CN112877090A - Coal direct liquefaction circulating solvent and preparation method and system thereof - Google Patents
Coal direct liquefaction circulating solvent and preparation method and system thereof Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 233
- 239000002904 solvent Substances 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 194
- 239000011280 coal tar Substances 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000005194 fractionation Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims description 120
- 239000001257 hydrogen Substances 0.000 claims description 88
- 229910052739 hydrogen Inorganic materials 0.000 claims description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 42
- 230000008569 process Effects 0.000 claims description 42
- 238000004821 distillation Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 36
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 30
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- -1 VIB group metals Chemical class 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 210000003918 fraction a Anatomy 0.000 claims 1
- 239000003921 oil Substances 0.000 description 184
- 239000000047 product Substances 0.000 description 45
- 238000010438 heat treatment Methods 0.000 description 22
- 239000002994 raw material Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 description 5
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910015427 Mo2O3 Inorganic materials 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011874 heated mixture Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Images
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
- C10G1/008—Controlling or regulating of liquefaction 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
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/12—Controlling or regulating
-
- 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
- C10G2300/4093—Catalyst stripping
-
- 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
- C10G2300/70—Catalyst aspects
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- 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 relates to a coal direct liquefaction circulating solvent and a preparation method and a system thereof, wherein the method comprises the following steps: s1, carrying out a first hydrogenation reaction on the direct coal liquefaction oil to obtain coal liquefaction hydrogenation stabilized oil; performing a second hydrogenation reaction on the coal tar to obtain coal tar hydrogenation stabilized oil; s2, performing first fractionation on the coal liquefaction hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c; performing second fractionation on the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e; s3, mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal liquefaction circulating solvent. According to the invention, the hydrogenated coal tar is introduced to replace part of the coal to directly liquefy the self-produced circulating solvent, so that the stability of the properties of the circulating solvent can be ensured while the performance of the circulating solvent is improved, and the liquefaction and conversion of the coal can be promoted.
Description
Technical Field
The invention relates to direct coal liquefaction, in particular to a direct coal liquefaction circulating solvent and a preparation method and a system thereof.
Background
The direct coal liquefaction technology refers to a process of converting coal into liquid fuel through hydrocracking under the action of hydrogen and a catalyst. The solvent is an important medium in the coal liquefaction reaction process, and the main functions of the solvent can be mainly summarized as the following: the method comprises the steps of dissolving and swelling, dispersing, providing active hydrogen, transferring the active hydrogen, dissolving gas-phase hydrogen and diluting a liquefied product, wherein the hydrogen providing effect is that hydrogen can be directly provided or transferred to coal hot free radical fragments in the direct coal liquefaction reaction process, so that free radicals can be stabilized in time and micromolecular oil is converted, and therefore the hydrogen providing performance of a solvent is directly related to the coal liquefaction conversion rate and the oil yield.
The current direct coal liquefaction hydrogen supply solvent is from the self coal liquefaction product and is obtained by adopting a hydrogenation mode. The method is characterized in that coal liquefaction crude oil obtained by directly liquefying coal is subjected to hydrotreating and recycled to a coal slurry preparation part, and the main effects of solvent hydrogenation comprise three parts: firstly, the aromatics are partially saturated by hydrogenation, so that the hydrogen energy capacity of the solvent is improved; secondly, the viscosity of the coal oil slurry can be reduced, and the transportation is convenient; and thirdly, removing the heteroatoms in the direct coal liquefaction oil, and providing qualified raw materials for further processing the direct coal liquefaction oil to produce qualified fuels and other chemical products. The hydrogen supply capacity of the solvent is directly related to the yield and the conversion rate of the direct coal liquefaction oil, and how to keep the high activity of the circulating solvent and the stability of the property of the circulating solvent so that the conversion rate and the oil yield of the coal can be kept all the time in the liquefaction reaction process is the key research direction in the field of direct coal liquefaction at present.
