlet of the reactor, and has an extended operation period. Chinese patent application No. 109967003A and No. 110102227A both disclose a biomass bio-oil hydrogenation reactor, but the reactor has the technical problems of uneven gas-liquid distribution of the primary distributor of the internal components, large operation fluctuation, low gas-liquid mass transfer rate and the like. The bio-oil can not be rapidly dispersed in the process of entering the reactor to react with the catalyst to generate hydrodeoxygenation reaction, thus causing inlet coking problem. Chinese patent 111004647A discloses a heavy oil hydrogenation upgrading process for producing hydrogen by coupling pyrolysis and reforming, which is used for regenerating a single fixed bed catalyst, and a plurality of reactors are connected in series for realizing continuous operation by suspending the reaction and alternately working, so that the device cost is high.
Chinese patent No. CN110511776a discloses a device and method for producing biodiesel by biomass pyrolysis, which comprises a biomass pyrolysis reactor, a modifying reactor and a catalyst regenerator, wherein the biomass pyrolysis reactor is disposed inside the catalyst regenerator. The invention utilizes the coke generated in the pyrolysis and modification processes to supply heat, thereby reducing energy consumption. However, the invention can lead the biological oil with higher oxygen content to directly enter the modifying reactor, which can lead to the problems of coking and inactivation of the catalyst, temperature runaway of the device, and the like. Chinese patent No. CN109628143a discloses a method for producing gasoline and diesel oil by co-refining biomass oil and straight-run wax oil by fast pyrolysis. The biomass oil is mixed with straight-run wax oil after light hydrogenation and enters an existing catalytic cracking device to be co-refined to obtain gasoline and diesel oil, but the technology for preparing the gasoline and diesel oil by completely converting biomass is not yet opened up by adding a large amount of straight-run wax oil.
The Chinese patent No. 103992823A discloses a method and a system for synthesizing methane and gasoline and diesel oil by using low-rank coal and biomass as raw materials, wherein the structure breaking of the low-rank coal and biomass is converted into synthetic gas by adopting a gasification coupling Fischer-Tropsch synthesis technology, so that the energy consumption is extremely high and the economic benefit is poor. Chinese patent No. 104560225A discloses a method for preparing high-quality fuel oil from biomass, which comprises the steps of carrying out microwave hydrolysis treatment, microwave dehydration treatment and microwave pyrolysis on biomass to obtain biological oil, and carrying out etherification reaction on the biological oil to obtain fuel oil rich in furanol ether, wherein the product is fuel containing oxygen furanol ether and the like, and cannot be directly used as vehicle fuel to replace gasoline and diesel.
In 2007, the U.S. department of energy organized multiple national laboratories and universities such as the national laboratory of iowa, the national laboratory of oak, the national laboratory of tribute, the national laboratory of pacific, the national renewable energy laboratory, the university of darlinger, subsidized about 3 billion dollars, developed a study of "biomass fast pyrolysis + hydro-upgrading gasoline and diesel" for 10 years, built a 50kg/h biomass fast pyrolysis and 1kg/h hydro-upgrading gasoline and diesel pilot plant, but it could not meet the long period steady operation requirements of major chemical plant, did not possess the economy of commercial test production, engineering interruption. In summary, although many methods and devices for producing gasoline and diesel by biomass drying-pyrolysis, bio-oil hydrodeoxygenation, bio-oil hydrogenation upgrading and biomass fast pyrolysis combined with hydrogenation upgrading have been presented at present, a complete set of treatment methods and devices for producing gasoline and diesel by biomass with long-period stable operation have not been found.
The long-period stable operation method and the device for producing the gasoline and the diesel by the biomass can effectively solve the technical problems in the single-step treatment process or the system treatment process of the existing biomass production gasoline and the diesel, provide a scheme with low energy consumption, high efficiency and stability, break the technical barrier of producing the gasoline and the diesel by the biomass and realize industrialized large-scale application.
Disclosure of Invention
The invention aims to solve the problems that the running cost of gasoline and diesel oil produced by biomass is high and long-period stable running is difficult to realize, and provides a long-period stable running method and device for producing gasoline and diesel oil by biomass.
In order to achieve the above purpose, the present invention is realized by adopting the following technical scheme.
The long-period stable operation method for producing gasoline and diesel oil by using biomass provided by the invention comprises the following steps:
a) Biomass is subjected to low-temperature, micro-positive pressure, second-level non-phase-change drying and rapid pyrolysis conversion to obtain low-water-content and low-oxygen-content biological oil;
b) The biological oil from the step A) and the injected hydrogen are subjected to hydrodeoxygenation reaction, the biological oil flows and shears to enable the hydrogen to be crushed into micro-nano hydrogen bubbles, and then hydrodeoxygenation reaction is carried out under the action of a catalyst to obtain deoxidized liquid;
C) The catalyst after the given period of the step B) is regenerated through on-line activation, and the regenerated catalyst is continuously added into the step B) to be used as a reaction catalyst;
d) The deoxidized liquid from the step B) is subjected to hydrogenation upgrading reaction in a cold hydrogen environment to obtain gasoline and diesel components;
e) The pyrolysis gas and pyrolytic carbon combustion exotherm from step a) provides heat for step B) and step D);
f) The heat generated by the reaction of the step B) and the step D) is used for the non-phase-change drying and the fast pyrolysis preheating of the biomass in the step A) through air heat exchange;
g) After the residual waste hydrogen from the step B) and the step D) is purified, the hydrogen is continuously returned to the step B) and the step D) to be used as circulating hydrogen, and the waste gas after the hydrogen purification is returned to the step A) to be used as a supplementary gas source for the fast pyrolysis reaction.
In the step A), non-phase-change drying is carried out under the conditions of 10-30 seconds, 30-90 ℃ and air flow speed of 3-8m/s and micro positive pressure of 2-8KPa, fast pyrolysis is carried out at 400-700 ℃, the heating rate is 1000K/s-10000K/s, the cooling rate of pyrolysis gas is carried out within 200-1000K/s, and the temperature of flue gas generated by pyrolysis treatment is 500-800 ℃. Part of pyrolysis gas generated by pyrolysis is supplied to hydrodeoxygenation and hydrogenation upgrading reactions to heat, and the other part is used for regeneration of a heat carrier. The water content of the biological oil obtained in the step is 10-30%, the oxygen content is 30-50%, and the viscosity is 20-100cp. The ratio of the pyrolytic carbon to the heat carrier in the pyrolysis process is 1/30-1/60, and the gas speed of the solid-solid separation and the lifting of the pyrolytic carbon and the heat carrier is 2.5-3m/s; the separation efficiency of the obtained pyrolytic carbon is 80-99%, and the separation efficiency of the heat carrier is 75-99%.
In the step B), the hydrodeoxygenation reaction temperature is 200-400 ℃, the pressure is 8-15MPa, and the reaction volume space velocity is 0.6-2.0h -1 The ratio of hydrogen to oil is 400:1-1000:1, the water content in the obtained low-viscosity deoxidizing liquid is 0.001-5%, the oxygen content is 5-10%, and the viscosity is 1-2cp. The micro-nano bubbles are bubbles with the size of 200-10000 microns formed by crushing a hydrogen gas phase under the shearing action of a bio-oil liquid phase, so that the effect of uniformly mixing the gas phase and the liquid phase in the axial direction is achieved, the proportion of the liquid phase sucked into the gas phase can reach 20% -80%, emulsified bio-oil is obtained, the hydrogen dissolving capacity of raw materials is improved, the requirement of circulating oil is reduced, the traditional liquid-liquid mixed phase feeding system can be replaced, and the bio-oil is prevented from coking at the inlet of the reactor. The catalyst is spherical particles (such as carbon-based, silicon-based and aluminum-based spherical particles) with the diameter of 0.2-5mm and the length-diameter ratio of 1-5, and the active metal loaded on the catalyst is transition metal elements from IIIB group to IIB group in the periodic table of elements, or/and alloy formed by any two or more of the transition metal elements. The loading of the catalyst particles accounts for 20-85% of the volume of the fluidized bed hydrogenation reactor used in the hydrodeoxygenation reaction.
In the step C), the catalyst online activation regeneration can be in-situ online rotational flow regeneration and/or external rotational flow regeneration, so that the service life of the catalyst is prolonged.
Further, the in-situ on-line rotational flow regeneration of the catalyst is that the catalyst performs rotational flow movement in the fluidized bed hydrodeoxygenation reactor, the ordered rotation and revolution force generated by rotational flow realizes the separation of the catalyst and the liquid phase in the pore canal, the catalyst particles are trapped in the reactor, and the clarified liquid phase without the catalyst particles is discharged out of the reactor. The revolution speed of the rotational flow regenerated catalyst is 0.3-1.3rad/s, the self-transmission speed is 4.0-20.0rad/s, and the catalyst regeneration efficiency is 80-99%.
Further, the on-line rotational flow regeneration outside the catalyst device is that a rotational flow regeneration device is arranged outside the fluidized bed hydrodeoxygenation reactor, the catalyst is discharged outside on line and enters the regeneration device, rotational flow regeneration of the catalyst is realized under the condition that an organic solvent exists, the organic solvent is further removed by rotational flow, dry catalyst particles are obtained, hydrogen reduction regeneration is carried out on the catalyst with high separation activity, and the obtained regenerated catalyst is added into the biomass bio-oil fluidized bed reactor on line for recycling. The organic solvent regenerated by the on-line rotational flow outside the catalyst comprises methanol, dodecane, n-hexane and the like, the rotational removal of the organic solvent is carried out by taking hydrogen at 150-350 ℃ as carrier gas and utilizing centrifugal force generated by rotational flow rotation, the activity classification is realized by sine-cosine waveform pulsating hydrogen flow and utilizing density difference of different active catalysts, the catalysts are reduced under the hot hydrogen at 150-350 ℃ and the regeneration time is 60-180 minutes.
In the step D), the deoxidizing liquid is mixed with part of hydrogen provided by a cold hydrogen box so as to reduce the material temperature, inhibit the device from flying to the temperature, avoid rapid coking and deactivation of the catalyst and prolong the operation period of the device. The deoxidized liquid is subjected to hydrogenation and upgrading reaction in a continuous cooling environment of a cold hydrogen box, the temperature of the deoxidized liquid hydrogenation and upgrading reaction is 150-450 ℃, the pressure is 5-20MPa, and the space velocity of the reaction volume is 1.0-4.0h -1 The hydrogen-oil ratio is 400:1-1200:1. The catalyst is a silicon-based and aluminum-based carrier, the macroscopic shape of the catalyst comprises clover, column and particle, and the active metal loaded on the catalyst is transition metal elements from IIIB to IIB in the periodic table of elements or/and alloy formed by any two or more of the transition metal elements. The gasoline and diesel oil components prepared by the method can meet the national fifth standard.
