CN117264650A - Biomass hydrogenation liquefaction system and method - Google Patents
Biomass hydrogenation liquefaction system and method Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 85
- 238000000926 separation method Methods 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003921 oil Substances 0.000 claims description 267
- 239000007789 gas Substances 0.000 claims description 92
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 239000010865 sewage Substances 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 12
- 239000010724 circulating oil Substances 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000006837 decompression Effects 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 208000035874 Excoriation Diseases 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000008161 low-grade oil Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241001520808 Panicum virgatum Species 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000029226 lipidation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010902 straw Substances 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
- C10G1/065—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 in the presence of a solvent
-
- 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
- C10G1/083—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 in the presence of a solvent
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a biomass hydrogenation liquefaction system and a method, and relates to the technical field of biomass liquid fuel production and processing, wherein the system comprises a stirring tank, a heat exchange tank, a reactor, a hot high-pressure separation tank and a hot low-pressure separation tank which are sequentially connected, wherein the feeding of the stirring tank comprises biomass and a catalyst, the reactor is provided with a hydrogenation component, a hot high-pressure gas-distributing pipe of the hot high-pressure separation tank is communicated with the heat exchange tank, the hot high-pressure gas-distributing pipe separated by the hot high-pressure separation tank is fully conveyed into slurry oil of the heat exchange tank for heat exchange, the hot low-pressure gas-distributing pipe of the hot low-pressure separation tank is communicated with a cold low-pressure separation tank for separating raw oil, the hot low-pressure gas-distributing pipe of the hot low-pressure separation tank is communicated with a decompression tower for fractionating the raw oil and circulating solvent oil, and the circulating solvent oil is conveyed to the stirring tank; the invention simplifies the equipment number of the system, reduces the complexity of the structural arrangement of the system, can further reduce the energy consumption and the occupied area of the whole system, and also reduces the vulcanizing dosage required to be additionally added in the system.
Description
Technical Field
The invention relates to the technical field of biomass liquid fuel production and processing, in particular to a biomass hydrogenation liquefaction system and method.
Background
Biomass liquefaction technology is mainly divided into a thermochemical method, a biochemical method, an esterification method and a chemical synthesis method, wherein the thermochemical method is mainly divided into a fast pyrolysis technology and a high-pressure liquefaction technology, the biochemical method is also divided into ethanol production by starch and butanol production by biomass fermentation, and the chemical synthesis method comprises indirect liquefaction to produce gasoline and diesel oil, alcohol ether, aviation kerosene production by lipidation hydrogenation and the like. Each technology now has a place to be improved and optimized, and applicable objects and ranges are different, so different challenges are faced.
Taking a thermochemical process as an example, in the existing thermochemical process technology, the fast pyrolysis technology is often suitable for low-water biomass, and the high-pressure liquefaction technology is often suitable for high-water biomass, so that the existing thermochemical process technology often has a certain raw material limitation.
Meanwhile, the existing thermochemical process is often to sequentially and respectively carry out biomass liquefaction reaction and hydrofining reaction, correspondingly, at least two reactors, at least two matched hydrogenation devices and at least two heating furnaces are often arranged in the existing thermochemical process system, so that on one hand, the quantity of equipment in the whole system is too large, the structure is complex, the occupied area and the investment cost of the whole system are not facilitated to be reduced, on the other hand, the inlet temperature of each reactor is required to be controlled respectively, the difficulty of temperature control in the whole system is increased, meanwhile, along with the heating temperature rise of the heating furnace on liquid components such as slurry oil and the like, coking hidden danger is easily caused in the furnace tube over time, and the risk of tube abrasion and breakage is also caused on the furnace tube by the liquid components such as slurry oil and the like, so that the system is not facilitated to stably operate for a long period.
In addition, in the existing thermochemical process, a certain proportion of vulcanizing agent (such as liquid sulfur or dimethyl disulfide) is often required to be added into the system feed so as to meet the purpose of vulcanizing the catalyst, but along with the running of sulfur-containing substances in the system, the whole system and the process often face environmental protection problems in running, and the production of sulfur-containing waste and the environmental protection treatment difficulty are also not facilitated to be reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a biomass hydrogenation liquefaction system and a method thereof, so as to solve the problems of the biomass liquefaction system in the prior art that the number of devices is too large, the structure is complex, and the amount of sulfur-containing waste in the system is large.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the utility model provides a living beings hydrogenation liquefaction system, includes agitator tank, heat transfer tank, reactor, hot high pressure knockout drum, the low branch jar of heat that connects gradually, the feeding of agitator tank includes living beings, catalyst, the reactor has hydrogenation subassembly, the high minute gas pipe of hot high pressure knockout drum and heat transfer tank intercommunication, the heat high minute gas that the high pressure knockout drum separated is whole carries the slurry oil of heat transfer tank in heat transfer tank, the low minute gas pipe of hot low minute jar communicates with cold low minute jar for isolate the raw oil, the low minute oil pipe of hot low minute jar communicates with the decompression tower for fractionate raw oil, circulating solvent oil is carried to the agitator tank.
Further, the high-pressure oil pipe of the high-pressure separating tank is respectively communicated with the low-pressure separating tank and the reactor, one part of high-pressure oil separated by the high-pressure separating tank is mixed with the oil slurry and enters the reactor, and the other part of high-pressure oil enters the low-pressure separating tank.
Further, the tower bottom oil pipe of the vacuum tower is connected with the solid-liquid separation unit, the solid-liquid separation unit is provided with a circulating oil pipe, the circulating oil pipe is communicated with the stirring tank, a side line reflux pipe is arranged on the vacuum middle section oil pipe of the vacuum tower, and the side line reflux pipe is respectively connected with the vacuum middle section oil pipe and the circulating oil pipe.
