CN116218560A - Coal hydrogenation upgrading method - Google Patents
Coal hydrogenation upgrading method Download PDFInfo
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- CN116218560A CN116218560A CN202310034392.2A CN202310034392A CN116218560A CN 116218560 A CN116218560 A CN 116218560A CN 202310034392 A CN202310034392 A CN 202310034392A CN 116218560 A CN116218560 A CN 116218560A
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- 239000003245 coal Substances 0.000 title claims abstract description 81
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 164
- 239000002904 solvent Substances 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000003250 coal slurry Substances 0.000 claims abstract description 31
- 239000010742 number 1 fuel oil Substances 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000007841 coal based oil Substances 0.000 claims abstract description 15
- 239000010865 sewage Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 230000006837 decompression Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 50
- 238000000926 separation method Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002815 homogeneous catalyst Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000003139 buffering effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000002817 coal dust Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 208000035874 Excoriation Diseases 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004939 coking 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
- 239000000446 fuel Substances 0.000 description 2
- 239000008161 low-grade oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a coal hydrogenation upgrading method, which comprises the following steps: mixing pulverized coal and circulating solvent oil to prepare coal oil slurry; mixing the heated coal oil slurry with the hot high-pressure oil, pressurizing and mixing with the heated hydrogen to obtain a reaction product; separating out hot high-pressure gas and hot high-pressure oil from the reaction product; mixing the hot high-pressure oil separating part with the coal oil slurry, and decompressing the other part, wherein the bottom oil is heavy circulating solvent oil and clean coal; separating cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage from the hot high-pressure gas; separating heavy circulating solvent oil and clean coal products from the bottom oil; the part of the light and medium hydrogen-supplying solvent oil in the middle section of the decompression is mixed with the heavy circulating solvent oil to be used as the circulating solvent oil for preparing coal slurry, and the other part is mixed with the cold low-pressure oil to be used as the coal-based oil product. The invention puts the coal liquefaction reaction, the liquefied oil and the hydrogenation reaction of the circulating solvent oil in one reaction system, reduces one set of solvent oil hydrogenation stabilizing device, and greatly reduces construction investment and total energy consumption.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a coal hydrogenation upgrading method.
Background
The direct coal liquefaction process is to mix pulverized coal with a circulating solvent, react with hydrogen at a certain temperature and pressure, and directly convert organic matters of coal into liquefied oil; the quality of liquefied oil is further improved by desulfurization and denitrification, so that the product can be processed in a common oil refinery to produce transportation fuel and chemical products. The direct coal liquefaction has the advantages of high oil yield and high thermal efficiency; the main disadvantage is that the hydrogenation process has more severe operation conditions, and the device has higher energy consumption and higher investment in order to pursue high conversion rate.
Disclosure of Invention
In view of the above, the invention aims to provide a coal hydrogenation upgrading method, which converts coal into high-quality clean coal and coal-based light oil through hydrogenation reaction, ensures that the device can realize long-period stable operation, and greatly reduces the energy consumption and investment of the device.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for improving the quality of coal hydrogenation, which comprises the following steps:
s1, mixing pulverized coal and circulating solvent oil in an oil slurry stirring tank to prepare oil-coal slurry, pressurizing the oil-coal slurry by a pressurizing pump, and then entering a heating tank, wherein the oil-coal slurry is directly contacted with hot high-pressure gas entering the heating tank to heat-exchange and heat the oil-coal slurry;
s2, mixing the heated coal oil slurry and the heated high-pressure oil in a heating tank, pressurizing by a relay pressurizing pump, mixing the pressurized coal oil slurry with heated hydrogen from a hydrogen heating furnace, and feeding the mixture into a ebullated bed reactor for reaction to obtain a reaction product;
s3, separating hot high-pressure gas and hot high-pressure oil from the reaction product by a hot high-pressure separation tank;
s4, enabling the hot high-pressure oil-separating part in the step S3 to enter a heating tank and oil-coal slurry at the bottom of the heating tank for mixing, enabling the other part to enter a hot low-pressure tank in a depressurizing mode, enabling low oil obtained in the hot low-pressure tank to enter a depressurizing tower for separation, enabling oil in the depressurizing middle section to be light and medium hydrogen-supplying solvent oil, and enabling bottom oil to be heavy circulating solvent oil and clean coal;
s5, cooling the hot high-pressure gas in the step S3 by a heating tank and an air cooler, and then separating cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage in a cold high-pressure tank, wherein the cold high-pressure gas enters a circulating hydrogen buffer tank to be buffered, enters a circulating hydrogen compressor to be boosted, is mixed with hydrogen entering from a new hydrogen compressor, enters a hydrogen heating furnace, and the cold high-pressure oil and sulfur-containing sewage enter a cold low-pressure tank to separate sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil;
s6, enabling the bottom oil in the step S4 to enter a solid-liquid separation unit to separate heavy circulating solvent oil and clean coal products;
s7, mixing part of the light and medium hydrogen supply solvent oil in the step S4 with the heavy circulating solvent oil in the step S6 to prepare circulating solvent oil of coal slurry, and mixing the other part of the light and medium hydrogen supply solvent oil with the cold low-pressure oil in the step S5 to prepare a coal-based oil product.