The hydrodeoxygenation reaction in the step B) and the hydro-upgrading reaction in the step D) can be in a single-stage mode or in a two-stage or multi-stage serial mode.
The invention further provides a long-period stable operation device for producing gasoline and diesel by biomass based on the long-period stable operation method for producing gasoline and diesel by biomass, which comprises the steps of adding waste biomass into a biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I) for non-phase-change drying pretreatment and fast pyrolysis reaction; the obtained biological oil directly enters a fluidized bed hydrodeoxygenation reactor, and is coupled with a micro-nano bubble reinforced mass transfer heat transfer generator and an in-device/out-device on-line cyclone regenerator to carry out hydrodeoxygenation reaction and catalyst regeneration activation treatment; the deoxidized liquid is separated from oil and water, oil phase is taken to enter a fixed bed hydrogenation quality-improving reactor for inhibiting the fly temperature, and is mixed with low-temperature hydrogen, and after the reaction is completed, the product of gasoline and diesel oil which can directly enter the traffic field is obtained through fractionation.
Based on the analysis, the long-period stable operation device for producing gasoline and diesel by biomass provided by the invention comprises a biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I), a bio-oil hydrodeoxygenation deoxidization liquid production system (II) and a deoxidization liquid hydrodeoxygenation quality improvement gasoline and diesel production system (III):
the biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) is used for carrying out low-temperature, micro-positive pressure and second-level non-phase-change drying pretreatment on biomass, and is coupled with rapid pyrolysis reaction to convert the biomass into bio-oil with low water content and low oxygen content;
the system (II) for preparing the deoxidizing liquid by hydrodeoxygenation of the biological oil is used for carrying out hydrodeoxygenation reaction on the biological oil under the action of micro-nano bubbles and a catalyst to obtain deoxidizing liquid;
the deoxidization liquid hydrogenation quality-improving gasoline and diesel oil preparing system (III) is used for carrying out hydrogenation quality-improving reaction on the deoxidization liquid to obtain gasoline and diesel oil components.
The biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) comprises a second-level non-phase-change dryer, a fast pyrolysis reactor, a thermal state gas-solid cyclone separator, a quenching tower, a gas holder, a pyrolysis regenerator, a gas supply device, a pyrolysis carbon collection device, a bio-oil collection device and a heat exchanger; the second-level non-phase-change dryer comprises more than one cyclone; when more than two cyclones are contained, the cyclones are connected in sequence through pipelines; the rapid pyrolysis reactor comprises a communicated downstream bed pyrolysis reactor and a pyrolytic carbon and heat carrier solid-solid separator; the downer pyrolysis reactor is respectively connected with the pyrolysis regenerator and pyrolysis reaction feeding equipment; the rapid pyrolysis reactor and the pyrolysis regenerator form a thermal circulation system; the outlet of the lower part of the thermal state gas-solid cyclone separator is communicated with the pyrolytic carbon collecting device, and the upper part of the thermal state gas-solid cyclone separator is connected with the lower ends of the pyrolytic carbon and the heat carrier solid separator; the gas outlet of the quenching tower is respectively communicated with a pyrolysis regenerator, a deoxidizing liquid system (II) for preparing the biological oil through hydrodeoxygenation and a gasoline and diesel oil system (III) through deoxidizing liquid hydrogenation and quality improvement; a heat exchanger forming a cold cycle with the quench tower is arranged on a branch line of the quench tower communicated with the biological oil collecting device; the biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I) further comprises an air supply device which is used for communicating the second-level non-phase-change dryer and the pyrolysis regenerator.
Further, the pyrolytic carbon and heat carrier solid-solid separator comprises an entrained flow separator, and the entrained flow separator comprises an inner pipe and an outer pipe which are sleeved together; the upper part of the outer tube is communicated with the dust removal tank, and the outer tube is sequentially connected with the pyrolytic carbon collection tank and the heat carrier collection tank from top to bottom; the bottom of the inner tube is connected with a feed bin, and the feed bin is connected with the lower end of the downer pyrolysis reactor; the outlet of the pyrolytic carbon collection tank is connected with the upper part of the thermal state gas-solid cyclone separator; the bottoms of the inner tube and the outer tube of the entrained flow separator are respectively connected with an air compressor for providing air flow.
Further, the air supply device comprises an air supply device, a gas heat exchanger and a gas mixer; the outlet of the air supply device is respectively connected with the inlets of the gas mixer and the gas heat exchanger; the inlet of the gas heat exchanger is also communicated with the upper part of the pyrolysis regenerator; the outlet of the gas heat exchanger is respectively communicated with the inlet of the gas mixer and the lower part of the pyrolysis regenerator; the outlet of the gas mixer is communicated with a second-level non-phase-change dryer.
The biological oil hydrodeoxygenation deoxidizing liquid system (II) comprises a hydrogen supercharging device, a circulating hydrogen press, a first booster pump, a first heating furnace, a second heater, a fluidized bed hydrodeoxygenation reactor, a first gas-liquid separator, a hydrogen purification device, a first oil-water separator and a water treatment facility which are sequentially communicated; the hydrogen pressurizing device and the circulating hydrogen press are used for providing hydrogen for the fluidized bed hydrodeoxygenation reactor; the inlet of the circulating hydrogen compressor is communicated with the hydrogen pressurizing device, and external hydrogen enters the circulating hydrogen compressor after being pressurized by the hydrogen pressurizing device; the first booster pump, the first heating furnace and the second heater are used for conveying biological oil raw materials to the fluidized bed hydrodeoxygenation reactor and the fixed bed hydrogenation upgrading reactor; the inlet of the first booster pump is communicated with the biological oil collecting device, and the outlet of the first booster pump is connected with the inlet of the fluidized bed hydrodeoxygenation reactor; the oil phase outlet of the first oil-water separator is provided with a second supercharger; a first heater and a second heater are respectively arranged on two branches from the first oil-water separator; the fluidized bed hydrodeoxygenation reactor is internally or/and externally provided with a catalyst on-line activation reactor and a micro-nano bubble generator, wherein the catalyst on-line activation reactor is used for on-line activation of the catalyst in the fluidized bed hydrodeoxygenation reactor, and the micro-nano bubble generator is used for fully mixing hydrogen and biological oil; the upper end of the first gas-liquid separator is respectively connected with a circulating hydrogen compressor and a hydrogen purification device, and the circulating hydrogen is subjected to a plurality of circulations to form waste hydrogen; the hydrogen outlet of the hydrogen purification device is connected with the circulating hydrogen press, and the waste gas outlet is connected with the fast pyrolysis reactor; the lower end of the first oil-water separator is connected with a water treatment facility, the deoxidized liquid from the first oil-water separator is divided into two paths, one path is mixed with hydrogen from a circulating hydrogen press and then returns to the fluidized bed hydrodeoxygenation reactor, and the other path is mixed with hydrogen from the circulating hydrogen press and then enters a deoxidized liquid hydrogenation quality improvement gasoline and diesel oil production system (III); the upper part of the fluidized bed hydrodeoxygenation reactor is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of a gas holder, and the gas outlet is communicated with a second-level non-phase-change dryer and a gas inlet pipeline of the fast pyrolysis reactor. The biological oil obtained by the second-level non-phase-change drying-pyrolysis biological oil preparation system (I) enters a fluidized bed hydrodeoxygenation reactor, and external hydrogen is converged with the biological oil through a supercharging device and enters the fluidized bed hydrodeoxygenation reactor; and (3) carrying out gas-liquid separation and oil-water separation on a product obtained after the reaction of the fluidized bed hydrodeoxygenation reactor through a gas-liquid separator to obtain deoxidized liquid.
Further, the loading of catalyst particles is 20-85% by volume of the fluidized bed hydrogenation reactor.
Further, the oil phase outlet of the first oil-water separator is provided with a second supercharger. The two branches from the first oil-water separator are respectively provided with a first heater and a second heater, and the first heater and the second heater are used for heating the two paths of deoxidized liquid from the first oil-water separator and respectively conveying the deoxidized liquid to the fluidized bed hydrodeoxygenation reactor and the fixed bed hydrodeoxygenation quality-improving reactor.
Further, the catalyst on-line activation reactor is based on the principle of cyclone regeneration to activate and regenerate the catalyst, and the specific structure can be seen in CN110066683B, which consists of a reagent discharge tank, a cyclone activation tank, a cyclone autorotation organic solvent remover, a catalyst activity separator, a reduction regeneration tank, a reagent adding tank and a pulsating airflow generator which are sequentially connected; the pulsating gas flow generator is communicated with the rotational flow self-rotation organic solvent remover through a pipeline between the shared rotational flow activation tank and the rotational flow self-rotation organic solvent remover, a bottom flow port of the rotational flow self-rotation organic solvent remover is communicated with a catalyst inlet of the catalyst activity separator, and an overflow port of the rotational flow self-rotation organic solvent remover is communicated with a gas inlet of the catalyst activity separator; the pulsating airflow generator generates pulsating airflow with sine and cosine waveforms, and the pulsation frequency is 1.5Hz-2.5Hz.
Further, the fluidized bed hydrodeoxygenation reactor also comprises an in-situ online cyclone regenerator arranged in the fluidized bed hydrodeoxygenation reactor, and specific structure can be seen in CN109999729B. The in-situ on-line cyclone regenerator consists of a column section, a cone section connected with the column section, a cyclone guide ring arranged in the column section, a catalyst return pipe connected with the cone section, a non-return guide cone connected with the catalyst return pipe, a liquid phase overflow pipe arranged in the column section and extending out of the column section, and a liquid phase eduction pipe connected with the column section; wherein the upper end surface of the liquid phase overflow pipe is higher than the liquid level in the fluidized bed hydrodeoxygenation reactor; the in-situ on-line cyclone regenerator in the reactor can be one or a plurality of in-situ on-line cyclone regenerators which are connected in parallel.
The deoxidization liquid hydrogenation upgrading gasoline and diesel oil production system (III) comprises a fixed bed hydrogenation upgrading reactor, a second gas-liquid separator and a second oil-water separator which are sequentially communicated; the upper end of the second gas-liquid separator is respectively connected with a circulating hydrogen press and a hydrogen purification device, circulating hydrogen enters the circulating hydrogen press, and waste hydrogen formed after a plurality of cycles of the circulating hydrogen enters the hydrogen purification device; the lower end of the second oil-water separator is connected with a water treatment facility, and the oil product obtained by the second oil-water separator is a gasoline and diesel oil product; the upper part of the fixed bed hydrogenation upgrading reactor is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of a gas holder, and the gas outlet is communicated with a second-level non-phase change dryer and a gas inlet pipeline of the fast pyrolysis reactor. The deoxidized liquid obtained by the deoxidized liquid system (II) is fed into a fixed bed hydrogenation upgrading reactor for hydrogenation upgrading reaction, and the reaction product is fed into a second gas-liquid separator and a second oil-water separator to obtain gasoline and diesel oil.