Further, the heat exchange tank is provided with a gas phase exit pipe, the heat exchange tank is communicated with the cold high-pressure separation tank through the gas phase exit pipe, a cold high-pressure separation pipe of the cold high-pressure separation tank is communicated with the cold low-pressure separation tank, and a cold high-pressure separation pipe of the cold high-pressure separation tank is communicated with the hydrogenation component of the reactor.
Further, the hydrogenation component comprises a hydrogen supply device and a hydrogen heating furnace, wherein the hydrogen supply device is communicated with an inlet of the hydrogen heating furnace, and an outlet of the hydrogen heating furnace is communicated with the reactor.
Further, a cold high-pressure gas distribution pipe of the cold high-pressure gas distribution tank is communicated with the circulating hydrogen buffer tank, and an outlet of the circulating hydrogen buffer tank is communicated with an inlet of the hydrogen heating furnace.
Further, the system comprises a catalyst loading and unloading tank, wherein the catalyst loading and unloading tank is communicated with the reactor, and a solid-liquid separator is arranged in the catalyst loading and unloading tank.
A biomass hydro-liquefaction method applied to the biomass hydro-liquefaction system, the method comprising: s1, adding biomass, a catalyst and circulating solvent oil into a stirring tank, and mixing to prepare slurry oil; s2, conveying the oil slurry to a heat exchange tank, and conveying the hot high-pressure separated gas to the heat exchange tank, wherein the oil slurry is in direct contact heat exchange with the hot high-pressure separated gas, so that the oil slurry is heated once; s3, mixing the oil slurry subjected to primary temperature rise with a part of hot high-pressure oil separated by a hot high-pressure separation tank to form oil slurry subjected to secondary temperature rise; s4, mixing the oil slurry with hydrogen, which is heated for the second time, into a reactor, and carrying out biomass liquefaction reaction and hydrofining reaction; the reaction product enters a thermal high-pressure separation tank and is separated into thermal high-pressure gas and thermal high-pressure oil, wherein all the thermal high-pressure gas is conveyed to a heat exchange tank and participates in the heat exchange process of the step S2, one part of thermal high-pressure oil participates in the mixing process of the step S3, and the other part of thermal high-pressure oil enters a thermal low-pressure tank; s5, separating the hot high-fraction oil into hot low-fraction gas and hot low-fraction oil through a hot low-fraction tank, separating the cold low-fraction oil from the hot low-fraction gas in a cold low-fraction tank, and separating the hot low-fraction oil into pressure reducing middle-section oil and tower bottom oil in a pressure reducing tower; s6, enabling the bottom oil to enter a solid-liquid separation unit to separate heavy circulating solvent oil and solid residues, wherein the heavy circulating solvent oil is mixed with part of pressure reducing middle section oil to be used as the circulating solvent oil in the step S1, and the other part of pressure reducing middle section oil is mixed with cold low-pressure separating oil to be used as raw oil.
In step S4, after the hot high-pressure gas is subjected to contact heat exchange with the slurry oil by the heat exchange tank, the hot high-pressure gas is conveyed to the air cooler to be cooled and then enters the cold high-pressure tank, the cold high-pressure gas and the cold high-pressure liquid are separated, and the cold high-pressure gas is mixed with hydrogen provided by the hydrogenation component, heated and sent to the reactor together after entering the circulating hydrogen buffer tank for buffering.
In step S5, the hot low-pressure gas and the cold high-pressure liquid separated from the cold high-pressure tank in step S4 are fed into the cold low-pressure tank together, and the sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil are separated.
Compared with the prior art, the biomass hydrogenation liquefaction system and the biomass hydrogenation liquefaction method have the following advantages:
according to the biomass hydrogenation liquefaction system and method, only one set of reactor with the hydrogenation component is arranged, the biomass liquefaction reaction and the hydrofining reaction of the slurry oil are combined in one reaction device, and the reaction heat of the two reactions is accumulated together, so that the process limit value A of the reaction inlet temperature can be reduced, the energy consumption can be reduced, and on the other hand, at least one reactor, one matched hydrogenation device and one heating furnace can be reduced, the number of devices in the biomass liquefaction system is simplified, the complexity of the structural arrangement of the system is reduced, the energy consumption and the occupied area of the whole system can be further reduced, and the investment cost of the system can be reduced.
In addition, this application is with the whole slurry oil that carries the heat high-pressure knockout drum in producing to the heat transfer jar, through the direct contact heat transfer of two, utilize the heat high-pressure knockout drum of high temperature to heat the slurry oil, firstly can carry out waste heat recovery effectively, be favorable to reducing the system energy consumption, second heat high-pressure knockout drum in solid content relatively very little, can not produce too much wearing and tearing to equipment, be favorable to the long period operation of device, thirdly, can utilize the hydrogen sulfide in the heat high-pressure knockout drum to contact the catalyst in the slurry oil and react, reach the purpose of vulcanization catalyst, be favorable to reducing the vulcanization dosage that needs extra to add in the system, be favorable to reducing the production of sulfur-containing waste material and the environmental protection treatment degree of difficulty, be favorable to improving environmental protection benefit.
Meanwhile, the oil slurry is heated in two stages through the hot high-pressure gas and the hot high-pressure oil, so that on one hand, the waste heat recovery can be effectively carried out, the energy consumption of the system is reduced, on the other hand, the actual temperature B of the oil slurry entering the reactor is improved, the actual temperature B of the oil slurry can be fully ensured, the temperature B is more than or equal to A, compared with the prior art, a matched oil slurry heating furnace is not required to be arranged at the inlet of the reactor, the equipment quantity in the system can be further simplified, the energy consumption and the occupied area of the system are reduced, the hidden coking trouble and the pipe body abrasion rupture risk of the heating furnace can be completely eliminated, and the long-period stable operation of the system is guaranteed.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 is a schematic structural diagram of a biomass-to-liquid system according to an embodiment of the present invention.