In the direct coal liquefaction process, as the solvent is from the self reaction product and continuously circulates in the system, the property of the solvent is easy to change, and substances which are not beneficial to the coal liquefaction reaction can aggregate, such as paraffin and cyclane; in addition, fluctuation occurs in the direct coal liquefaction process, and the influence on the properties of the circulating solvent is also caused, for example, secondary cracking is serious and the reaction depth is insufficient when the coal liquefaction process is operated at low load, the hydrogenation depth of the circulating solvent is too high, so that the aromatic hydrocarbon hydrogenation supersaturation is caused, the amount of the circulating solvent is slightly insufficient, and the like are unfavorable phenomena. These all cause the conversion rate and oil yield of coal to be reduced, and are a vicious circle, which directly influences the benefit of direct coal liquefaction.
CN105925304A discloses a coal direct liquefaction circulating solvent and a preparation method thereof. The method comprises the steps of firstly fractionating the direct coal liquefaction oil, cutting the direct coal liquefaction oil into heavy oil fraction, medium fraction and light fraction, independently hydrogenating the heavy fraction, and then mixing the heavy fraction and the medium fraction to be used as a circulating solvent, wherein although the hydrogenation effect of the heavy fraction is improved, the medium fraction is not hydrogenated and has higher content, so that the hydrogen supply performance of the solvent cannot be effectively improved; in addition, the viscosity of the coal oil slurry is also increased, which puts higher requirements on transportation and also has adverse effects on downstream product processing devices.
CN103468315A discloses a coal direct liquefaction circulating solvent and a preparation method thereof. According to the method, the anthracene oil in the coal tar and the direct coal liquefaction oil are jointly hydrogenated, and the direct coal liquefaction oil is obtained after fractionation to obtain the circulating solvent.
In conclusion, the existing processing method of the circulating solvent for direct coal liquefaction has the defects of poor hydrogen supply capability of the circulating hydrogen solvent, complex process route, high investment cost for device construction, high operation difficulty and the like, and the problems of deterioration of hydrogen supply property of the circulating solvent and maintenance of high activity of the solvent are not thoroughly solved, so that the existing processing method of the circulating solvent still needs to be improved.
Disclosure of Invention
The invention aims to solve the problems of poor hydrogen supply capability and poor liquefaction activity stability of a direct coal liquefaction circulating solvent in the prior art, and provides the direct coal liquefaction circulating solvent and a preparation method and a system thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a coal direct liquefaction recycled solvent, comprising the steps of:
s1, in the presence of a hydrogen-containing gas and a first hydrogenation catalyst, carrying out a first hydrogenation reaction on the coal direct liquefaction oil to obtain a first hydrogenation product, and carrying out first separation on the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil; and
performing a second hydrogenation reaction on the coal tar in the presence of a hydrogen-containing gas and a second hydrogenation catalyst to obtain a second hydrogenation product, and performing second separation on the second hydrogenation product to obtain coal tar hydrogenation stable oil;
s2, performing first fractionation on the coal liquefaction hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c; and
performing second fractionation on the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
s3, mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal liquefaction circulating solvent.
The invention provides a coal direct liquefaction circulating solvent prepared by the method.
The third aspect of the invention provides a system for preparing a coal direct liquefaction circulating solvent, which comprises a coal direct liquefaction oil treatment system and a coal tar treatment system which are respectively communicated with a mixing system;
the coal direct liquefaction oil treatment system comprises:
the direct coal liquefaction oil tank is used for storing direct coal liquefaction oil;
the first hydrogenation reactor is used for carrying out first hydrogenation reaction on the direct coal liquefaction oil from the direct coal liquefaction oil tank to obtain a first hydrogenation product;
the first separation system is used for separating the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil;
the first fractionating tower is used for fractionating the coal liquefied hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c;
the coal tar treatment system comprises:
the coal tar tank is used for storing direct coal liquefaction oil;
the second hydrogenation reactor is used for carrying out second hydrogenation reaction on the direct coal liquefaction oil from the coal tar tank to obtain a second hydrogenation product;
the second separation system is used for separating the second hydrogenation product to obtain coal tar hydrogenation stabilized oil;
the second fractionating tower is used for fractionating the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
and the mixing system is used for mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal direct liquefaction circulating solvent.