Furthermore, the fixed bed hydrogenation upgrading reactor can be internally provided with a micro-nano bubble generator, and biological oil flows and shears to enable hydrogen to be crushed into micro-nano hydrogen bubbles, so that the effect of uniformly mixing gas phase and liquid phase in the axial direction is achieved; then further blending with low-temperature hydrogen to carry out hydrogenation upgrading reaction.
Furthermore, the fixed bed hydrogenation upgrading reactor also comprises a cold hydrogen box for providing low-temperature hydrogen and cooling the deoxidized liquid. The cold hydrogen box structure can be seen in CN111659320B, and comprises a cold hydrogen pipe, a liquid collecting plate, a liquid collecting pipe and a dispersing plate which are arranged on the inner wall from top to bottom along the shell of the fixed bed hydrogenation upgrading reactor; the cold hydrogen pipe is a ring pipe and is arranged close to the inner wall of the reactor shell; the liquid collecting plate is in a right circular cone shape and is positioned in an annular cavity formed by the cold hydrogen pipe, and the edge of the liquid collecting plate is positioned below the cold hydrogen pipe; the liquid collecting pipe is a circular pipe with an arc-shaped section and is arranged right below the cold hydrogen pipe; the dispersing plate is arranged below the liquid collecting pipe; the pipe wall of the cold hydrogen pipe facing the liquid collecting plate is provided with a spray hole facing the liquid collecting plate, and the pipe wall of the cold hydrogen pipe facing the liquid collecting pipe is provided with a spray hole facing the liquid collecting pipe. Fixed bed hydrogenation reactors typically provide multiple catalyst beds with a cold hydrogen box between the catalyst beds. The main functions of the cold hydrogen tank are two aspects: the hydrogen needed by the reaction is supplemented by injecting cold hydrogen, and the temperature of the reaction oil gas is reduced to ensure that the reaction is carried out at a proper temperature.
Compared with the prior art, the long-period stable operation method and device for producing gasoline and diesel by using biomass provided by the invention have the following beneficial effects:
1) The biomass is directly converted into high-quality gasoline and diesel oil which can be directly used in the traffic field, and the substitution of petroleum-based products is realized.
2) The operation cost is low, and the energy cascade utilization and the hydrogen recycling of the biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I), the bio-oil hydrodeoxygenation deoxidization liquid production system (II) and the deoxidization liquid hydrogenation quality improvement gasoline and diesel production system (III) are included.
3) The micro-nano bubbles are formed, so that the biological oil in the hydrodeoxygenation reaction is high in dispersion degree, and the coking of the inlet of the reactor is effectively inhibited; under the action of micro-nano hydrogen bubbles, the hydrogenation and quality improvement reaction temperature of the deoxidizing liquid is reduced to 20-50 ℃ and the pressure is reduced to 2-5 Mpa.
4) Through setting up cold hydrogen case, can effectively restrain the flight and alleviate catalyst coking in deoxidization liquid hydrogenation upgrading process.
5) The two-step treatment technology of hydrodeoxygenation and hydrogenation upgrading is coupled through the on-line activation of the catalyst inside/outside the catalyst device, so that the coking problem in the hydrodeoxygenation process is broken through, and the long-period stable operation of the device is realized.
6) The biomass has wide applicability, comprises all agricultural and forestry wastes and industrial organic wastes, and can ensure the source of raw materials.
Drawings
FIG. 1 is a schematic flow chart of a long-period steady operation device for producing gasoline and diesel by using biomass provided by the embodiment of the invention;
FIG. 2 is a schematic diagram of a second-order non-phase change dryer;
FIG. 3 is a schematic diagram of a fast pyrolysis reactor;
FIG. 4 is a pyrolytic carbon and heat carrier solid-solid separator;
FIG. 5 is a schematic diagram of a fixed bed hydrogenation upgrading reactor structure;
parts, parts and numbers in the figures: 1. the second-level non-phase change dryer comprises 1-1, a motor, 1-2, a screw feeder, 1-3, a temperature controller, 1-4, a fan, 1-5, a first cyclone, 1-6, a second cyclone, 2, a fast pyrolysis reactor, 2-1, pyrolysis reaction feeding equipment, 2-2, a downer pyrolysis reactor, 2-3 pyrolytic carbon and heat carrier solid separators, 2-3-1, an entrained flow separation system, 2-3-2, a bin, 2-3-3, a ball valve, 2-3-4, a pyrolytic carbon collection tank, 2-3-5, a heat carrier collection tank, 2-3-6, a dust removal tank, 2-3-7, an air compressor, 2-3-8, an air purifier, 2-3-9, a pressure reducing valve, 2-3-10, a gas flowmeter, 3, a thermal state gas solid separator, 4, a quenching tower, 5, a gas holder, 6, a pyrolysis regenerator, 7, a gas heat exchanger, 8, an air supply device, 9, a gas mixer, 10, a pyrolytic carbon collecting device, 11, a biological oil collecting device, 12, a heat exchanger, 13, a fluidized bed hydrodeoxygenation reactor, 14, a catalyst on-line activation reactor, 15, a first gas-liquid separator, 16, a first oil-water separator, 17, a fixed bed hydrogenation upgrading reactor, 17-1, an oil-gas inlet, 17-2, a hydrogen inlet, 17-3, a sampling port, 18, a second gas-liquid separator, 19, a second oil-water separator, 20, a hydrogen pressurizing device, 21, a circulating hydrogen press, 22, a first heating furnace, 23 and a second heating furnace, 24. water treatment facilities 25, hydrogen purification device, 26, first booster pump, 27, second booster pump.
Detailed Description
In order to clearly and fully describe the technical solutions of the various embodiments of the invention, reference should be made to the accompanying drawings, it is apparent that the described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The long-period stable operation device for producing gasoline and diesel by biomass provided by the embodiment of the invention comprises a biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I) as shown in figure 1; a deoxidizing liquid system (II) for preparing the deoxidizing liquid by hydrodeoxygenation of the biological oil; and (3) a deoxidizing liquid hydrogenation quality improvement gasoline and diesel oil production system (III).
1. System (I) for preparing bio-oil by biomass second-level non-phase-change drying-pyrolysis
The biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) is used for carrying out low-temperature, micro-positive pressure and second-level non-phase-change drying pretreatment on biomass, and is coupled with rapid pyrolysis reaction conversion to obtain the bio-oil with low water content and oxygen content. The biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I) comprises a second-level non-phase-change dryer 1, a fast pyrolysis reactor 2, a thermal state gas-solid cyclone 3, a quenching tower 4, a gas holder 5, a pyrolysis regenerator 6, a gas supply device, a pyrolytic carbon collection device 10, a bio-oil collection device 11 and a heat exchanger 12.
The air supply device comprises an air supply device 8, a gas heat exchanger 7 and a gas mixer 9, wherein the outlet of the air supply device 8 is respectively connected with the inlet of the gas mixer 9 and the inlet of the gas heat exchanger 7, and the outlet of the gas heat exchanger 7 is connected with the inlet of the gas mixer 9.
The outlet of the gas mixer 9 is connected into the second-level non-phase-change dryer 1. The outlet of the second-level non-phase change dryer 1 is communicated with the upper end of the fast pyrolysis reactor 2; the outlet of the fast pyrolysis reactor is connected with the inlet of the thermal state gas-solid cyclone 3, and the outlet of the lower part of the fast pyrolysis reactor is connected with the inlet of the lower part of the pyrolysis regenerator; the outlet of the thermal state gas-solid cyclone separator 3 is connected with the inlet of the quenching tower 4, and the outlet of the lower part of the thermal state gas-solid cyclone separator 3 is communicated with the pyrolytic carbon collecting device; the upper outlet of the quenching tower 4 is communicated with the gas holder 5, the lower outlet is communicated with the biological oil collecting device 11, and the other products from the quenching tower 4 are returned to the quenching tower 4 through the heat exchanger 12; the outlet of the gas holder 5 is respectively connected with the inlet of the lower part of the pyrolysis regenerator 6, the deoxidizing liquid system (II) for preparing the bio-oil hydrodeoxygenation and the deoxidizing liquid hydrogenation quality-improving gasoline and diesel oil system (III). The upper part of the pyrolysis regenerator 6 is connected with the upper part of the fast pyrolysis reactor 2, and the inlet of the lower part of the pyrolysis regenerator 6 is also connected with the outlet of the gas heat exchanger. The fast pyrolysis reactor and the pyrolysis regenerator form a thermal circulation system.
As shown in fig. 2, the second-order non-phase-change dryer includes two cyclones (a first cyclone 1-5 and a second cyclone 1-6) connected in series. The inlet of the first cyclone 1-5 is respectively communicated with the screw feeder 1-2 and the air inlet unit. The screw feeder is driven by a motor 1-1. The air inlet unit comprises a fan 1-4 and a temperature controller 1-3; the inlet of the blower fan 1-4 is communicated with the gas mixer 9; the temperature controller 1-3 is arranged between the outlet of the fan 1-4 and the inlet of the cyclone.
As shown in fig. 3, the fast pyrolysis reactor comprises a horizontal down-bed pyrolysis reactor 2-2 and a pyrolytic carbon and heat carrier solid-solid separator 2-3 communicated with the horizontal down-bed pyrolysis reactor, wherein the down-bed pyrolysis reactor 2-2 is respectively communicated with a pyrolysis regenerator 6 and pyrolysis reaction feeding equipment 2-1; the pyrolysis reaction feeding device 2-1 is connected with the outlet of the second-level non-phase-change dryer; the pyrolysis regenerator 6 is also communicated with the lower part of the pyrolysis carbon and heat carrier solid-solid separator 2-3, and is used for lifting the heat carrier and realizing the recovery and regeneration of the heat carrier. In this example, aluminum oxide was used as the heat carrier.
As shown in fig. 4, the pyrolytic carbon and heat carrier solid-solid separator is used for efficient separation of pyrolytic carbon and heat carrier. The pyrolytic carbon and heat carrier solid-solid separator 2-3 comprises an entrained flow separator 2-3-1, a storage bin 2-3-2, a ball valve 2-3-3, a pyrolytic carbon collection tank 2-3-4, a heat carrier collection tank 2-3-5, a dust removal tank 2-3-6, an air compressor 2-3-7, an air purifier 2-3-8, a pressure reducing valve 2-3-9 and a gas flowmeter 2-3-10. The lower part of the down bed pyrolysis reactor 2-2 is connected with a feed bin 2-3-2. The entrained flow separator 2-3-1 comprises an inner pipe and an outer pipe which are sleeved together, wherein the upper parts of the inner pipe and the outer pipe are communicated with each other through openings; the upper part of the outer tube is communicated with the dust removal tank 2-3-6, and the outer tube is connected with the pyrolytic carbon collection tank 2-3-4 and the heat carrier collection tank 2-3-5 in sequence from top to bottom; the bottom of the inner tube is connected with the outlet of a feed bin 2-3-2, and the inlet of the feed bin is connected with the lower end of a downer pyrolysis reactor 2-2; the air compressor 2-3-7 is connected with the air purifier 2-3-8, the pressure reducing valve 2-3-9 and the two gas flow meters 2-3-10 in sequence; the two gas flow meters are respectively connected with the inner pipe and the outer pipe of the entrained flow separator and are used for controlling the gas flow speed entering the inner pipe and the outer pipe. The air flow speed of the inner pipe is 2.5-3m/s, and the air flow speed of the outer pipe is 1-1.4m/s.