Reference numerals illustrate:
1. a stirring tank; 2. a booster pump; 3. a heat exchange tank; 4. a hydrogen gas heating furnace; 5. a reactor; 6. a thermal high pressure separator tank; 7. an air cooler; 8. a catalyst loading and unloading tank; 9. a thermal low-pressure separating tank; 10. cold high-pressure separating tank; 11. cold low-pressure separating tank; 12. a recycle hydrogen compressor; 13. a new hydrogen compressor; 14. a circulating hydrogen buffer tank; 15. a pressure reducing tower; 16. a heat exchange cooling system; 17. and a pressurizing pump.
Detailed Description
The inventive concepts of the present disclosure will be described below using terms commonly used by those skilled in the art to convey the substance of their work to others skilled in the art. These inventive concepts may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. Unless otherwise specifically indicated, and unless otherwise specifically noted, all biomass-related mixtures in liquid flow regimes in this application are simply referred to as "slurries"; the term "feedstock" in this application refers to the final target product "biodiesel feedstock" of biomass hydro-liquefaction, all of which are herein simply referred to as "feedstock".
The invention will be described in detail below with reference to the drawings in connection with embodiments.
In order to solve the problems of the prior art that the biomass liquefaction system has a large number of devices and a complex structure and the system has a large amount of sulfur-containing waste, the embodiment provides a biomass hydrogenation liquefaction system and a method, as shown in fig. 1, the system comprises a stirring tank 1, a heat exchange tank 3, a reactor 5, a hot high-pressure separation tank 6 and a hot low-pressure separation tank 9 which are sequentially connected, wherein the feeding of the stirring tank 1 comprises biomass and a catalyst, the reactor 5 is provided with a hydrogenation component, the hot high-pressure gas pipe of the hot high-pressure separation tank 6 is communicated with the heat exchange tank 3 and is used for conveying all the hot high-pressure gas separated by the hot high-pressure separation tank 6 into slurry in the heat exchange tank 3 for heat exchange, the hot low-pressure gas pipe of the hot low-pressure separation tank 9 is communicated with a cold low-pressure separation tank 11 and is used for separating raw oil, the hot low-pressure separation tank 9 is communicated with a decompression tower 15 and is used for fractionating raw oil and circulating solvent oil, and the circulating solvent oil is conveyed to the stirring tank 1.
Therefore, the application only sets up a set of reactor 5 that has hydrogenation subassembly, merges biomass liquefaction reaction, the hydrofining reaction of slurry oil in a reaction equipment to add the reaction heat accumulation of two reactions together, on the one hand can reduce the technology limit value A of reaction entry temperature, be favorable to reducing the energy consumption, on the other hand can reduce a reactor at least, a hydrogenation unit and a heating furnace that match, simplified the equipment quantity in the biomass liquefaction system, reduced the complexity of system structural arrangement, can also further reduce the energy consumption of entire system, area, be favorable to reducing the investment cost of system.
In addition, this application is with the whole slurry oil that carries heat transfer tank 3 of heat high-pressure separation jar 6 in the high-pressure gas that produces, through the direct contact heat transfer of two, utilize high-temperature high-pressure gas to heat the slurry oil, firstly can carry out waste heat recovery effectively, be favorable to reducing the system energy consumption, second heat high-pressure gas in solid content relatively very little, can not produce too much wearing and tearing to equipment, be favorable to the long period operation of device, thirdly, can utilize the hydrogen sulfide in the high-pressure gas to contact the catalyst in the slurry oil and react, reach the purpose of vulcanization catalyst, be favorable to reducing the vulcanization dosage that needs extra to add in the system, be favorable to reducing the volume of production and the environmental protection treatment degree of difficulty of sulfur waste material, be favorable to improving environmental protection benefit.
The high-pressure oil pipe of the high-pressure separating tank 6 is respectively communicated with the low-pressure separating tank 9 and the reactor 5, so that part of high-pressure oil separated by the high-pressure separating tank 6 is mixed with oil slurry and enters the reactor 5, and the other part of high-pressure oil enters the low-pressure separating tank 9. Compared with the prior art, the oil slurry heating furnace matched with the inlet of the reactor 5 is not required, and the specific reasons are that: after the slurry oil is heated by the hot high-pressure gas in the heat exchange tank 3, part of the hot high-pressure oil separated by the hot high-pressure separation tank 6 is mixed and enters the reactor 5, so that on one hand, the overall solid content of the slurry oil in the reactor 5 is reduced, the abrasion to equipment pipe fittings is reduced, on the other hand, the slurry oil is mixed with the slurry oil by utilizing the hot high-pressure oil with relatively high temperature, the slurry oil is secondarily heated, the actual temperature B of the slurry oil entering the reactor 5 is improved, and the mixing amount of the hot high-pressure oil is regulated, so that B is more than or equal to A, a matched slurry oil heating furnace is not required to be arranged at the inlet of the reactor 5, thereby not only further simplifying the equipment quantity in the system, reducing the energy consumption and the occupied area of the system, but also completely avoiding the hidden coking trouble and the abrasion and cracking risk of a pipe body of the heating furnace, and being beneficial to guaranteeing the long-period stable operation of the system.