According to the technical scheme, the coal tar is obtained in the coal pyrolysis process, the composition of the coal tar is similar to that of coal, aromatic hydrocarbon is mainly used, the content of the aromatic hydrocarbon is higher than that of a coal direct liquefaction circulating solvent, and the coal tar subjected to independent hydrogenation is introduced in the coal direct liquefaction process, so that the hydrogen supply capacity of the coal liquefaction circulating solvent is improved;
secondly, by introducing hydrogenated coal tar to replace part of the coal to directly liquefy the self-produced circulating solvent, the properties of the circulating solvent can be ensured to be stable while the performance of the circulating solvent is improved, and high hydrogen supply performance is kept, so that the coal liquefaction conversion is facilitated, and high oil yield is obtained;
in addition, in the coal liquefaction process, the coal tar is introduced as a solvent, so that the coal and the coal tar are co-refined, the processing mode and the processing difficulty of the coal tar are widened, more target products can be replaced, and the direct coal liquefaction economic benefit is favorably improved.
Drawings
Fig. 1 is a flow chart of a process for preparing a recycled solvent for direct coal liquefaction according to an embodiment of the present invention.
Description of the reference numerals
1. Direct coal liquefaction oil 2 and coal tar
3. Hydrogen-containing gas 4, circulating hydrogen
5. Tail gas 6, light distillate oil a
7. Middle distillate oil b 8 and heavy distillate oil c
9. Light fraction oil d 10, heavy fraction oil e
110. Coal direct liquefaction oil tank 120 and first heating furnace
130. A first hydrogenation reactor 140, a first hot high pressure separator
150. First high-pressure heat exchanger 160, first cold high-pressure separator
170. Third heating furnace 180, first fractionating column
101. A first high-pressure raw material pump 102 and a first circulating pump
103. The first recycle hydrogen compressor 210, a coal tar tank
220. Second heating furnace 230 and second hydrogenation reactor
240. Second heat high-pressure separator 250, second high-pressure heat exchanger
260. Second cold high-pressure separator 270, fourth heating furnace
280. Second fractionating column 201, second high-pressure feedstock pump
202. Second circulation pump 203, second circulation hydrogen compressor
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing a coal direct liquefaction circulating solvent, which comprises the following steps:
s1, in the presence of a hydrogen-containing gas and a first hydrogenation catalyst, carrying out a first hydrogenation reaction on the coal direct liquefaction oil to obtain a first hydrogenation product, and carrying out first separation on the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil; and
performing a second hydrogenation reaction on the coal tar in the presence of a hydrogen-containing gas and a second hydrogenation catalyst to obtain a second hydrogenation product, and performing second separation on the second hydrogenation product to obtain coal tar hydrogenation stable oil;
s2, performing first fractionation on the coal liquefaction hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c; and
performing second fractionation on the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
s3, mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal liquefaction circulating solvent.
In the invention, the direct coal liquefaction oil and the coal tar are respectively subjected to hydrogenation reaction, so that the partial saturation of aromatic hydrocarbons in the direct coal liquefaction oil and the coal tar is realized, the hydrogen supply performance of a circulating solvent is improved, and qualified raw materials are provided for downstream product processing. Fractionating the coal liquefaction hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c, and fractionating the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e; the heavy fractions (heavy distillate c and heavy distillate e) and part of the medium fraction (medium distillate b) are mixed and then used as a circulating hydrogen supply solvent, the coal tar is from the coal pyrolysis process, the coal tar mainly contains aromatic hydrocarbon, the aromatic hydrocarbon content is higher than that of the direct coal liquefaction circulating solvent, and the hydrogen supply performance of the coal tar is superior to that of the direct coal liquefaction circulating solvent after hydrogenation, so that the coal tar subjected to independent hydrogenation is introduced to replace part of the circulating solvent in the direct coal liquefaction process, and the hydrogen supply capacity of the direct coal liquefaction circulating solvent is improved.