2. System (II) for preparing deoxidized liquid by hydrodeoxygenation of biological oil
The system (II) for preparing the deoxidizing liquid by hydrodeoxygenation of the biological oil is used for carrying out hydrodeoxygenation reaction on the biological oil under the action of micro-nano bubbles and a catalyst to obtain the deoxidizing liquid. The biological oil hydrodeoxygenation deoxidizing liquid system (II) comprises a fluidized bed hydrodeoxygenation reactor 13, a first gas-liquid separator 15, a first oil-water separator 16, a hydrogen pressurizing device 20, a circulating hydrogen compressor 21, a first heating furnace 22, a second heating furnace 23, a first booster pump 26 and a second booster pump 27. The inlet of the fluidized bed hydrodeoxygenation reactor 13 is connected with the biological oil collecting device 11, and is connected with a first booster pump 26 in parallel, and the first booster inlet is connected with the biological oil outlet; the upper outlet of the fluidized bed hydrodeoxygenation reactor 13 is connected with the upper inlet of the first gas-liquid separator 15, the upper outlet of the first gas-liquid separator is respectively connected with the circulating hydrogen press 21 and the hydrogen purification device 25, and circulating hydrogen enters the circulating hydrogen press; the waste hydrogen formed by recycling the circulating hydrogen enters a hydrogen purification device, a hydrogen outlet of the hydrogen purification device 25 is connected with a circulating hydrogen press 21, and an exhaust outlet is connected with a fast pyrolysis reactor 2; the outlet of the lower part of the first oil-water separator 16 is connected with a water treatment facility 24, the deoxidized liquid from the first oil-water separator 16 is divided into two paths by a second booster pump 27, one path is mixed with hydrogen from a circulating hydrogen compressor after passing through a first heater 22 and returns to the fluidized bed hydrodeoxygenation reactor, and the other path is mixed with hydrogen from the circulating hydrogen compressor after passing through a second heater 23 and enters a fixed bed hydrogenation quality improvement reactor 17. The inlet of the circulating hydrogen compressor 21 is communicated with the hydrogen pressurizing device 20, and external hydrogen enters the circulating hydrogen compressor 21 after being pressurized by the hydrogen pressurizing device 20. The upper part of the fluidized bed hydrodeoxygenation reactor 13 is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of the gas holder 5, and heat generated by pyrolysis is used as a heat source for hydrogenation reaction through the gas holder, so that the cascade utilization of the heat is realized; the gas outlet is communicated with the gas inlet pipelines of the second-level non-phase-change dryer 1 and the fast pyrolysis reactor 2 and is used for providing preheating energy for the biomass non-phase-change reaction and the fast pyrolysis reaction, so that the gradient utilization of the energy is realized.
The catalyst used in the fluidized bed hydrodeoxygenation reactor is carbon-based spherical particles, and the active metals loaded on the catalyst are nickel and molybdenum. The loading of catalyst particles was 20% of the volume of the fluidized bed hydrogenation reactor.
In the embodiment, a catalyst on-line activation reactor is arranged outside the fluidized bed hydrodeoxygenation reactor, and an in-situ on-line cyclone regenerator and a micro-nano bubble generator are arranged inside the fluidized bed hydrodeoxygenation reactor, wherein the in-situ on-line cyclone regenerator is arranged at the top of the fluidized bed hydrodeoxygenation reactor, and the micro-nano bubble generator is arranged at the bottom of the fluidized bed hydrodeoxygenation reactor; the catalyst in the fluidized bed hydrodeoxygenation reactor is subjected to on-line activation by the catalyst on-line activation reactor, and the micro-nano bubble generator is used for fully mixing hydrogen and biological oil, so that the hydrogen dissolving capacity and the mass and heat transfer effect of the biological oil are improved.
The catalyst online activation reactor is based on a cyclone regeneration principle to activate and regenerate the catalyst, and the specific structure can be seen in CN110066683B, and the catalyst online activation reactor consists of a reagent discharge tank, a cyclone activation tank, a cyclone autorotation organic solvent remover, a catalyst activity separator, a reduction regeneration tank, a reagent adding tank and a pulsating airflow generator which are sequentially connected; the pulsating gas flow generator is communicated with the rotational flow self-rotation organic solvent remover through a pipeline between the shared rotational flow activation tank and the rotational flow self-rotation organic solvent remover, a bottom flow port of the rotational flow self-rotation organic solvent remover is communicated with a catalyst inlet of the catalyst activity separator, and an overflow port of the rotational flow self-rotation organic solvent remover is communicated with a gas inlet of the catalyst activity separator; the pulsating airflow generator generates pulsating airflow with sine and cosine waveforms, and the pulsation frequency is 1.5Hz-2.5Hz. The catalyst is discharged out on line and enters a regeneration device to realize rotational flow regeneration of the catalyst in the presence of organic solvent methanol, hydrogen at 200 ℃ is further used as carrier gas to remove the organic solvent by rotational flow through centrifugal force generated by rotational flow rotation, dry catalyst particles are obtained, activity classification is realized through sine and cosine waveform pulsating hydrogen flow and density difference of different active catalysts, the catalyst with high separation activity is subjected to hydrogen reduction regeneration at 300 ℃ for 120 minutes, and the obtained regenerated catalyst is added into a biomass bio-oil fluidized bed reactor on line for recycling.
The fluidized bed hydrodeoxygenation reactor also comprises an in-situ online cyclone regenerator arranged in the fluidized bed hydrodeoxygenation reactor, and specific structure can be seen in CN109999729B. The in-situ on-line cyclone regenerator consists of a column section, a cone section connected with the column section, a cyclone guide ring arranged in the column section, a catalyst return pipe connected with the cone section, a non-return guide cone connected with the catalyst return pipe, a liquid phase overflow pipe arranged in the column section and extending out of the column section, and a liquid phase eduction pipe connected with the column section; wherein the upper end surface of the liquid phase overflow pipe is higher than the liquid level in the fluidized bed hydrodeoxygenation reactor.
3. Deoxidizing liquid hydrogenation quality improvement gasoline and diesel oil system (III)
The deoxidizing liquid hydrogenation quality-improving gasoline and diesel oil preparing system (III) is used for carrying out hydrogenation quality-improving reaction on the deoxidizing liquid under the action of micro-nano bubbles and a catalyst to obtain gasoline and diesel oil components. The deoxidized liquid hydrogenation upgrading gasoline and diesel oil production system (III) comprises a fixed bed hydrogenation upgrading reactor 17, a second gas-liquid separator 18 and a second oil-water separator 19. The lower outlet of the fixed bed hydrogenation upgrading reactor 17 is connected with the upper inlet of the second gas-liquid separator 18, the upper outlet of the second gas-liquid separator 18 is respectively connected with the circulating hydrogen press 21 and the hydrogen purification device 25, the lower outlet is connected with the inlet of the second oil-water separator 19, the lower outlet of the second oil-water separator 19 is connected with the water treatment facility 24, and the oil phase separated by the second oil-water separator is the gasoline and diesel oil product.
In the embodiment, a micro-nano bubble generator is arranged in the top of the fixed bed hydrogenation upgrading reactor and is used for fully mixing hydrogen and biological oil, so that the hydrogen dissolving capacity and the mass and heat transfer effect of the biological oil are improved.
In this embodiment, a plurality of catalyst beds are disposed in the fixed bed hydrogenation upgrading reactor, and a cold hydrogen tank is disposed between the catalyst beds.
As shown in fig. 5, the fixed bed hydrogenation upgrading reactor 17 comprises a reactor body, an oil gas sample inlet 17-1, a hydrogen gas sample inlet 17-2 and a sampling port 17-3 which are arranged on the reactor body; the oil gas injection port 17-1 is connected with a mixture of deoxidizing liquid and hydrogen; the hydrogen gas injection port 17-2 is connected with a circulating hydrogen press 21 to introduce hydrogen gas into a cold hydrogen tank; the sampling port 17-3 is connected with the upper inlet of the second gas-liquid separator 18.
The cold hydrogen box structure can be seen in CN111659320B, and comprises a cold hydrogen pipe, a liquid collecting plate, a liquid collecting pipe and a dispersing plate which are arranged on the inner wall from top to bottom along the shell of the fixed bed hydrogenation upgrading reactor; the cold hydrogen pipe is a ring pipe and is arranged close to the inner wall of the reactor shell; the liquid collecting plate is in a right circular cone shape and is positioned in an annular cavity formed by the cold hydrogen pipe, and the edge of the liquid collecting plate is positioned below the cold hydrogen pipe; the liquid collecting pipe is a circular pipe with an arc-shaped section and is arranged right below the cold hydrogen pipe; the dispersing plate is arranged below the liquid collecting pipe; the pipe wall of the cold hydrogen pipe facing the liquid collecting plate is provided with a spray hole facing the liquid collecting plate, and the pipe wall of the cold hydrogen pipe facing the liquid collecting pipe is provided with a spray hole facing the liquid collecting pipe. The hydrogen entering the cold hydrogen box is sprayed out from the cold hydrogen pipe spray hole to cool the deoxidizing liquid, so that the deoxidizing liquid reacts with the hydrogen at a proper temperature, and the quality of the gasoline and diesel products is improved.
The upper part of the fixed bed hydrogenation upgrading reactor 17 is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of the gas holder 5, and heat generated by pyrolysis is used as a heat source for hydrogenation reaction through the gas holder, so that the cascade utilization of the heat is realized; the gas outlet is communicated with the gas inlet pipelines of the second-level non-phase-change dryer 1 and the fast pyrolysis reactor 2 and is used for providing preheating energy for the biomass non-phase-change reaction and the fast pyrolysis reaction, so that the gradient utilization of the energy is realized.
The catalyst used in the fixed bed hydrogenation upgrading reactor is aluminum oxide, and the active metals loaded on the catalyst are nickel, molybdenum and zirconium.
The device comprises a thermal state gas-solid cyclone separator, a quenching tower, a gas cabinet, a heat exchanger, a gas heat exchanger, a micro-nano bubble generator, a first gas-liquid separator, a first oil-water separator, a second gas-liquid separator, a second oil-water separator, a circulating hydrogen press, a hydrogen supercharging device and a hydrogen purifying device which all adopt conventional equipment in the field.