The bottom of the heat exchange tank 3 is provided with a feeding distribution pipe, an inlet of the feeding distribution pipe is connected with a high-temperature gas-distributing pipe of the high-temperature high-pressure separation tank 6, so that high-temperature gas-distributing gas can be uniformly introduced into slurry oil in the heat exchange tank 3, and the slurry oil is heated by utilizing high-temperature gas-distributing gas through direct contact heat exchange of the two. In order to improve the heating effect, the residence time of the slurry oil in the heat exchange tank 3 is 20-120 min.
Because the hot high-pressure gas source is continuously and completely introduced into the heat exchange tank 3, the heat exchange tank 3 is provided with a gas-phase outlet pipe, the heat exchange tank 3 is communicated with the cold high-pressure tank 10 through the gas-phase outlet pipe, a cold high-pressure liquid-separating pipe of the cold high-pressure tank 10 is communicated with the cold low-pressure tank 11, and a cold high-pressure gas-separating pipe of the cold high-pressure tank 10 is communicated with a hydrogenation component of the reactor 5. So that the gas phase component (mainly hot high-pressure gas after heat exchange) discharged from the heat exchange tank 3 is separated into cold high-pressure gas and cold high-pressure liquid (comprising cold high-pressure oil and sulfur-containing sewage) by the cold high-pressure tank 10, the cold high-pressure gas is recycled into the reactor 5 as circulating hydrogen, and the cold high-pressure liquid enters the cold low-pressure tank 11 for continuous separation.
Because the gas phase components discharged from the heat exchange tank 3 still have a certain higher temperature, an air cooler 7 or other heat exchange equipment is arranged in the gas phase outlet pipe so as to reduce the temperature of the gas phase components discharged from the heat exchange tank 3, and the subsequent separation of the cold high-pressure separation tank 10 is facilitated. Correspondingly, a heat exchange cooling system 16 is also arranged in the heat low-pressure gas pipe of the heat low-pressure gas tank 9, and the heat exchange cooling system 16 can be an air cooler or other heat exchange equipment so as to reduce the temperature of the heat low-pressure gas separated from the heat low-pressure gas tank 9 and facilitate the separation of the subsequent cold low-pressure gas tank 11.
For the cold low-pressure separator 11, the cold high-pressure separator 10 and the hot low-pressure separator 9 enter the cold low-pressure separator 11 to separate sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure separator oil, wherein the cold low-pressure separator oil can be used as a part of the final raw oil.
For the vacuum tower 15, the thermal low-pressure oil in the thermal low-pressure tank 9 enters the vacuum tower 15, and the vacuum middle-stage oil and the bottom oil are separated, wherein the vacuum middle-stage oil is light hydrogen-supplying solvent oil and medium hydrogen-supplying solvent oil, the vacuum middle-stage oil can be used as a part of final raw oil, and the bottom oil is heavy circulating solvent oil and solid residues. Correspondingly, the pressure reducing tower 15 is provided with a pressure reducing middle oil pipe and a tower bottom oil pipe.
The bottom oil pipe of the vacuum tower 15 is connected with a solid-liquid separation unit, the solid-liquid separation unit is provided with a circulating oil pipe, and the circulating oil pipe is communicated with the stirring tank 1, so that after the bottom oil is separated by the solid-liquid separation unit, solid residues are separated, and heavy circulating solvent oil is conveyed to the stirring tank 1 through the circulating oil pipe. The pressure reducing middle section oil pipe of the pressure reducing tower 15 is provided with a side line backflow pipe, and the side line backflow pipe is respectively connected with the pressure reducing middle section oil pipe and the circulating oil pipe, so that a part of the pressure reducing middle section oil is circulated and flows back to the stirring tank 1. Specific: a part of the pressure reducing middle section oil separated by the pressure reducing tower 15 and the cold low-pressure oil in the cold low-pressure tank 11 are used as raw oil together; the other part of the pressure-reducing middle oil separated by the pressure-reducing tower 15 and the heavy circulating solvent oil are circulated back to the stirring tank 1 as circulating solvent oil.
The vacuum tower 15 preferably adopts vacuum cutting type separation, mainly ensures the cutting requirement through vacuum degree and steam stripping, and can avoid arranging a feeding heating furnace, thereby reducing the coking risk in a furnace tube caused by heating of the heating furnace, reducing the risk of abrasion and rupture of oil slurry to the furnace tube, and being beneficial to long-period stable operation of the device.
For the reactor 5, the reactor 5 has a hydrogenation assembly comprising a hydrogen supply device, a hydrogen heating furnace 4, the hydrogen supply device being in communication with an inlet of the hydrogen heating furnace 4, an outlet of the hydrogen heating furnace 4 being in communication with the reactor 5 for delivering hydrogen into the reactor 5 to maintain the hydrofinishing reaction of the slurry oil. The hydrogen gas supply device includes a new hydrogen compressor 13 so as to regulate the supply pressure, supply flow rate, and the like of the hydrogen gas.
The cold high-pressure gas-distributing pipe of the cold high-pressure gas-distributing tank 10 is communicated with the hydrogenation component of the reactor 5, specifically, the cold high-pressure gas-distributing pipe of the cold high-pressure gas-distributing tank 10 is communicated with the circulating hydrogen buffer tank 14 for buffering the cold high-pressure gas, and the outlet of the circulating hydrogen buffer tank 14 is communicated with the inlet of the hydrogen heating furnace 4, so that the cold high-pressure gas and the hydrogen provided by the hydrogen supply device are mixed and enter the hydrogen heating furnace 4 for heating, and then enter the reactor 5. The outlet of the circulating hydrogen buffer tank 14 is provided with a circulating hydrogen compressor 12 so as to carry out pressure boosting conveying on the cold high-pressure gas.