Further, in the step S1, the mass ratio of the pulverized coal to the circulating solvent oil is 1:0.8-2.
Further, in step S1, the pulverized coal, the circulating solvent oil and the first catalyst are mixed in a slurry stirring tank to prepare a coal oil slurry, and the catalyst is selected from a homogeneous catalyst or a granular catalyst.
In step S2, the mass ratio of the coal oil slurry to the hot high-pressure oil is 1:0.5-5.
In step S2, the heated coal oil slurry, the hot high-pressure oil and the second catalyst are mixed in a heating tank, and the second catalyst is a microsphere catalyst.
Further, in step S2, the ebullated-bed reactor is one ebullated-bed reactor or a plurality of ebullated-bed reactors connected in series.
In step S2, the reaction temperature is 340-450 ℃, the reaction pressure is 6-20 MPa, and the volume ratio of hydrogen to hot high-pressure oil is 450-1500.
Further, in step S2, a catalyst loading and unloading tank for intermittent operation is disposed at the bottom of the ebullated bed reactor, and a solid-liquid separator is disposed inside the catalyst loading and unloading tank for separating the spent catalyst from the coal slurry.
In step S4, the cutting distillation range of the solid residue oil contained in the bottom of the vacuum tower is 420-550 ℃.
Further, in step S4, the cutting requirements of the vacuum tower are ensured by injecting stripping steam.
The clean coal product obtained by the invention can be used as clean fuel for power generation, metallurgy and the like, and can also be used as raw materials for producing calcium carbide, ferroalloy and the like; the properties of the coal-based oil product are superior to those of the coal tar product, and the coal-based oil product can be used as a raw material for producing aromatic hydrocarbon products and a high-quality raw material for producing coal-based hydrogenated oil products.
Compared with the direct coal liquefaction technology in the prior art, the method for improving the quality of coal hydrogenation has the following advantages: the main target products of coal hydrogenation and upgrading are crystal clean coal and coal-based light oil, the yield of the oil is not pursued, and more high-quality clean coal is produced, so that the operation conditions are relatively mild, and the energy consumption of the device is low; meanwhile, the coal liquefaction reaction, the liquefied oil and the hydrogenation reaction of the circulating solvent oil are placed in a reaction system, and compared with the direct coal liquefaction technology, a set of solvent oil hydrogenation stabilizing device is reduced, and the construction investment and the total energy consumption are greatly reduced.
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 flow chart of a method for upgrading coal by hydrogenation according to the invention.
Reference numerals illustrate:
1. an oil slurry stirring tank; 2. a pressurizing pump; 3. a heating tank; 4. a hydrogen gas heating furnace; 5. a ebullated bed 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 exchanger; 17. a solid-liquid separation unit; 18. and a relay pressurizing pump.