The method for producing the gasoline and diesel oil by using the long-period stable operation device for producing the gasoline and diesel oil by using the biomass as a raw material comprises the following steps of:
a) The biomass is subjected to low-temperature, micro-positive pressure and second-level non-phase-change drying pretreatment in a non-phase-change drying-pyrolysis bio-oil preparation system (I), and is coupled with rapid pyrolysis reaction to be converted into bio-oil with low water content and oxygen content.
In the embodiment, waste straws are used as biomass, the biomass is added from the top of the second-level non-phase-change dryer 1 and is dried, the drying time is 10 seconds, the drying temperature is 70 ℃, the air flow speed is 5m/s, the micro positive pressure is 5kPa, and the moisture of the biomass is reduced from 25% to 10%. The dried biomass is discharged from the bottom of the second-level non-phase-change dryer 1, enters the fast pyrolysis reactor 2 through the top of the fast pyrolysis reactor 2, is rapidly heated to 600 ℃ and then undergoes fast thermal cracking reaction, the temperature rising rate of 1000K/s is selected in the pyrolysis process, and the pyrolysis gas cooling rate of 500K/s is realized by adjusting the length of the downstream bed pyrolysis reactor. The pyrolysis product enters a pyrolytic carbon and heat carrier solid-solid separator 2-3 to separate the pyrolytic carbon from the heat carrier; the mixture of the pyrolytic carbon and the heat carrier enters an entrained flow separation system 2-3-1 from a feed bin 2-3-2 through a ball valve 2-3-3, and the mixture is rapidly fluidized to form a conveying bed; the particle group rises along with the airflow and is sprayed out from an outlet at the upper end of the entrained flow separation system 2-3-1, a small part of finely divided particles are carried by the airflow or rise through inertia action, enter a dust removal tank and are trapped, and most of the particles enter an outer tube of the entrained flow separation system 2-3-1 under the action of gravity; the outer tube mixture is fluidized at a low gas velocity (1.0 m/s) to form a bubbling bed, so that particles with particle size and density difference show different descending distances in the process, thereby the pyrolytic carbon and the heat carrier are separated, lighter pyrolytic carbon particles are suspended on the surface of the bed layer and collected by the pyrolytic carbon collection tank 2-3-4, and heavier heat carrier particles are collected by the heat carrier collection tank 2-3-5. The ratio of the biochar to the heat carrier in the pyrolysis process is 1/40, the gas speed for solid-solid separation and lifting of the biochar and the heat carrier is 2.5m/s (inner tube), the separation efficiency of the obtained biochar is 90%, and the separation efficiency of the heat carrier is 92%. The separated pyrolytic carbon enters a thermal state gas-solid cyclone separator 3, and the pyrolytic carbon separated by the thermal state gas-solid cyclone separator 3 enters a pyrolytic carbon collecting device 10; quenching high-temperature oil gas generated by pyrolysis to obtain biological oil at 60-70 ℃ through a quenching tower 4, further cooling part of the quenched biological oil to 30-40 ℃ through a heat exchanger 12, returning to the quenching tower to spray the high-temperature oil gas from a thermal state gas-solid cyclone 3, and introducing the other part of the quenched biological oil into a biological oil collecting device 11, wherein the properties of the biological oil are shown in tables 1 and 2; one part of noncondensable gas discharged from the quenching tower enters the fluidized bed hydrodeoxygenation reactor 13 and the fixed bed hydrogenation upgrading reactor through the gas holder 5 and is used as a heat source, and the other part of noncondensable gas enters the pyrolysis regenerator 6 to be combusted and then regenerates a heat carrier, and the regenerated heat carrier returns to the fast pyrolysis reactor 2. Part of the cold air provided by the air supply device 8 is heated to 350-450 ℃ by the high-temperature tail gas of the pyrolysis regenerator 6 in the gas heat exchanger 7 and then used as combustion-supporting gas for combustion of the pyrolysis regenerator 6.
B) The biological oil and hydrogen from the step A) firstly form micro-nano bubbles through a micro-nano bubble generator, and then the deoxidization liquid is obtained through hydrodeoxygenation reaction under the action of a catalyst in a fluidized bed hydrodeoxygenation reactor. The hydrogen generated in the step is purified and then used as recycle hydrogen, and the purified waste gas returns to the step A) to be used as a supplementary gas source for the fast pyrolysis reaction.
The external hydrogen is conveyed to a circulating hydrogen compressor 21 through a hydrogen pressurizing device 20, then is converged with the circulating hydrogen and enters an inlet of a first heating furnace 22, the hydrogen is mixed with the biological oil conveyed by a biological oil collecting device 11 and then is conveyed to a micro-nano bubble generator at the bottom of a fluidized bed hydrodeoxygenation reactor 13 through a first booster pump 26, the hydrogen is crushed into micro-nano bubbles under the shearing action of biological oil liquid, the size of an outlet bubble is 200-1000 microns, the effect of uniformly mixing gas and liquid phases in the circumferential direction is achieved, the gas and the liquid phases are dispersed into the reactor, and the biological oil, hydrogen mixture and spherical catalyst are rapidly heated, mixed and diluted under the high-speed disturbance of the fluidized bed hydrodeoxygenation reactor 13 to carry out hydrodeoxygenation reaction. The fluidization state of the hydrodeoxygenation catalyst is controlled by controlling the amount of the circulating oil and is made to satisfy the operation region of the fluidized bed reactor. The hydrogen-oil ratio of the hydrodeoxygenation reaction is controlled by controlling the amount of circulating hydrogen, and the catalyst in the example is a carbon sphere catalyst loaded with active metal nickel, wherein the volume ratio of hydrogen to oil is 500:1. The space velocity of the reaction volume in this example was 1h -1 The reaction pressure was 13.0MPa and the reaction temperature was 300 ℃. The product obtained by hydrodeoxygenation reaction enters a first gas-liquid separator 15 for separation. The waste hydrogen formed after the circulating hydrogen is subjected to a plurality of cycles enters a hydrogen purification device 25, the purified hydrogen is conveyed to a circulating hydrogen press 21 for the circulation of a hydrogenation system, and the rest mixed gas is returned to the fast pyrolysis reactor 2 to be used as a gas source for pyrolysis reaction. The liquid from the first gas-liquid separator 15 is separated by the second oil-water separationAfter the device 16, the water phase enters a water treatment facility 24, part of the oil phase is circulated back to the fluidized bed hydrodeoxygenation reactor through the first heating furnace 22 after being pressurized by the second booster pump 27, the deoxygenation liquid has the properties shown in tables 1 and 2, and the other part of the oil phase enters the fixed bed hydrodeoxygenation reactor 17 through the second heating furnace 23. The gas discharged from the fluidized bed hydrodeoxygenation reactor 13 is returned to the second-order non-phase-change dryer 1 and the fast pyrolysis reactor 2 to provide preheating energy for non-phase-change drying and fast pyrolysis of biomass.
C) And B), carrying out on-line activation and regeneration on the catalyst after the reaction in the step B) through an external catalyst on-line activation reactor, and continuously adding the regenerated catalyst into the step B) for reaction.
After a certain period of reaction, the activity of the catalyst is reduced, so that the liquid-solid two-phase mixture containing catalyst particles enters an in-situ on-line cyclone regenerator in a fluidized bed hydrodeoxygenation reactor 13, the revolution speed of the cyclone regenerated catalyst is 1.0rad/s, the rotation speed is 10.0rad/s, the rotational flow of the liquid-solid mixture is formed, the catalyst particles do revolution motion around the central axis of a cyclone activity restorer and do rotation motion around the central axis of the cyclone activity restorer, the centrifugal acting force applied to the carbon deposition precursor and an initial carbon deposition layer in the surface and pore channels of the catalyst is alternately changed, and the catalyst regeneration efficiency is 95%; the carbon deposition precursor and the initial carbon deposition layer on the surface of the final catalyst and in the pore canal are removed due to the alternate oscillation effect, so that the active sites on the surface of the catalyst and in the pore canal are re-exposed, the purpose of recovering the activity of the catalyst is achieved, and the carrying-out amount of the catalyst with the diameter of 0.5mm is controlled to be less than 2.5 mug/g. Further, the partially severely deactivated catalyst discharged from the hydrodeoxygenation reaction of the fluidized bed hydrodeoxygenation reactor 13 cannot be returned to the fluidized bed reactor for reuse, and the catalyst entering the online activation reactor 14 is subjected to online cyclone regeneration. The discharged catalyst and the organic solvent are subjected to rotational flow and autorotation activation in the online activation reactor 14, hot hydrogen at 200 ℃ is used as carrier gas in the rotational flow process to obtain catalyst containing the organic solvent and concentrated organic solvent, the concentrated organic solvent is discharged, and the catalyst containing the organic solvent is continuously subjected to rotational flow and autorotation to remove the organic reagent, so that dry catalyst particles are obtained. The dried catalyst particles continue to carry out catalyst activity sorting, the severely deactivated catalyst is discharged as waste agent, the renewable and reusable catalyst carries out reduction reaction, and then the catalyst returns to the fluidized bed hydrodeoxygenation reactor 13 for use.
D) The deoxidizing liquid from the step B) firstly forms micro-nano bubbles through a micro-nano bubble generator, then enters a fixed bed hydrogenation upgrading reactor with the function of suppressing the flying temperature, and carries out hydrogenation upgrading reaction while suppressing the flying temperature to obtain the gasoline and diesel components. The hydrogen generated in the step is purified and then is continuously used as recycle hydrogen, and the purified waste gas returns to the step A) to be used as a supplementary gas source for the fast pyrolysis reaction.
The partial deoxidized liquid from the first oil-water separator 16 is mixed with partial hydrogen from the circulating hydrogen compressor 21, heated to a set temperature by a second heating furnace 23, and then enters a fixed bed hydrogenation upgrading reactor 17 with a micro-nano bubble generator and a cold hydrogen tank for reaction. The hydrogen is crushed into micro-nano bubbles under the shearing action of the bio-oil liquid, the size of the bubbles at the outlet is 200-1000 microns, the effect of uniformly mixing the gas phase and the liquid phase in the circumferential direction is achieved, and then the gas phase and the liquid phase are dispersed into the reactor. In this example, the hydrogen-oil ratio was 700:1. The hydrocracking catalyst in this example was a clover-type alumina-based catalyst, and the space velocity of the reaction volume in this example was 2.0h -1 The reaction pressure was 15.0MPa and the reaction temperature was 300 ℃. The oxygen in the deoxidizing liquid is further removed, and simultaneously the macromolecular substances are cracked into small molecular substances, the oxygen is basically completely removed, and the sulfur content is less than 10ppm. The reacted product enters the second gas-liquid separator 18, and the gas from the second gas-liquid separator 18 is recycled back to the inlet. After the liquid from the second gas-liquid separator 18 passes through the second oil-water separator 19, the water phase enters the water treatment facility 24, and the oil phase is the finally obtained gasoline and diesel oil product. The waste hydrogen formed after the circulating hydrogen is subjected to a plurality of cycles enters the hydrogen purification device 25, the hydrogen purification device is started at the moment, the hydrogen purified by the hydrogen purification device 25 is conveyed to the circulating hydrogen press 21 for the circulation of the hydrogenation system, and the rest of mixed gas returns to the fast pyrolysis reactor 2 to be used as a gas source for pyrolysis reaction. The gas discharged from the fixed bed hydrogenation upgrading reactor 17 is returned to the second-level non-phase-change dryer 1 and the fast pyrolysis reaction The device 2 provides preheating energy for non-phase change drying and fast pyrolysis of biomass.