The reactor 5 is preferably an ebullated-bed reactor, which may comprise one or more series of ebullated-bed units. The reactor 5 is filled with microsphere catalyst, which not only can provide active center for liquefied oil and circulating oil hydrogenation and ensure the depth of hydrofining reaction, but also is convenient for loading and unloading catalyst.
The system comprises a catalyst loading and unloading tank 8, wherein the catalyst loading and unloading tank 8 is communicated with the reactor 5 and is used for discharging, filling and renewing the catalyst in the reactor 5, and a solid-liquid separator is arranged in the catalyst loading and unloading tank 8 and is used for separating slurry oil and the catalyst; specifically, the catalyst loading and unloading tank 8 is provided with a feeding pipe, a material returning pipe and an outer discharge pipe, the feeding pipe is respectively connected with the catalyst loading and unloading tank 8 and the reactor 5, the material returning pipe is respectively connected with the catalyst loading and unloading tank 8 and the reactor 5, and the catalyst loading and unloading tank 8 discharges the separated dead catalyst and the large-particle cokes outside through the outer discharge pipe. So that the catalyst loading and unloading tank 8 can discharge large-particle cokes and catalysts with reduced activity generated in the reactor 5, and simultaneously, the high-activity catalysts are timely supplemented into the reactor 5, thereby being beneficial to ensuring the long-period stable operation of the device.
In the system, since a certain pressure is required to be additionally provided for conveying part of materials, a conventional pump body can be correspondingly arranged to meet the requirements of material conveying, for example: a booster pump 2 is arranged between the outlet of the stirring tank 1 and the heat exchange tank 3 to pressurize the slurry oil so as to flow into the heat exchange tank 3; a pressurizing pump 17 is arranged between the slurry outlet of the heat exchange tank 3 and the reactor 5, so that the pressurized slurry and the heated hydrogen are mixed and enter the reactor 5 for reaction.
On the basis of the biomass hydrogenation liquefaction system, the embodiment provides a biomass hydrogenation liquefaction method, which comprises the following steps:
s1, adding biomass, a catalyst and circulating solvent oil into a stirring tank 1, and mixing to prepare slurry oil;
s2, conveying the slurry oil to a heat exchange tank 3, conveying the hot high-pressure separated gas from the hot high-pressure separation tank 6 to the heat exchange tank 3, and enabling the slurry oil and the hot high-pressure separated gas to be in direct contact heat exchange so as to heat the slurry oil for one time;
s3, mixing the oil slurry subjected to primary temperature rise with a part of hot high-pressure oil separated by the hot high-pressure separation tank 6 to form oil slurry subjected to secondary temperature rise;
s4, mixing the oil slurry with hydrogen, which is heated for the second time, into a reactor 5 for biomass liquefaction reaction and hydrofining reaction; the reaction product enters a thermal high-pressure separation tank 6 and is separated into thermal high-pressure gas and thermal high-pressure oil, wherein all the thermal high-pressure gas is conveyed to a heat exchange tank 3 and participates in the heat exchange process of the step S2, one part of the thermal high-pressure oil participates in the mixing process of the step S3, and the other part of the thermal high-pressure oil enters a thermal low-pressure tank 9;
s5, separating the hot high-fraction oil into hot low-fraction gas and hot low-fraction oil through a hot low-fraction tank 9, wherein the hot low-fraction gas enters a cold low-fraction tank 11 to be separated into cold low-fraction oil, and the hot low-fraction oil enters a pressure reducing tower 15 to be separated into pressure reducing middle-section oil and bottom oil;
s6, enabling the bottom oil to enter a solid-liquid separation unit to separate heavy circulating solvent oil and solid residues, wherein the heavy circulating solvent oil is mixed with part of pressure reducing middle section oil to be used as the circulating solvent oil in the step S1, and the other part of pressure reducing middle section oil is mixed with cold low-pressure separating oil to be used as raw oil.
Therefore, the biomass liquefaction reaction and the hydrofining reaction of the slurry oil are combined in one reactor, and the reaction heat of the two reactions is accumulated together, so that on one hand, the process limit value A of the reaction inlet temperature can be reduced, the energy consumption is reduced, on the other hand, the equipment quantity in the biomass liquefaction system is simplified, the complexity of the system structural arrangement is reduced, the energy consumption and the occupied area of the whole system can be further reduced, and the investment cost of the system is reduced.
Meanwhile, the slurry oil is heated in two stages through the hot high-pressure gas and the hot high-pressure oil, so that on one hand, the waste heat recovery can be effectively carried out, the energy consumption of a system is reduced, on the other hand, the actual temperature B of the slurry oil entering the reactor 5 is improved, the actual temperature B of the slurry oil can be fully ensured, the B is more than or equal to A, a matched slurry oil heating furnace is not required to be arranged at an inlet of the reactor 5, the equipment quantity in the system can be further simplified, the energy consumption and the occupied area of the system are reduced, the hidden coking trouble and the abrasion and cracking risk of a pipe body of the heating furnace can be completely eradicated, and the long-period stable operation of the system is guaranteed. In addition, in the direct contact heat exchange process of the hot high-pressure gas and the slurry oil, the hydrogen sulfide in the hot high-pressure gas is in contact reaction with the catalyst in the slurry oil, so that the purpose of vulcanizing the catalyst is achieved, the additional vulcanizing amount required in the system is reduced, the yield of sulfur-containing waste materials and the environmental protection treatment difficulty are reduced, and the environmental protection benefit is improved.