Secondly, because of the direct coal liquefaction process, the coal liquefaction self-production solvent is in the continuous circulation process, the unfavorable component saturated hydrocarbon in the circulation solvent can be aggregated, the property of the circulation solvent is deteriorated, meanwhile, the fluctuation in the direct coal liquefaction reaction process can also cause the recycling solvent to be incapable of being recovered, the property of the circulation solvent is poor, the coal liquefaction reaction is not facilitated, the coal tar hydrogenation stable oil is introduced to replace part of the direct coal liquefaction self-production circulation solvent, the property stability of the circulation solvent can be ensured while the property of the circulation solvent is improved, and the high hydrogen supply performance is kept, so that the coal liquefaction conversion can be facilitated, and the high oil yield can be obtained.
In addition, in the coal liquefaction process, the coal tar is introduced as a solvent, so that the coal and the coal tar can be co-refined, the processing mode and the processing difficulty of the coal tar are widened, more target products can be replaced, and the direct coal liquefaction economic benefit can be improved.
In the invention, in order to improve the hydrogen supply capacity of the circulating solvent, the coal direct liquefaction oil is coal direct liquefaction full distillate oil or coal direct liquefaction distillate oil with the distillation range of more than 200 ℃; preferably, the distillation range of the coal direct liquefaction distillate oil is 220-500 ℃, the saturated hydrocarbon content is low, the unsaturated aromatic hydrocarbon content is high, and a circulating solvent with higher hydrogen supply capacity can be obtained after catalytic hydrogenation and fractionation.
In the invention, in order to improve the hydrogen supply capacity of the circulating solvent, the distillation range of the coal tar is less than 500 ℃; preferably, the distillation range of the coal tar is 220-500 ℃, more preferably 220-400 ℃, the coal tar distillate oil with the distillation range of 220-500 ℃ has low content of saturated hydrocarbon and higher content of unsaturated aromatic hydrocarbon and does not contain asphaltene, the circulating solvent with stronger hydrogen supply capability can be obtained after catalytic hydrogenation and fractionation, the coal tar distillate oil with the distillation range of 220-400 ℃ has lower content of saturated hydrocarbon and higher content of unsaturated aromatic hydrocarbon, hydrogenation saturation reaction is easier to occur, the addition amount of the coal tar can be increased, the circulating solvent with better hydrogen supply performance can be obtained after catalytic hydrogenation and fractionation, and more target products can be produced.
In the invention, in order to further improve the hydrogen supply capacity of the circulating solvent, the aromatic hydrocarbon content in the coal tar is more than 70 wt%, preferably more than 85 wt% based on the total weight of the coal tar under the preferable conditions.
In a preferred embodiment of the invention, in order to obtain the recycled solvent with better hydrogen supply performance, the distillation range of the coal tar is 220-500 ℃, and the weight content of aromatic hydrocarbon in the coal tar is more than 70 wt% based on the total weight of the coal tar, more preferably, the distillation range of the coal tar is 220-400 ℃, and the weight content of aromatic hydrocarbon in the coal tar is more than 85 wt%.
The distillation range of the washing oil and the anthracene oil is narrow, the distillation range is less than 400 ℃, the aromatic hydrocarbon content is more than 90 wt%, and the coal tar does not contain asphaltene, and is selected from the washing oil and/or the anthracene oil under the preferable condition in order to further improve the hydrogen supply performance of the circulating solvent.