Detailed Description
The invention is further described below in conjunction with the detailed description. It should be noted that the data in the following examples are obtained by the inventors through a lot of experiments, and are only shown in some of the descriptions, and those skilled in the art can understand and practice the present invention under the data. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that after reading the present disclosure, those skilled in the art may make various changes or modifications to the present disclosure, which also fall within the scope of the present disclosure.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
As shown in FIG. 1, the method for improving the quality of coal hydrogenation comprises the following steps:
s1, mixing pulverized coal and circulating solvent oil in an oil slurry stirring tank 1 to prepare oil-coal slurry, pressurizing the oil-coal slurry by a pressurizing pump 2, and then entering a heating tank 3, wherein the oil-coal slurry is directly contacted with hot high-pressure gas entering the heating tank 3 to enable the oil-coal slurry to exchange heat and raise the temperature;
specifically, the pulverized coal is at least one selected from peat with low coalification degree, bituminous coal and lignite.
In step S1, the mass ratio of the pulverized coal to the circulating solvent oil is 1:0.8-2.
Further, in step S1, coal dust, circulating solvent oil and a first catalyst are mixed in a slurry stirring tank 1 to prepare a coal oil slurry, wherein the first catalyst is selected from a homogeneous catalyst or a granular catalyst. The homogeneous catalyst is a water-soluble catalyst or a soluble catalyst obtained by mixing one or more metals of Ni, co, mo and W; the particle type catalyst is iron-based metal, and the particle type catalyst is loaded on coal dust. Further, the first catalyst is used in an amount of 100 to 10000ppmw based on the dry coal dust.
Further, in step S1, a hot high-pressure gas feeding distribution pipe is disposed at the bottom of the heating tank 3, so as to uniformly distribute the hot high-pressure gas entering the heating tank 3. The residence time of the heating tank 3 is 20 to 120 minutes.
The hot high-pressure gas is adopted to heat the oil-coal slurry, so that the abrasion to equipment is avoided, the service life is reduced, the long-period operation of the device is facilitated, and the purpose of vulcanizing the catalyst can be achieved by utilizing the contact reaction of hydrogen sulfide in the hot high-pressure gas and the catalyst. The hydrogen sulfide generated by the reaction is utilized to save a vulcanizing agent (liquid sulfur or dimethyl disulfide and the like) needed by catalyst vulcanization, so that the cost of environmental protection treatment of the hydrogen sulfide is greatly reduced.
S2, mixing the heated coal oil slurry and the heated high-pressure oil in a heating tank 3, pressurizing by a relay pressurizing pump 18, mixing the pressurized coal oil slurry with heated hydrogen from a hydrogen heating furnace 4, and reacting in a ebullated bed reactor 5 to obtain a reaction product;
in step S2, the mass ratio of the coal oil slurry to the hot high-pressure oil is 1:0.5-5.
Further, in step S2, the ebullated-bed reactor 5 is one ebullated-bed reactor 5 or a plurality of ebullated-bed reactors 5 are connected in series.
Further, in step S2, the heated coal oil slurry, the hot high-pressure oil and the second catalyst are mixed in the heating tank 3, and the second catalyst is a microsphere catalyst. The microsphere catalyst is supported, and the active metal is one or more metals selected from Ni, co, mo and W. Further, if the microspherical catalyst is selected to be loaded, the ratio of the loading of the microspherical catalyst to the dry coal dust volume is 0.2-3:1. Further, the ratio of the loading of the microspherical catalyst to the dry coal dust volume is 0.5-1.5:1.
In step S2, the reaction temperature is 340-450 ℃, the reaction pressure is 6-20 MPa, and the volume ratio of hydrogen to hot high-pressure oil is 450-1500. In step S2, the reaction temperature is 360-410 ℃, the reaction pressure is 6-16 MPa, and the volume ratio of hydrogen to hot high-pressure oil is 600-1200.
Further, in step S2, a catalyst loading tank 8 for batch operation is provided at the bottom of the ebullated bed reactor 5. The catalyst loading and unloading tank 8 is internally provided with a solid-liquid separator for separating deactivated catalyst and coal oil slurry.
The coal liquefaction reaction, the liquefied oil and the hydrorefining reaction of the circulating solvent oil are combined in the boiling bed reactor 5, and the reaction heat of the two reactions is accumulated together, so that the temperature of a reaction inlet can be reduced, a set of solvent oil hydrogenation device can be reduced, the investment is saved, and the energy consumption and the occupied area are reduced.