And (2) conveying the hot high-pressure gas in the step (S4) to an air cooler (7) for cooling after carrying out contact heat exchange with slurry oil through a heat exchange tank (3), and then entering a cold high-pressure tank (10) to separate cold high-pressure gas and cold high-pressure liquid (comprising cold high-pressure oil and sulfur-containing sewage), wherein the cold high-pressure gas enters a circulating hydrogen buffer tank (14) for buffering, is mixed with hydrogen provided by a hydrogenation component, heated and then is sent to a reactor (5) together, and the cold high-pressure liquid and the hot low-pressure gas separated by a hot low-pressure tank (9) enter a cold low-pressure tank (11) together to separate sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil.
The biomass is a biomass powder, and the biomass in the present application may be agricultural residues (bran, straw, bagasse, stalk, etc.), woody waste (sawdust, chipper, etc.), woody plants (eucalyptus, mixed poplar, willow, korean pine, etc.), herbaceous plants (sugarcane, sorghum, switchgrass, etc.), oil crops (oil coconut, rape, soybean, etc.), papermaking black liquor, etc.
The catalyst in the step S1 is a homogeneous catalyst or a particle catalyst; the homogeneous catalyst is a water-soluble catalyst or an oil-soluble catalyst obtained by mixing one or more metals of Ni, co, mo and W; the particle type catalyst is formed by loading iron-based metal on a biomass matrix.
In the step S1, the dosage ratio between the catalyst and the biomass is 100 PPMw-10000 PPMw, and the mass ratio between the biomass and the circulating solvent oil is 1: 0.8-2.
In the step S3, in the mixing process of the oil slurry and the hot high-pressure oil after primary temperature rising, the mass ratio of the oil slurry to the hot high-pressure oil after primary temperature rising is 1:0.5-5.
The reactor 5 is preferably packed with a supported microspherical catalyst whose active metal is one or more metals of Ni, co, mo and W. The filling amount (volume) of the microsphere catalyst is 0.2-3 times, preferably 0.5-1.5 times, the volume of the biomass in the step S1.
In the step S4, the reaction temperature in the reactor 5 is 340-450 ℃, the reaction pressure is 3-20 MPa, and the hydrogen-oil volume ratio is 350-1500 (specifically, the volume ratio of hydrogen and slurry oil fed into the reactor 5 in the step S4). Preferably, it is: the reaction temperature is 360-410 ℃, the reaction pressure is 6-16 MPa, and the hydrogen-oil volume ratio is 600-1200.
In step S5, the vacuum tower 15 is not provided with a feeding heating furnace, but the cutting requirement of the vacuum tower 15 is ensured by injecting stripping steam, the consumption of the stripping steam is 0.3% -2% (mass ratio) of the feeding amount of the vacuum tower 15, and the cutting distillation range of the bottom oil of the vacuum tower 15 is 350 ℃ -520 ℃.
In the application, the yield of the finally produced solid residues accounts for 1% -10% (mass ratio) of the biomass proportion, and the yield of the finally produced raw oil accounts for 60% -95% (mass ratio) of the biomass proportion.
Example 1
(1) Mixing circulating solvent oil, dry biomass powder below 200 meshes and a catalyst to prepare slurry oil, wherein the circulating solvent oil and the dry biomass powder are mixed according to the proportion of 1:1, and the adding amount of the catalyst is 0.5% of the mass of the biomass powder;
(2) The slurry oil in the step (1) is conveyed into a heat exchange tank 3 after being boosted, and is contacted with the reacted hot high-pressure gas for heat exchange and temperature rise, and the residence time of the slurry oil in the heat exchange tank 3 is 30min;
(3) Mixing the heated slurry oil with the hot high-pressure oil, further pressurizing, mixing with the heated hydrogen gas into a reactor 5, and reacting at 380 ℃ under the reaction pressure of 8.0MPaG in the reactor 5, wherein the weight ratio of the microsphere catalyst filled in the reactor 5 to the dry biomass powder is 1:1, and the hydrogen oil volume ratio is 800;
(4) Separating the reaction product obtained after the reaction in the step (3) into hot high-pressure gas and hot high-pressure oil by a hot high-pressure separating tank 6;
(5) Mixing the hot high-pressure oil separating part with slurry oil at the bottom of the heat exchange tank 3, wherein the mixing mass ratio is 1:1; the waste heat high-pressure oil is decompressed and enters a thermal low-pressure separating tank 9, the thermal low-pressure separated gas of the thermal low-pressure separating tank 9 enters a cold low-pressure separating tank 11, the thermal low-pressure separated oil of the thermal low-pressure separating tank 9 directly enters a decompression tower 15 for separation, the residual pressure at the top of the decompression tower 15 is 40mmHg, and the injected stripping steam amount is 1% w of the feeding amount; the pressure reducing middle section oil is light and medium hydrogen supply solvent oil, and the bottom oil is heavy circulating solvent oil and solid residues; the initial boiling point of the bottom oil cut of the vacuum tower 15 is 400 ℃;
(6) The hot high-pressure gas in the step (4) passes through a heat exchange tank 3, is cooled to 50 ℃ by an air cooler 7, and enters a cold high-pressure tank 10 to separate cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage; the cold high-pressure separated gas enters a circulating hydrogen buffer tank 14 for buffering, then enters a circulating hydrogen compressor 12 for boosting to 8.5MPaG, and is mixed with new hydrogen of 8.5MPaG, enters a hydrogen heating furnace 4 for heating to 430 ℃, and the cold high-pressure separated oil, the sulfur-containing sewage and the hot low-pressure separated gas separated by a hot low-pressure separated tank 9 enter a cold low-pressure separated tank 11 together for separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure separated oil;
(7) In the step (5), the bottom oil of the vacuum tower 15 enters a solid-liquid separation unit to separate heavy circulating solvent oil and solid residues;
(8) The light and medium hydrogen-supplying solvent oil part in the step (5) is mixed with the heavy circulating solvent oil in the step (7) to be used as the circulating solvent oil for preparing the slurry oil in the step (1), and the rest light and medium hydrogen-supplying solvent oil part is mixed with the cold low-grade oil in the step (6) to be used as the raw oil for producing the high-quality biodiesel, wherein the sulfur content of the raw oil product is 0.1 percent w, the nitrogen content is 0.35 percent w, and the oxygen content is 0.05 percent w.