The device for producing gasoline and diesel by using biomass of the embodiment can realize long-period stable operation for half a year, and the hydrogenation quality-improving product oil still reaches the gasoline and diesel standard after half a year. The energy consumption of the whole process can be reduced by 30%, and the total yield of gasoline and diesel is improved by 50%.
TABLE 1 Properties of deoxygenated liquid produced by the hydrodeoxygenation reaction of biological oil
TABLE 2 analysis of biological oil and deoxygenation liquid GCMS results
/>
Example 2
In this example, the other operating conditions and process flows were the same as in example 1, as compared to example 1, which did not include a micro-nano bubble generator. Table 3 shows the properties of the deoxidizing liquid obtained by the reaction of the bio-oil with hydrodeoxygenation in example 2, and Table 4 shows the analysis of the results of GCMS of the bio-oil and deoxidizing liquid in example 2.
TABLE 3 deoxidizing liquid vs. example 2 and example 1
TABLE 4 analysis of the results of deoxygenated liquid GCMS of example 2 and example 1
By comparing with the long-period stable operation method and device for producing gasoline and diesel oil by using the biomass in the embodiment 1, the embodiment 2 without the micro-nano bubble generator has the problems of uneven gas-liquid distribution, large operation fluctuation, low gas-liquid mass transfer rate and the like, so that after the raw oil and the hydrogen enter the fluidized bed hydrodeoxygenation reactor 13 for reaction, the mass transfer rate is lower, and the quality of the deoxidized liquid is lower than that of the embodiment 1. As can be seen from tables 3 and 4, the deoxidizing liquid product obtained without the micro-nano bubble enhanced mass transfer heat generator has lower heat value than that of example 1, increased oxygen content, increased output of alcohols, lipids, ketones, aldehydes and other substances, and reduced output of alkanes and aromatic hydrocarbon products, which is generally unfavorable for the subsequent hydrogenation and upgrading reactions. The deoxidized liquid has too high oxygen content, is easy to cause coking in the subsequent hydrogenation upgrading reaction, has the problems of reactor runaway temperature and the like, and reduces the system operation period from half a year to 5 months in the embodiment 1.
Example 3
In this example, the fluidized bed hydrodeoxygenation reactor 13 was not provided with an in-situ on-line cyclone regenerator, as compared to example 1, and other operating conditions and process flows were the same as in example 1. Table 5 shows the comparison of the properties of the deoxidizing liquid in example 3 and example 1, and Table 6 shows the analysis of the results of the deoxidizing liquid GCMS in example 3 and example 1.
TABLE 5 comparison of deoxygenated liquid properties for example 3 and example 1
TABLE 6 analysis of the results of deoxygenated liquid GCMS of example 3 and example 1
After half a year of continuous operation, the deoxidizing liquid obtained in this example is compared with that of example 1, as shown in tables 5 and 6. Compared with the process in the embodiment 1, the process in the embodiment 3 is difficult to realize in-situ on-line removal of the carbon deposition precursor and the initial carbon deposition layer on the catalyst particles, so that the catalyst is regenerated and activated by means of on-line rotational flow of a device, the activation efficiency and the degree are lower than those in the embodiment 1, and the running period of the device is shortened. As can be seen from tables 5 and 6, the quality of the deoxidized liquid obtained by not arranging the in-situ on-line cyclone regenerator is obviously reduced compared with that of the deoxidized liquid obtained in the example 1, the heat value of the deoxidized liquid is reduced from 45MJ/kg to 40MJ/kg, the oxygen content is increased from 8.7wt.% to 20.4wt.%, the yield of substances such as alcohols, lipids, ketones and aldehydes is increased, the total amount of alkane and aromatic hydrocarbons is reduced from 74.34% to 54.36%, and the quality of the deoxidized liquid is poor, which is unfavorable for the subsequent hydrogenation and upgrading reaction.
Example 4
In this example, the other operating conditions and the process flow were the same as in example 1, compared to example 1 in which the catalyst in-line activation reactor 14 was not provided. The partially seriously deactivated catalyst discharged from the fluidized bed hydrodeoxygenation reactor 13 cannot be activated on line, and cannot be returned to the fluidized bed reactor for reuse, so that the catalyst consumption is increased, the cost is increased, the engineering amplification is not facilitated, and the operation period is reduced from half a year to 3 months.
Example 5
In this example, the fixed bed hydrogenation upgrading reactor 17 was not provided with a cold hydrogen tank, and other operating conditions and process flows were the same as in example 1, as compared to example 1. Table 7 shows the gasoline and diesel properties of example 5 in comparison with those of example 1.
Table 7 comparison of gasoline and diesel properties of example 5 and example 1
The comparison of the gasoline and diesel oil obtained in this example with example 1 is shown in Table 7. Compared with the process in the embodiment 1, the process in the embodiment 5 is characterized in that the deoxidized solution enters a fixed bed hydrogenation upgrading reactor without a cold hydrogen box for deep hydrogenation, and the hydrogenation reaction is a strong exothermic reaction, so that the fixed bed hydrogenation upgrading reactor has the condition that the exothermic reaction heat release rate is greater than the heat removal rate in the production process, the device temperature is out of control, the phenomenon of 'flying temperature' occurs, and sintering, structural collapse, deactivation and the like of the metal active components of the catalyst are caused. As shown in table 7, the gasoline and diesel oil obtained in example 5 has higher oxygen content than that in example 1, which is probably because the fixed bed hydrogenation upgrading reactor without cold hydrogen box has unstable device temperature, which causes sintering and deactivation of the active metal of the catalyst, so that the hydrogenation upgrading effect is poor, long-period stable operation is difficult to realize, and the operation period is shortened from half a year of example 1 to 4 months. From the results, the long-term stable operation method and the device for producing the gasoline and diesel by using the biomass formed by coupling the biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I), the bio-oil hydrodeoxygenation deoxidization liquid production system (II) and the deoxidization liquid hydrogenation quality improvement gasoline and diesel production system (III) can also meet the related standard requirements of the gasoline and diesel for the traffic field. The implementation result shows that the method and the device can realize high-quality conversion of biomass to gasoline and diesel oil, realize long-period stable operation for more than half a year, and greatly improve the productivity of the final product of the device, thereby further improving the economy of the invention.
Example 6
In this example, compared with example 1, the bio-oil system (I) and the deoxygenation liquid system (II) and the deoxygenation liquid hydrogenation upgrading gasoline and diesel system (III) are independently operated. The waste hydrogen generated by the hydrogenation systems (II) and (III) is directly discharged without a hydrogen purification device, the usage amount of the hydrogen in the whole process and the gas source required by pyrolysis is increased, and the energy consumption in the whole process is increased by 15% compared with that in the embodiment 1.
In conclusion, the long-period stable operation device for producing gasoline and diesel oil by using biomass provided by the invention has the advantages that biomass is dried at the micro-positive pressure level and the second level below 100 ℃ and is subjected to coupling pyrolysis reaction, so that low-energy-consumption pyrolysis is realized to prepare the bio-oil; the purified hydrogen is supplied to a hydrodeoxygenation quality-improving hydrogen source through a hydrogen supercharging device; the fluidized bed hydrodeoxygenation reactor (comprising a micro-nano bubble reinforced mass transfer heat transfer generator and an in-situ on-line catalyst activation reactor) is provided with a catalyst on-line activation reactor outside the coupler, so that the catalyst is regenerated and recycled; the hydrogenation quality improvement of the fixed bed for suppressing the fly temperature is realized to prepare gasoline and diesel oil reactor, so that the device can stably run for a long period; waste hydrogen generated by the fluidized bed and the fixed bed reactor is purified and conveyed to a hydrogen pressurizing device for recycling, and other mixed gases are conveyed to a fast pyrolysis reactor to be supplied to a pyrolysis reaction supplemental gas source, so that the device can realize that the energy consumption of the whole process is reduced by 30%, the total yield of gasoline and diesel is improved by 50%, and the device continuously and stably operates. The biomass-based gasoline and diesel oil products reach the national six standards, can be directly applied to the existing fuel oil vehicles in any proportion, and reduce the carbon dioxide emission by more than 66% compared with petroleum-based products.
Those of ordinary skill in the art will recognize that the embodiments described herein are for the purpose of aiding the reader in understanding the principles of the present invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (8)
1. The long-period stable operation method for producing gasoline and diesel oil by biomass is characterized by comprising the following steps of:
a) Biomass is subjected to low-temperature, micro-positive pressure, second-level non-phase-change drying and rapid pyrolysis conversion to obtain low-water-content and low-oxygen-content biological oil; the biomass non-phase change drying is carried out by rotational flow dehydration under the conditions of 10-30 seconds, 30-90 ℃ and air flow speed of 3-8m/s and micro positive pressure of 2-8KPa, the rapid pyrolysis temperature is 400-700 ℃, the heating rate is 1000K/s-10000K/s, the pyrolysis flue gas temperature is 500-800 ℃, and the cooling rate of pyrolysis gas is 200-1000K/s; the obtained biological oil has water content of 10-30% and oxygen content of 30-50%; the ratio of the pyrolytic carbon to the heat carrier in the pyrolysis process is 1/30-1/60, and the gas speed of the solid-solid separation and the lifting of the pyrolytic carbon and the heat carrier is 2.5-3m/s; the separation efficiency of the obtained pyrolytic carbon is 80-99%, and the separation efficiency of the heat carrier is 75-99%;
B) The biological oil from the step A) and the injected hydrogen are subjected to hydrodeoxygenation reaction, the biological oil flows and shears to enable the hydrogen to be crushed into micro-nano hydrogen bubbles, and then hydrodeoxygenation reaction is carried out under the action of a catalyst to obtain deoxidized liquid;
c) The catalyst after the given period of the step B) is regenerated through on-line activation, and the regenerated catalyst is continuously returned to the step B) to be used as a reaction catalyst;
d) The deoxidized liquid from the step B) is subjected to hydrogenation upgrading reaction in a cold hydrogen environment to obtain gasoline and diesel components;
e) The pyrolysis gas and pyrolytic carbon combustion exotherm from step a) provides heat for step B) and step D);
f) The heat generated by the reaction of step B) and step D) is used for biomass non-phase change drying and fast pyrolysis biomass preheating in step A) through air heat exchange;
g) After the residual waste hydrogen from the step B) and the step D) is purified, the hydrogen is continuously returned to the step B) and the step D) to be used as circulating hydrogen, and the waste gas after the hydrogen purification is returned to the step A) to be used as a supplementary gas source for the fast pyrolysis reaction.