In the invention, in order to obtain a better coal direct liquefaction circulating solvent, the distillation range of the light distillate oil a is less than 220 ℃ under the preferable condition, and more preferably less than 200 ℃; under the preferable conditions, the distillation range of the middle distillate oil b is 200-350 ℃, and more preferably 220-350 ℃; preferably, the distillation range of the heavy distillate oil c is more than 200 ℃; preferably, the distillation range of the heavy distillate oil e is more than 220 ℃, more preferably more than 350 ℃. The coal liquefaction hydrogenation stable oil and the coal tar hydrogenation stable oil are fractionated according to the mode, so that the hydrogen supply component and the non-hydrogen supply component (or weak hydrogen supply component) in the hydrogenation product of the direct coal liquefaction oil can be more fully separated, and the final direct coal liquefaction circulating solvent has higher content of aromatic hydrocarbon, so that the direct coal liquefaction circulating solvent has better hydrogen supply performance.
In the present invention, in order to further increase the content of aromatic hydrocarbons in the recycle solvent and improve the hydrogen-donating performance of the recycle solvent, the weight content of aromatic hydrocarbons in the heavy distillate oil e is greater than 80 wt% based on the total weight of the heavy distillate oil e under the preferable conditions.
In the invention, in order to improve the content of aromatic hydrocarbon in the circulating solvent, improve the hydrogen supply performance and stability of the circulating solvent and produce more target products, the weight content of the heavy distillate oil c is 20-35 wt%, the weight content of the heavy distillate oil e is not higher than 80 wt% and the weight content of the medium distillate oil b is 0-80 wt% based on the total weight of the coal direct liquefaction circulating solvent; further preferably, the weight content of the heavy distillate oil c is 25-35 wt%, the weight content of the heavy distillate oil e is 30-65 wt%, and the weight content of the medium distillate oil b is 0-45 wt%.
In the present invention, the first hydrogenation catalyst and the second hydrogenation catalyst may be known to those skilled in the art. In a preferred embodiment of the present invention, in order to make the catalyst have better hydrogenation saturation activity and hydrodenitrogenation, oxygen and sulfur activities, the hydrogenation reaction is facilitated to be performed, the generation amount of partial saturated aromatic hydrocarbons in the hydrogenation reaction is increased, the content of active hydrogen in the coal liquefaction circulating solvent is increased, and further, the hydrogen supply capacity of the circulating hydrogen supply solvent is improved. Under preferred conditions, the first hydrogenation catalyst comprises a first carrier and a first active component loaded on the first carrier, and the second hydrogenation catalyst comprises a second carrier and a second active component loaded on the second carrier; the first active component and the second active component are respectively and independently selected from at least one of VIB group metals and/or VIII group metals; further preferably, the group VIB metal is selected from molybdenum and/or tungsten; the group VIII metal is selected from cobalt and/or nickel.
Preferably, the first support and the second support are each independently at least one selected from amorphous oxides and silicates.
Preferably, the weight content of the first active component in terms of oxide is 10-40 wt% based on the total amount of the first hydrogenation catalyst; the weight content of the second active component calculated by oxide is 10-40 wt% based on the total amount of the second hydrogenation catalyst.
In a preferred embodiment of the present invention, the first hydrogenation catalyst and the second hydrogenation catalyst are the same, the carrier is aluminum silicate, and the active components are Mo and Ni.