Example 2
(1) Mixing circulating solvent oil, dry biomass powder below 200 meshes and a catalyst to prepare slurry oil, wherein the circulating solvent oil and the dry biomass powder are mixed according to the proportion of 1.5:1, and the adding amount of the catalyst is 0.1% of the mass of the dry biomass powder;
(2) The slurry oil in the step (1) is conveyed into a heat exchange tank 3 after being boosted, and is contacted with the reacted hot high-pressure gas for heat exchange and temperature rise, and the residence time of the slurry oil in the heat exchange tank 3 is 60min;
(3) Mixing the heated slurry oil with the hot high-pressure oil, further pressurizing, mixing with the heated hydrogen gas, entering a reactor 5, and reacting at the temperature of 410 ℃ in the reactor 5 under the reaction pressure of 12.0MPaG, wherein the weight ratio of the microsphere catalyst filled in the reactor 5 to the dry biomass powder is 1.5:1, and the hydrogen oil volume ratio is 1000;
(4) Separating the reaction product obtained after the reaction in the step (3) into hot high-pressure gas and hot high-pressure oil by a hot high-pressure separating tank 6;
(5) Mixing the hot high-pressure oil separating part with slurry oil at the bottom of the heat exchange tank 3, wherein the mixing mass ratio is 1:1; the waste heat high-pressure oil is decompressed and enters a thermal low-pressure separating tank 9, the thermal low-pressure separated gas of the thermal low-pressure separating tank 9 enters a cold low-pressure separating tank 11, the thermal low-pressure separated oil of the thermal low-pressure separating tank 9 directly enters a decompression tower 15 for separation, the residual pressure at the top of the decompression tower 15 is 20mmHg, and the injected stripping steam amount is 0.5 percent w of the feeding amount; the pressure reducing middle section oil is light and medium hydrogen supply solvent oil, and the bottom oil is heavy circulating solvent oil and solid residues; the initial boiling point of the bottom oil cut of the vacuum tower 15 is 380 ℃;
(6) The hot high-pressure gas in the step (4) passes through a heat exchange tank 3, is cooled to 50 ℃ by an air cooler 7, and enters a cold high-pressure tank 10 to separate cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage; the cold high-pressure separated gas enters a circulating hydrogen buffer tank 14 for buffering, then enters a circulating hydrogen compressor 12 for boosting to 12.5MPaG and 12.5MPaG, and then enters a hydrogen heating furnace 4 for heating to 470 ℃, and the cold high-pressure separated oil, the sulfur-containing sewage and the hot low-pressure separated gas separated by a hot low-pressure separated tank 9 enter a cold low-pressure separated tank 11 together for separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure separated oil;
(7) In the step (5), the bottom oil of the vacuum tower 15 enters a solid-liquid separation unit to separate heavy circulating solvent oil and solid residues;
(8) The light and medium hydrogen-supplying solvent oil part in the step (5) is mixed with the heavy circulating solvent oil in the step (7) to be used as the circulating solvent oil for preparing the slurry oil in the step (1), and the rest light and medium hydrogen-supplying solvent oil part is mixed with the cold low-grade oil in the step (6) to be used as the raw oil for producing the high-quality biodiesel, wherein the sulfur content of the raw oil product is 0.08 percent w, the nitrogen content is 0.22 percent w, and the oxygen content is 0.01 percent w.
The solid residue yield and the raw oil yield were measured in example 1 and example 2, respectively, and the specific experimental measurement results are shown in table 1.
TABLE 1
| Yield of solid residue/% | Yield of raw oil/% | |
| Example 1 | 4.5 | 80 |
| Example 2 | 2.5 | 91 |
Wherein, solid residue yield = solid residue mass/dry basis biomass powder mass x 100%; raw oil yield= (cold low-split oil quality generated in the whole process + pressure-reducing middle-stage oil quality of the discharge device)/dry biomass powder quality x 100%, cold low-split oil refers to cold low-split oil separated by the cold low-split tank 11, and pressure-reducing middle-stage oil refers to pressure-reducing middle-stage oil (excluding the part of pressure-reducing middle-stage oil as circulating solvent oil) extracted by the pressure-reducing tower 15.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The utility model provides a living beings hydrogenation liquefaction system, its characterized in that, the system includes agitator tank (1), heat transfer tank (3), reactor (5), hot low pressure knockout drum (6), the low knockout drum (9) of connecting gradually, the feeding of agitator tank (1) includes living beings, catalyst, reactor (5) have hydrogenation subassembly, the high gas-phase of hot high pressure knockout drum (6) is with heat transfer tank (3) intercommunication, the heat transfer is carried in the slurry of heat transfer tank (3) to the high gas-phase of hot separated in hot high pressure knockout drum (6), the low gas-phase of hot low knockout drum (9) is with cold low knockout drum (11) intercommunication for isolate the raw materials oil, the low gas-phase of hot low knockout drum (9) is with reducing tower (15) intercommunication, is used for fractionating out raw materials oil, circulating solvent oil is carried to agitator tank (1).