2. The method for long-period stable operation of producing gasoline and diesel oil from biomass according to claim 1, characterized in that in step B), the hydrodeoxygenation reaction is carried out at a temperature of 200 ℃ to 400 ℃, at a pressure of 8 MPa to 15MPa, and at a reaction volume space velocity of 0.6 h to 2.0h -1 The ratio of hydrogen to oil is 400:1-1000:1, the water content in the obtained deoxidized liquid is 0.001-5%, the oxygen content is 5-10%, and the viscosity is 1-2cp.
3. The long-period stable operation method for producing gasoline and diesel oil by biomass according to claim 1 or 2, characterized in that the catalyst in the step B) is self-assembled spherical particles with a diameter of 0.2-5mm and an aspect ratio of 1-5, and the active metal loaded on the self-assembled spherical particles is a transition metal element from group IIIB to group IIB in the periodic table of elements, or/and an alloy formed by any two or more of the transition metal elements; in the step C), the catalyst can be regenerated by online activation in situ and/or online cyclone regeneration outside the reactor.
4. The method for producing gasoline and diesel oil by using biomass according to claim 1, wherein in the step B, micro-nano bubbles are bubbles with the size of 200-10000 microns formed by crushing a hydrogen gas phase under the shearing action of a bio-oil liquid phase, so that the effect of uniformly mixing gas phase and liquid phase in the axial direction is achieved, and the proportion of the liquid phase absorbed into the gas phase is 20% -80%.
5. The biomass production steam of claim 1The long-period stable operation method of diesel oil is characterized in that in the step D), the deoxidizing liquid hydrogenation and upgrading reaction temperature is 150-450 ℃, the pressure is 5-20MPa, and the reaction volume airspeed is 1.0-4.0h -1 The hydrogen-oil ratio is 400:1-1200:1.
6. The long-period stable operation device for producing gasoline and diesel oil by biomass is characterized by comprising a biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I), a bio-oil hydrodeoxygenation deoxidization liquid production system (II) and a deoxidization liquid hydrogenation quality improvement gasoline and diesel oil production system (III):
the biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) is used for carrying out low-temperature, micro-positive pressure and second-level non-phase-change drying pretreatment on biomass, and is coupled with rapid pyrolysis reaction to convert the biomass into bio-oil with low water content and low oxygen content; the biomass second-level non-phase-change drying-pyrolysis bio-oil preparation system (I) comprises a second-level non-phase-change dryer, a fast pyrolysis reactor, a thermal state gas-solid cyclone separator, a quenching tower, a gas holder, a pyrolysis regenerator, a gas supply device, a pyrolysis carbon collection device, a bio-oil collection device and a heat exchanger; the second-level non-phase-change dryer comprises more than one cyclone; when more than two cyclones are contained, the cyclones are connected in sequence through pipelines; the rapid pyrolysis reactor comprises a communicated downstream bed pyrolysis reactor and a pyrolytic carbon and heat carrier solid-solid separator; the downer pyrolysis reactor is respectively connected with the pyrolysis regenerator and pyrolysis reaction feeding equipment; the rapid pyrolysis reactor and the pyrolysis regenerator form a thermal circulation system; the outlet of the lower part of the thermal state gas-solid cyclone separator is communicated with the pyrolytic carbon collecting device, and the upper part of the thermal state gas-solid cyclone separator is connected with the lower ends of the pyrolytic carbon and the heat carrier solid separator; the gas outlet of the quenching tower is respectively communicated with a pyrolysis regenerator, a deoxidizing liquid system (II) for preparing the biological oil through hydrodeoxygenation and a gasoline and diesel oil system (III) through deoxidizing liquid hydrogenation and quality improvement; a heat exchanger forming a cold cycle with the quench tower is arranged on a branch line of the quench tower communicated with the biological oil collecting device; the biomass second-level non-phase-change drying-pyrolysis bio-oil production system (I) further comprises an air supply device which is used for communicating the second-level non-phase-change dryer and the pyrolysis regenerator;
The system (II) for preparing the deoxidizing liquid by hydrodeoxygenation of the biological oil is used for carrying out hydrodeoxygenation reaction on the biological oil under the action of micro-nano bubbles and a catalyst to obtain deoxidizing liquid; the biological oil hydrodeoxygenation deoxidization liquid system (II) comprises a hydrogen supercharging device, a circulating hydrogen press, a first booster pump, a first heating furnace, a second heater and a fluidized bed hydrodeoxygenation reactor, a first gas-liquid separator, a hydrogen purification device, a first oil-water separator and a water treatment facility which are sequentially communicated; the hydrogen pressurizing device and the circulating hydrogen press are used for providing hydrogen for the fluidized bed hydrodeoxygenation reactor; the inlet of the circulating hydrogen compressor is communicated with the hydrogen pressurizing device, and external hydrogen enters the circulating hydrogen compressor after being pressurized by the hydrogen pressurizing device; the first booster pump, the first heating furnace and the second heater are used for conveying biological oil raw materials to the fluidized bed hydrodeoxygenation reactor and the fixed bed hydrogenation upgrading reactor; the inlet of the first booster pump is communicated with the biological oil collecting device, and the outlet of the first booster pump is connected with the inlet of the fluidized bed hydrodeoxygenation reactor; the oil phase outlet of the first oil-water separator is provided with a second supercharger; a first heater and a second heater are respectively arranged on two branches from the first oil-water separator; the fluidized bed hydrodeoxygenation reactor is internally or/and externally provided with a catalyst on-line activation reactor and a micro-nano bubble generator, wherein the catalyst on-line activation reactor is used for on-line activation of the catalyst in the fluidized bed hydrodeoxygenation reactor, and the micro-nano bubble generator is used for fully mixing hydrogen and biological oil; the upper end of the first gas-liquid separator is respectively connected with the circulating hydrogen press and the hydrogen purification device; the hydrogen outlet of the hydrogen purification device is connected with the circulating hydrogen press, and the waste gas outlet is connected with the fast pyrolysis reactor; the lower end of the first oil-water separator is connected with a water treatment facility, the deoxidized liquid from the first oil-water separator is divided into two paths, one path is mixed with hydrogen from a circulating hydrogen press and then returns to the fluidized bed hydrodeoxygenation reactor, and the other path is mixed with hydrogen from the circulating hydrogen press and then enters a deoxidized liquid hydrogenation quality improvement gasoline and diesel oil production system (III); the upper part of the fluidized bed hydrodeoxygenation reactor is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of a gas holder, and the gas outlet is communicated with a second-level non-phase-change dryer and a gas inlet pipeline of the fast pyrolysis reactor;
The deoxidization liquid hydrogenation quality-improving gasoline and diesel oil preparing system (III) is used for carrying out hydrogenation quality-improving reaction on the deoxidization liquid to obtain gasoline and diesel oil components; the deoxidization liquid hydrogenation quality-improving gasoline and diesel oil production system (III) comprises a fixed bed hydrogenation quality-improving reactor, a second gas-liquid separator and a second oil-water separator which are sequentially communicated; a micro-nano bubble generator is arranged in the fixed bed hydrogenation upgrading reactor; the upper end of the second gas-liquid separator is respectively connected with the circulating hydrogen press and the hydrogen purification device; the lower end of the second oil-water separator is connected with a water treatment facility, and the oil product obtained by the second oil-water separator is a gasoline and diesel oil product; the upper part of the fixed bed hydrogenation upgrading reactor is also provided with a gas inlet and a gas outlet, the gas inlet is communicated with a gas outlet pipeline of a gas holder, and the gas outlet is communicated with a second-level non-phase change dryer and a gas inlet pipeline of the fast pyrolysis reactor.
7. The long-period stable operation device for producing gasoline and diesel oil by biomass according to claim 6, wherein the pyrolytic carbon and heat carrier solid-solid separator comprises an entrained flow separator, and the entrained flow separator comprises an inner pipe and an outer pipe which are sleeved together; the upper part of the outer tube is communicated with the dust removal tank, and the outer tube is sequentially connected with the pyrolytic carbon collection tank and the heat carrier collection tank from top to bottom; the bottom of the inner tube is connected with a feed bin, and the feed bin is connected with the lower end of the downer pyrolysis reactor; the outlet of the pyrolytic carbon collection tank is connected with the upper part of the thermal state gas-solid cyclone separator; the bottoms of the inner tube and the outer tube of the entrained flow separator are respectively connected with an air compressor for providing air flow.