The fluidized bed 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 to obtain high quality coal-based light oil, but also can discharge large-particle cokes and catalyst with reduced activity generated in the fluidized bed reactor 5 through a matched catalyst loading and unloading tank 8, and simultaneously, the high-activity catalyst is timely supplemented into the fluidized bed reactor 5, thereby ensuring long-period stable operation of the device.
The high-temperature oil separation circulation is used for mixing with the coal oil slurry, so that the solid content in the coal slurry is reduced, and the abrasion to equipment pipe fittings is reduced; and the inlet temperature of the ebullated bed reactor 5 is increased, and a set of oil-coal slurry heating furnace is reduced. The coking risk in the furnace tube caused by heating of the heating furnace can be reduced, the risk of abrasion and cracking of the furnace tube caused by coal oil slurry is reduced, and the long-period stable operation of the device is facilitated.
S3, separating hot high-pressure gas and hot high-pressure oil from the reaction product by a hot high-pressure separation tank 6;
further, the hot high-pressure separation gas entering the heating tank 3 comes from the hot high-pressure separation tank 6. The hot high-pressure separation oil entering the heating tank 3 comes from the hot high-pressure separation tank 6.
S4, enabling a part of the hot high-pressure oil in the step S3 to enter a heating tank 3 and oil-coal slurry at the bottom of the heating tank 3 to be mixed, enabling the other part of the hot high-pressure oil to enter a hot low-pressure tank 9 in a depressurizing mode, enabling low oil obtained by the hot low-pressure tank 9 to enter a depressurizing tower 15 for separation, enabling middle-pressure oil to be light and medium hydrogen-supplying solvent oil, and enabling bottom oil to be heavy circulating solvent oil and clean coal;
in step S4, the cutting distillation range of the solid residue oil contained in the bottom of the vacuum tower 15 is 420-550 ℃. Further, the cutting distillation range of the solid residue oil contained at the bottom of the vacuum tower 15 is 460-520 ℃.
Further, in step S4, the vacuum tower 15 is not provided with a vacuum tower feeding heating furnace, and the cutting requirement of the vacuum tower 15 is ensured by injecting stripping steam, so that the coking risk in the furnace tube caused by the temperature rise of the heating tank 3 is reduced, the risk of furnace tube rupture caused by the abrasion of the coal oil slurry to the furnace tube is reduced, and the long-period stable operation of the device is facilitated. The steam stripping amount is 0.3-2% w of the feeding amount of the vacuum tower 15.
S5, cooling the hot high-pressure gas in the step S3 through a heating tank 3 and an air cooler 7, then separating cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage in a cold high-pressure tank 10, buffering the cold high-pressure gas in a circulating hydrogen buffer tank 14, then pressurizing the cold high-pressure gas in a circulating hydrogen compressor 12, mixing the cold high-pressure gas with hydrogen entering from a new hydrogen compressor 13, then entering a hydrogen heating furnace 4, and separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil in a cold low-pressure tank 11;
s6, enabling the bottom oil in the step S4 to enter a solid-liquid separation unit 17 to separate heavy circulating solvent oil and clean coal products;
further, in step S6, the yield of the clean coal product accounts for 30-60% w of the weight of the dry coal dust. Further, the clean coal product yield is 40-50% w of the dry coal powder weight.
S7, mixing part of the light and medium hydrogen supply solvent oil in the step S4 with the heavy circulating solvent oil in the step S6 to prepare circulating solvent oil of coal slurry, and mixing the other part of the light and medium hydrogen supply solvent oil with the cold low-pressure oil in the step S5 to prepare a coal-based oil product.
Further, in step S7, the yield of the coal-based oil product accounts for 15-35% w of the weight of the dry coal dust. Further, the yield of the coal-based oil product is 20-30% w of the weight of the dry coal dust.
Compared with the direct coal liquefaction technology, the method for improving the quality by hydrogenating the coal has the following advantages: the main target products of coal hydrogenation and upgrading are clean coal and coal-based light oil, the yield of the oil is not pursued, and more high-quality clean coal is produced, so that the operation conditions are relatively mild, and the energy consumption of the device is low; meanwhile, the coal liquefaction reaction, the liquefied oil and the hydrogenation reaction of the circulating solvent oil are placed in a reaction system, and compared with the direct coal liquefaction technology, a set of solvent oil hydrogenation stabilizing device is reduced, and the construction investment and the total energy consumption are greatly reduced.