2. The biomass hydrogenation liquefaction system according to claim 1, wherein the high-pressure hot separation tank (6) is respectively communicated with the low-pressure hot separation tank (9) and the reactor (5), a part of high-pressure hot separation oil separated by the high-pressure hot separation tank (6) is mixed with slurry oil and enters the reactor (5), and the other part of high-pressure hot separation oil enters the low-pressure hot separation tank (9).
3. The biomass hydrogenation liquefaction system according to claim 1, wherein a tower bottom oil pipe of the vacuum tower (15) is connected with a solid-liquid separation unit, the solid-liquid separation unit is provided with a circulating oil pipe, the circulating oil pipe is communicated with the stirring tank (1), a side return pipe is arranged on a vacuum middle section oil pipe of the vacuum tower (15), and the side return pipe is respectively connected with the vacuum middle section oil pipe and the circulating oil pipe.
4. The biomass hydrogenation liquefaction system according to claim 1, wherein the heat exchange tank (3) is provided with a gas phase outlet pipe, the heat exchange tank (3) is communicated with a cold high-pressure separation tank (10) through the gas phase outlet pipe, a cold high-pressure separation pipe of the cold high-pressure separation tank (10) is communicated with a cold low-pressure separation tank (11), and a cold high-pressure separation pipe of the cold high-pressure separation tank (10) is communicated with a hydrogenation component of the reactor (5).
5. The biomass-to-liquid system according to claim 4, wherein the hydrogenation assembly comprises a hydrogen supply device and a hydrogen heating furnace (4), the hydrogen supply device is communicated with an inlet of the hydrogen heating furnace (4), and an outlet of the hydrogen heating furnace (4) is communicated with the reactor (5).
6. The biomass-to-liquid system of claim 5, wherein the cold high-pressure gas pipe of the cold high-pressure gas tank (10) is communicated with a circulating hydrogen buffer tank (14), and the outlet of the circulating hydrogen buffer tank (14) is communicated with the inlet of the hydrogen heating furnace (4).
7. A biomass-to-liquid system according to claim 1, characterized in that the system comprises a catalyst loading tank (8), the catalyst loading tank (8) being in communication with the reactor (5), a solid-liquid separator being provided in the catalyst loading tank (8).
8. A method for the hydroliquefaction of biomass, characterized in that it is applied to the system for the hydroliquefaction of biomass according to any one of claims 1 to 7, said method comprising:
s1, adding biomass, a catalyst and circulating solvent oil into a stirring tank (1), and mixing to prepare slurry oil;
s2, conveying the slurry oil to a heat exchange tank (3), and conveying the hot high-pressure gas separated by the hot high-pressure separation tank (6) to the heat exchange tank (3), wherein the slurry oil and the hot high-pressure gas are in direct contact heat exchange, so that the slurry oil is heated once;
s3, mixing the oil slurry subjected to primary temperature rise with a part of hot high-pressure oil separated by a hot high-pressure separation tank (6) to form oil slurry subjected to secondary temperature rise;
s4, mixing the oil slurry with hydrogen, which is heated for the second time, into a reactor (5) for biomass liquefaction reaction and hydrofining reaction; the reaction product enters a thermal high-pressure separation tank (6) and is separated into thermal high-pressure gas and thermal high-pressure oil, all the thermal high-pressure gas is conveyed to a heat exchange tank (3) and participates in the heat exchange process of the step S2, one part of the thermal high-pressure oil participates in the mixing process of the step S3, and the other part of the thermal high-pressure oil enters a thermal low-pressure tank (9);
s5, separating the hot high-pressure oil into hot low-pressure gas and hot low-pressure oil through a hot low-pressure tank (9), wherein the hot low-pressure gas enters a cold low-pressure tank (11) to be separated into cold low-pressure oil, and the hot low-pressure oil enters a pressure reducing tower (15) to be separated into pressure reducing middle-section oil and tower bottom oil;
s6, enabling the bottom oil to enter a solid-liquid separation unit to separate heavy circulating solvent oil and solid residues, wherein the heavy circulating solvent oil is mixed with part of pressure reducing middle section oil to be used as the circulating solvent oil in the step S1, and the other part of pressure reducing middle section oil is mixed with cold low-pressure separating oil to be used as raw oil.
9. The method for liquefying biomass by hydrogen according to claim 8, wherein in step S4, the hot high-pressure gas is conveyed to an air cooler (7) to be cooled after being subjected to contact heat exchange with slurry oil by a heat exchange tank (3), and then enters a cold high-pressure tank (10) to separate cold high-pressure gas and cold high-pressure liquid, and the cold high-pressure gas is mixed with hydrogen provided by a hydrogenation assembly, heated and fed into a reactor (5) together after entering a circulating hydrogen buffer tank (14) to be buffered.
10. The method for the hydroliquefaction of biomass according to claim 9, wherein in the step S5, the hot low-pressure gas and the cold high-pressure liquid separated from the cold high-pressure tank (10) in the step S4 are fed into the cold low-pressure tank (11) together, and the sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil are separated.
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| CN105505429A (en) * | 2016-01-14 | 2016-04-20 | 江苏大学 | Oil preparation and gas production system and technology by conducting pressurization, hydrogenation and pyrolysis on large-sized seaweeds |
| CN108130116A (en) * | 2016-12-01 | 2018-06-08 | 何巨堂 | Preposition solvent oil hydrogenation reaction process and coal hydrogenation liquefaction reaction process combined method |
| CN116218560A (en) * | 2023-01-10 | 2023-06-06 | 孙少哲 | Coal hydrogenation upgrading method |
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