8. The long-period steady operation device for producing gasoline and diesel oil by using biomass according to claim 6, wherein the air supply device comprises an air supply device, a gas heat exchanger and a gas mixer; the outlet of the air supply device is respectively connected with the inlets of the gas mixer and the gas heat exchanger; the inlet of the gas heat exchanger is also communicated with the upper part of the pyrolysis regenerator; the outlet of the gas heat exchanger is respectively communicated with the inlet of the gas mixer and the lower part of the pyrolysis regenerator; the outlet of the gas mixer is communicated with a second-level non-phase-change dryer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310049602.5A CN116286067B (en) | 2023-02-01 | 2023-02-01 | Long-period stable operation method and device for producing gasoline and diesel oil by biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310049602.5A CN116286067B (en) | 2023-02-01 | 2023-02-01 | Long-period stable operation method and device for producing gasoline and diesel oil by biomass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116286067A CN116286067A (en) | 2023-06-23 |
| CN116286067B true CN116286067B (en) | 2024-03-15 |
Family
ID=86824767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310049602.5A Active CN116286067B (en) | 2023-02-01 | 2023-02-01 | Long-period stable operation method and device for producing gasoline and diesel oil by biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116286067B (en) |
Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831328A (en) * | 2010-05-21 | 2010-09-15 | 张小红 | Green fuel oil and preparation method thereof |
| WO2010127182A1 (en) * | 2009-04-29 | 2010-11-04 | Evolugate, Llc | Adapting microorganisms for agricultural products |
| CN102459518A (en) * | 2009-04-07 | 2012-05-16 | 瓦斯技术研究所 | Hydropyrolysis of biomass for producing high quality liquid fuels |
| WO2012071005A1 (en) * | 2010-11-25 | 2012-05-31 | Yang Weihong | A method of producing bio oil using ultra high temperature steam pyrolysis of carbonaceous solids |
| CN102653691A (en) * | 2012-02-29 | 2012-09-05 | 东南大学 | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil |
| CA2832529A1 (en) * | 2011-04-08 | 2012-10-11 | Ulrich Wirtz | Methods and apparatus for the production of fuel |
| WO2015006269A1 (en) * | 2013-07-08 | 2015-01-15 | Battelle Memorial Institute | Upgrading of bio-oil by reaction with olefins in the presence of a catalyst |
| CN104845667A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Deoxidization bio-oil hydrogenation device with long operation cycle |
| CN104845668A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Method for prolonging operation cycle of deoxidized biomass oil hydrogenation device |
| CN204676039U (en) * | 2015-05-15 | 2015-09-30 | 河南百优福生物能源有限公司 | The deoxidation bio-oil hydrogenation unit that the cycle of operation is long |
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN105950195A (en) * | 2016-07-18 | 2016-09-21 | 中国石油大学(华东) | Cocurrent downward circulating fluidized bed millisecond pyrolysis and liquefaction technology for biomass |
| WO2016173958A1 (en) * | 2015-04-27 | 2016-11-03 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass or residual waste material to biofuels |
| CA3005405A1 (en) * | 2015-11-23 | 2017-06-01 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass into a liquid hydrocarbon material |
| CN106939171A (en) * | 2017-03-22 | 2017-07-11 | 中国石油大学(华东) | Biomass downlink cycle bed millisecond pyrolysis liquefaction technique |
| CN107460005A (en) * | 2017-07-26 | 2017-12-12 | 天津大学 | The method and device of aromatic hydrocarbon and alkene is prepared using bio oil catalytic hydrogenation coupling and catalyzing cracking |
| CN107723012A (en) * | 2017-09-15 | 2018-02-23 | 王树宽 | The system and method for coal-tar gas is produced in multistage fluidized bed pulverized coal pyrolysis and dedusting coupling |
| CN110028985A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid prepares high-quality fuel oil and/or industrial chemicals |
| CN110028986A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid prepares fuel oil |
| US10479943B1 (en) * | 2018-08-17 | 2019-11-19 | Chevron U.S.A. Inc. | Fluid catalytic cracking process employing a lipid-containing feedstock |
| CN110511776A (en) * | 2018-08-16 | 2019-11-29 | 中国石油大学(华东) | A kind of biomass pyrolytic produces the device and method of biological petrol and diesel oil |
| WO2020215464A1 (en) * | 2019-04-26 | 2020-10-29 | 上海华畅环保设备发展有限公司 | Method and apparatus for in-situ online cyclonic activity recovery of catalyst in ebullated bed hydrogenation reactor |
| CN112940765A (en) * | 2021-02-07 | 2021-06-11 | 四川大学 | System for biomass non-phase change drying coupled downer pyrolysis |
| CN113321182A (en) * | 2021-04-13 | 2021-08-31 | 云南齐裕经济技术发展有限公司 | System and method for producing hydrogen by coupling sludge |
| CN113337317A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by indirect liquefaction of biomass |
| CN113652272A (en) * | 2021-08-18 | 2021-11-16 | 中科博格(湖州)环保科技有限公司 | Preparation method and application of biodiesel and aviation fuel |
-
2023
- 2023-02-01 CN CN202310049602.5A patent/CN116286067B/en active Active
Patent Citations (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459518A (en) * | 2009-04-07 | 2012-05-16 | 瓦斯技术研究所 | Hydropyrolysis of biomass for producing high quality liquid fuels |
| WO2010127182A1 (en) * | 2009-04-29 | 2010-11-04 | Evolugate, Llc | Adapting microorganisms for agricultural products |
| CN101831328A (en) * | 2010-05-21 | 2010-09-15 | 张小红 | Green fuel oil and preparation method thereof |
| WO2012071005A1 (en) * | 2010-11-25 | 2012-05-31 | Yang Weihong | A method of producing bio oil using ultra high temperature steam pyrolysis of carbonaceous solids |
| CA2832529A1 (en) * | 2011-04-08 | 2012-10-11 | Ulrich Wirtz | Methods and apparatus for the production of fuel |
| CN102653691A (en) * | 2012-02-29 | 2012-09-05 | 东南大学 | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil |
| WO2013127215A1 (en) * | 2012-02-29 | 2013-09-06 | 东南大学 | Device and method for preparing oxygen-containing liquid fuel by bio-oil catalytic conversion |
| WO2015006269A1 (en) * | 2013-07-08 | 2015-01-15 | Battelle Memorial Institute | Upgrading of bio-oil by reaction with olefins in the presence of a catalyst |
| WO2016173958A1 (en) * | 2015-04-27 | 2016-11-03 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass or residual waste material to biofuels |
| CN104845667A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Deoxidization bio-oil hydrogenation device with long operation cycle |
| CN104845668A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Method for prolonging operation cycle of deoxidized biomass oil hydrogenation device |
| CN204676039U (en) * | 2015-05-15 | 2015-09-30 | 河南百优福生物能源有限公司 | The deoxidation bio-oil hydrogenation unit that the cycle of operation is long |
| CA3005405A1 (en) * | 2015-11-23 | 2017-06-01 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass into a liquid hydrocarbon material |
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN105950195A (en) * | 2016-07-18 | 2016-09-21 | 中国石油大学(华东) | Cocurrent downward circulating fluidized bed millisecond pyrolysis and liquefaction technology for biomass |
| CN106939171A (en) * | 2017-03-22 | 2017-07-11 | 中国石油大学(华东) | Biomass downlink cycle bed millisecond pyrolysis liquefaction technique |
| CN107460005A (en) * | 2017-07-26 | 2017-12-12 | 天津大学 | The method and device of aromatic hydrocarbon and alkene is prepared using bio oil catalytic hydrogenation coupling and catalyzing cracking |
| WO2019019539A1 (en) * | 2017-07-26 | 2019-01-31 | 天津大学 | Method and apparatus for preparing arene and olefin by means of catalytic hydrogenation coupled with catalytic cracking of bio-fuel |
| CN107723012A (en) * | 2017-09-15 | 2018-02-23 | 王树宽 | The system and method for coal-tar gas is produced in multistage fluidized bed pulverized coal pyrolysis and dedusting coupling |
| CN110511776A (en) * | 2018-08-16 | 2019-11-29 | 中国石油大学(华东) | A kind of biomass pyrolytic produces the device and method of biological petrol and diesel oil |
| US10479943B1 (en) * | 2018-08-17 | 2019-11-19 | Chevron U.S.A. Inc. | Fluid catalytic cracking process employing a lipid-containing feedstock |
| CN110028986A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid prepares fuel oil |
| CN110028985A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | A kind of method that biomass pyrolysis liquid prepares high-quality fuel oil and/or industrial chemicals |
| WO2020216062A1 (en) * | 2019-04-26 | 2020-10-29 | 河南百优福生物能源有限公司 | Method for preparing fuel from biomass pyrolysis liquid |
| WO2020216061A1 (en) * | 2019-04-26 | 2020-10-29 | 河南百优福生物能源有限公司 | Method for preparing high-quality fuel oil and/or chemical raw material from biomass pyrolysis liquid |
| WO2020215464A1 (en) * | 2019-04-26 | 2020-10-29 | 上海华畅环保设备发展有限公司 | Method and apparatus for in-situ online cyclonic activity recovery of catalyst in ebullated bed hydrogenation reactor |
| CN112940765A (en) * | 2021-02-07 | 2021-06-11 | 四川大学 | System for biomass non-phase change drying coupled downer pyrolysis |
| CN113321182A (en) * | 2021-04-13 | 2021-08-31 | 云南齐裕经济技术发展有限公司 | System and method for producing hydrogen by coupling sludge |
| CN113337317A (en) * | 2021-06-29 | 2021-09-03 | 海南盈科生物科技有限公司 | Method for preparing biodiesel by indirect liquefaction of biomass |
| CN113652272A (en) * | 2021-08-18 | 2021-11-16 | 中科博格(湖州)环保科技有限公司 | Preparation method and application of biodiesel and aviation fuel |
Non-Patent Citations (3)
| Title |
|---|
| 张波 ; 仲兆平 ; 于点 ; 黄荡 ; .生物质快速热解制取液体燃料的技术经济分析.东南大学学报(自然科学版).2016,(第06期),第1227-1233页. * |
| 李海燕 ; 肖军 ; 沈来宏 ; 袁言言 ; .生物质热解加氢制汽柴油系统的㶲分析.热科学与技术.2015,(第03期),第230-238页. * |
| 生物油精炼提质工艺研究;孙培勤;王高恩;孙绍晖;陈俊武;;中外能源;20170215(第02期);第61-66页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116286067A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103074097B (en) | Method and system for direct coal liquefaction | |
| CN102653691B (en) | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil | |
| CN107460005B (en) | The method and device of aromatic hydrocarbon and alkene is prepared using bio oil catalytic hydrogenation coupling and catalyzing cracking | |
| CN103265967B (en) | Method for preparing bio-oil by liquefying biomass by high efficiency hydro-thermal method | |
| CN106336879A (en) | Biomass pyrolysis-reforming hydrogen production method | |
| CN105505429A (en) | Oil preparation and gas production system and technology by conducting pressurization, hydrogenation and pyrolysis on large-sized seaweeds | |
| US20200181500A1 (en) | Use of cooling media in biomass conversion process | |
| CN106701142B (en) | The device and method that fuel is produced in catalysis pyrolysis are blended in high and low effective hydrogen-carbon ratio raw material | |
| CN110511776B (en) | Device and method for producing biodiesel through biomass pyrolysis | |
| CN109054875B (en) | Efficient biomass conversion method | |
| Kaur et al. | Commercial or pilot-scale pyrolysis units for conversion of biomass to bio-oils: state of the art | |
| CN201148414Y (en) | Spout circulating fluid bed woody biomass rapid pyrogenation equipment | |
| CN102250641A (en) | Method and apparatus for preparing ethylene and propylene with maximized yield | |
| CN114106865B (en) | Processing method and system for waste plastics | |
| AU2013397663A1 (en) | Reactor and method for pyrolyzing hydrocarbon materials by solid heat carrier | |
| CN116286067B (en) | Long-period stable operation method and device for producing gasoline and diesel oil by biomass | |
| CN201695001U (en) | Device for preparing ethylene and propylene | |
| CN109111935B (en) | Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas | |
| CN104017597B (en) | A kind of catalytic pyrolysis of biomass system and method | |
| CN103666514B (en) | Method for on-line catalytic cracking of biomass through gushing bed-revolving bed two-step method | |
| CN202543163U (en) | Device for preparing oxygen-containing liquid fuel by performing catalytic conversion on bio oil | |
| Deng et al. | State of art of biomass fast pyrolysis for bio-oil in China: a review | |
| CN110511773B (en) | Device and method for coupling biomass pyrolysis and catalytic cracking reaction | |
| CN205109602U (en) | Preparation equipment of biological aromatic hydrocarbon | |
| CN106635153A (en) | Processing method of medium and low-temperature coal tar whole distillate |
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 |