The invention will be further described with reference to specific examples.
Example 1
S1, mixing circulating solvent oil, coal dust below 200 meshes and a homogeneous catalyst to prepare coal-oil slurry, wherein the circulating solvent oil and the coal dust are mixed according to a mass ratio of 1:1, and the adding amount of the catalyst is 0.5% of the mass of the coal dust. And (3) after the oil-coal-slurry is boosted, conveying the oil-coal-slurry into the heating tank 3, and carrying out heat exchange by contacting with the reacted hot high-pressure gas to raise the temperature, wherein the residence time of the oil-coal-slurry in the heating tank 3 is 30min.
S2, mixing the heated coal oil slurry with the hot high-pressure oil, pressurizing by a relay pressurizing pump 18, mixing the pressurized coal oil slurry with hydrogen heated by a hydrogen heating furnace 4, and feeding the mixture into a ebullated bed reactor 5 for reaction to obtain a reaction product. The temperature in the ebullated bed reactor 5 was 380℃and the reaction pressure was 8.0MPa. Filling a microspherical catalyst in the ebullated bed reactor 5, wherein the weight ratio of the microspherical catalyst to the pulverized coal is 1:1; the volume ratio of hydrogen to hot high-fraction oil was 800.
S3, separating the reaction product in the step S2 into hot high-pressure gas and hot high-pressure oil through a hot high-pressure separation tank 6.
S4, the hot high-pressure oil-separating part in the step S3 enters the heating tank 3 and is mixed with the coal oil slurry at the bottom of the heating tank 3, wherein the mixing ratio is 1:1. The rest of the hot high-pressure oil is decompressed and enters a hot low-pressure tank 9, the low-pressure oil of the hot low-pressure tank 9 directly enters a decompression tower 15 for separation, the residual pressure at the top of the decompression tower 15 is 40mmHg, stripping steam is injected, and the stripping steam amount is 1% w of the feeding amount; the pressure reducing middle section oil is light and medium hydrogen-supplying solvent oil, and the bottom oil is heavy circulating solvent oil and clean coal. The cleavage initial distillation point of the heavy circulating solvent oil at the bottom of the vacuum tower 15 is 500 ℃.
S5, the hot high-pressure gas in the step S3 passes through the heating tank 3 and enters the air cooler 7 to be cooled to 50 ℃, and then enters the 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, enters a circulating hydrogen compressor 12 for boosting to 8.5MPag, is mixed with hydrogen of 8.5MPag entering through a new hydrogen compressor 13, enters a hydrogen heating furnace 4 for heating to 430 ℃, and enters a cold low-pressure separated tank 11 for separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure separated oil.
S6, enabling the bottom oil in the step S4 to enter a solid-liquid separation unit 17 to separate heavy circulating solvent oil and clean coal products;
s7, mixing the part of the light and medium hydrogen supply solvent oil in the step S4 and the heavy circulating solvent oil in the step S6 to prepare the circulating solvent oil of the coal slurry, and mixing the rest light and medium hydrogen supply solvent oil and the cold low-grade oil in the step S5 to prepare a coal-based oil product, wherein the sulfur content of the coal-based oil product is 0.1% w, and the nitrogen content of the coal-based oil product is 0.25% w.
Example 2
S1, mixing circulating solvent oil, coal dust below 200 meshes and a homogeneous catalyst to prepare coal-oil slurry, wherein the circulating solvent oil and the coal dust are mixed according to a mass ratio of 1.5:1, and the adding amount of the catalyst is 0.1% of the mass of the coal dust. And (3) conveying the oil-coal-slurry with high pressure into a heating tank 3, and carrying out heat exchange and temperature rise by contacting with the reacted hot high-pressure gas, wherein the residence time of the oil-coal-slurry in the heating tank 3 is 60min.
S2, mixing the heated coal oil slurry with the hot high-pressure oil, pressurizing by a relay pressurizing pump 18, mixing the pressurized coal oil slurry with hydrogen heated by a hydrogen heating furnace 4, and feeding the mixture into a ebullated bed reactor 5 for reaction to obtain a reaction product. The temperature in the ebullated bed reactor 5 was 410℃and the reaction pressure was 12.0MPa. Filling a microspherical catalyst in the ebullated bed reactor 5, wherein the weight ratio of the microspherical catalyst to the pulverized coal is 1.5:1; the volume ratio of hydrogen to hot high-fraction oil was 1000.
S3, separating the reaction product in the step S2 into hot high-pressure gas and hot high-pressure oil through a hot high-pressure separation tank 6.
S4, the hot high-pressure oil-separating part in the step S3 enters the heating tank 3 and is mixed with the coal oil slurry at the bottom of the heating tank 3, wherein the mixing ratio is 1:1. The rest of the hot high-pressure oil is decompressed and enters a hot low-pressure tank 9, the low-pressure oil of the hot low-pressure tank 9 directly enters a decompression tower 15 for separation, the residual pressure at the top of the decompression tower 15 is 20mmHg, stripping steam is injected, and the stripping steam amount is 0.5% w of the feeding amount; the pressure reducing middle section oil is light and medium hydrogen-supplying solvent oil, and the bottom oil is heavy circulating solvent oil and clean coal. The initial boiling point of the heavy circulating solvent oil at the bottom of the vacuum tower 15 is 480 ℃.
S5, the hot high-pressure gas in the step S3 passes through the heating tank 3 and enters the air cooler 7 to be cooled to 50 ℃, and then enters the 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, enters a circulating hydrogen compressor 12 for boosting to 12.5MPag, is mixed with hydrogen which enters the circulating hydrogen buffer tank 13 and is subjected to 12.5MPag, enters a hydrogen heating furnace 4 for heating to 470 ℃, and cold high-pressure separated oil and sulfur-containing sewage enter a cold low-pressure separated tank 11 for separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure separated oil.
S6, enabling the bottom oil in the step S4 to enter a solid-liquid separation unit 17 to separate heavy circulating solvent oil and clean coal products;
s7, mixing the part of the light and medium hydrogen supply solvent oil in the step S4 and the heavy circulating solvent oil in the step S6 to prepare the circulating solvent oil of the coal slurry, and mixing the rest light and medium hydrogen supply solvent oil and the cold low-grade oil in the step S5 to prepare a coal-based oil product, wherein the sulfur content of the coal-based oil product is 0.08% w, and the nitrogen content of the coal-based oil product is 0.22% w.
In order to demonstrate the effect of coal hydrogenation upgrading according to the invention, experimental measurements were made on the above examples 1 and 2.
Clean coal yield = clean coal mass/dry base coal fines mass x 100%;
coal-based oil yield= (cold low-split oil quality generated in the whole process + pressure reduction middle section oil quality of the discharging device)/dry-based coal dust quality x 100%.
The specific measurement results are shown in Table 1.
TABLE 1 coal and oil Co-refining results
| Clean coal yield/% | Coal base oil yield/% | |
| Example 1 | 48.5 | 27.8 |
| Example 2 | 41.9 | 31.4 |
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 coal hydrogenation upgrading method is characterized by comprising the following steps of:
s1, mixing pulverized coal and circulating solvent oil in an oil slurry stirring tank (1) to prepare oil-coal slurry, pressurizing the oil-coal slurry by a pressurizing pump (2), and then entering a heating tank (3), wherein the oil-coal slurry is directly contacted with hot high-pressure gas entering the heating tank (3) to enable the oil-coal slurry to exchange heat and raise the temperature;
s2, mixing the heated coal oil slurry and the heated high-pressure oil in a heating tank (3), pressurizing by a relay pressurizing pump (18), mixing the pressurized coal oil slurry with heated hydrogen from a hydrogen heating furnace (4), and reacting in a fluidized bed reactor (5) to obtain a reaction product;
s3, separating hot high-pressure gas and hot high-pressure oil from the reaction product by a hot high-pressure separation tank (6);
s4, enabling a part of the hot high-pressure oil in the step S3 to enter a heating tank (3) and oil-coal slurry at the bottom of the heating tank (3) for mixing, enabling the other part of the hot high-pressure oil to enter a hot low-pressure tank (9) in a decompression mode, enabling low oil obtained by the hot low-pressure tank (9) to enter a decompression tower (15) for separation, enabling middle-pressure oil to be light and medium hydrogen-supplying solvent oil, and enabling bottom oil to be heavy circulating solvent oil and clean coal;
s5, cooling the hot high-pressure gas in the step S3 through a heating tank (3) and an air cooler (7), then separating cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage in a cold high-pressure tank (10), buffering the cold high-pressure gas in a circulating hydrogen buffer tank (14), then pressurizing the circulating hydrogen compressor (12), mixing the cold high-pressure gas with hydrogen entering from a new hydrogen compressor (13), and then entering a hydrogen heating furnace (4), wherein the cold high-pressure oil and the sulfur-containing sewage enter a cold low-pressure tank (11), and separating sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil;
s6, enabling the bottom oil in the step S4 to enter a solid-liquid separation unit (17) to separate heavy circulating solvent oil and clean coal products;
s7, mixing part of the light and medium hydrogen supply solvent oil in the step S4 with the heavy circulating solvent oil in the step S6 to prepare circulating solvent oil of coal slurry, and mixing the other part of the light and medium hydrogen supply solvent oil with the cold low-pressure oil in the step S5 to prepare a coal-based oil product.
2. The method for upgrading coal hydrogenation according to claim 1, wherein in the step S1, the mass ratio of the pulverized coal to the circulating solvent oil is 1:0.8-2.
3. The method for the hydrogenation and upgrading of coal according to claim 1, wherein in the step S1, the pulverized coal, the circulating solvent oil and the first catalyst are mixed in a slurry stirring tank (1) to prepare a coal oil slurry, and the catalyst is selected from a homogeneous catalyst or a granular catalyst.
4. The method for upgrading coal according to claim 1, wherein in the step S2, the mass ratio of the coal oil slurry to the hot high-fraction oil is 1:0.5-5.
5. The method for improving the quality of coal hydrogenation according to claim 1, wherein in the step S2, the warmed coal oil slurry, the hot high-pressure oil and the second catalyst are mixed in a heating tank (3), and the second catalyst is a microsphere catalyst.
6. The method for upgrading coal hydrogenation according to claim 1, wherein in step S2, the ebullated-bed reactor (5) is one ebullated-bed reactor (5) or a plurality of ebullated-bed reactors (5) are connected in series.
7. The method for upgrading coal hydrogenation according to claim 1, wherein in the step S2, the reaction temperature is 340-450 ℃, the reaction pressure is 6-20 MPa, and the volume ratio of hydrogen to hot high-fraction oil is 450-1500.
8. The method for upgrading coal hydrogenation according to claim 1, wherein in the step S2, a catalyst loading tank (8) operated intermittently is arranged at the bottom of the ebullated bed reactor (5), and a solid-liquid separator is arranged inside the catalyst loading tank (8) for separating spent catalyst from coal slurry oil.
9. The method for upgrading coal according to claim 1, wherein in step S4, the cutting distillation range of the solid residuum contained in the bottom of the vacuum tower (15) is 420-550 ℃.
10. The method for the upgrading of coal according to claim 1, characterized in that in step S4 the cutting requirements of the vacuum column (15) are ensured by injecting stripping steam.
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| CN107118799A (en) * | 2017-04-20 | 2017-09-01 | 神华集团有限责任公司 | DCL/Direct coal liquefaction circulation solvent and preparation method thereof |
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| CN109181770A (en) * | 2018-07-11 | 2019-01-11 | 上海英保能源化工科技有限公司 | A method of refining production oil product and chemicals altogether for inferior heavy oil, coal |
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| CN205152158U (en) * | 2015-11-13 | 2016-04-13 | 中石化洛阳工程有限公司 | Coal tar suspension bed hydrocracking unit |
| 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 |
| CN107118799A (en) * | 2017-04-20 | 2017-09-01 | 神华集团有限责任公司 | DCL/Direct coal liquefaction circulation solvent and preparation method thereof |
| CN109181770A (en) * | 2018-07-11 | 2019-01-11 | 上海英保能源化工科技有限公司 | A method of refining production oil product and chemicals altogether for inferior heavy oil, coal |
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| CN117264650A (en) * | 2023-11-17 | 2023-12-22 | 上海竣铭化工工程设计有限公司成都分公司 | Biomass hydrogenation liquefaction system and method |
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