The hydrogenation reaction of the direct coal liquefaction oil and the coal tar is mainly aromatic saturation reaction, and the aromatic hydrogenation is reversible reaction and is influenced by reaction kinetics and thermodynamics. In the present invention, in order to increase the content of part of saturated aromatic hydrocarbons in the hydrogenation reaction and increase the content of active hydrogen to further improve the hydrogen supply capacity of the recycled hydrogen supply solvent, preferably, the first hydrogenation reaction is performed under at least the following conditions: the reaction temperature is 320-400 ℃, and preferably 350-390 ℃; the reaction pressure is 8-22MPa, preferably 12-19 MPa; the hydrogen-oil ratio is 300-1000 and the volume space velocity is 0.5-2.0h-1(ii) a Further preferably, the second hydrogenation reaction is performed under conditions at least satisfying: the reaction temperature is 320-400 ℃, and preferably 350-390 ℃; the reaction pressure is 8-22MPa, preferably 12-19 MPa; the hydrogen-oil ratio is 300-1000 and the volume space velocity is 0.5-2.0h-1。
In order to improve the hydrogen donating ability and stability of the circulating solvent, it is preferable that the first separation comprises, in step S1: carrying out first hot high separation on the first hydrogenation product to obtain first hot high separation gas and first hot high separation liquid, and then carrying out first cold high separation on the first hot high separation gas to obtain first hydrogen-containing gas and first cold low separation liquid; and mixing the first hot high separation liquid and the first cold low separation liquid to obtain the coal liquefaction hydrogenation stabilized oil. Further preferably, the conditions of the first thermal high separation at least satisfy: the temperature is 230-: the temperature is 230 ℃ and 350 ℃, and the pressure is 12-19 MPa; preferably, the first cold-high separation condition at least satisfies: the temperature is 45-54 deg.C, and the pressure is 8-22MPa, preferably 12-19 MPa.
In order to improve the hydrogen donating ability and stability of the recycled solvent, under preferable conditions, in step S1, the second separation comprises: performing second hot high separation on the second hydrogenation product to obtain second hot high separation gas and second hot high separation liquid, and then performing second cold high separation on the second hot high separation gas to obtain second hydrogen-containing gas and second cold low separation liquid; mixing the second hot high separation liquid and the second cold low separation liquid to obtain coal tar hydrogenation stabilized oil; further preferably, the second thermal high separation condition at least satisfies: the temperature is 230-270 ℃, the pressure is 8-22MPa, more preferably the temperature is 230-350 ℃, and the pressure is 12-19 MPa; preferably, the conditions of the second cold high separation at least satisfy the following conditions: the temperature is 45-54 deg.C, and the pressure is 8-22MPa, preferably 12-19 MPa.
In the present invention, in order to obtain a coal direct liquefaction recycle solvent with better hydrogenation performance, it is preferable that the first fractionation condition at least satisfies: the pressure is 0.1-0.2MPa, and the temperature is 300-350 ℃; the second fractionation is performed under conditions at least satisfying: the pressure is 0.1-0.2MPa, and the temperature is 300-350 ℃.
In the invention, the solvent with strong hydrogen supply capacity can be obtained by adopting the specific steps and the process parameters, and the stability of the property of the circulating solvent is ensured. In a preferred embodiment of the invention, the remaining medium fraction b and the total light fraction d are mixed to form the coal liquefaction product. The coal liquefaction product is obtained while the circulating hydrogen supply solvent is prepared by the process steps. The method is beneficial to widening the hydrogenation path of the coal tar, reducing the processing difficulty of the coal tar, improving the economy of the coal liquefaction device and providing qualified raw materials for further processing of downstream coal liquefaction products. The coal liquefaction product can be used for producing liquid fuel or used as a chemical product raw material after downstream processing.
The invention also provides a coal direct liquefaction circulating solvent prepared by the method, wherein the weight content of saturated aromatic hydrocarbon in the coal direct liquefaction circulating solvent is 80-90 wt%; the weight content of paraffinic hydrocarbons is less than 5 wt%; the content of naphthenes is less than 15 wt%; further preferably, the weight content of saturated aromatic hydrocarbon in the coal direct liquefaction circulating solvent is 81-89 wt%; the weight content of paraffinic hydrocarbons is from 2 to 3 wt%; the content of naphthenes is 10.8-13 wt%.
Fig. 1 is a flow chart of a process for preparing a coal direct liquefaction circulating solvent according to an embodiment of the present invention, and as shown in fig. 1, the present invention also provides a system for preparing a coal direct liquefaction circulating solvent, including: the system comprises a mixing system, a coal direct liquefaction oil treatment system and a coal tar treatment system which are respectively communicated with the mixing system;
the coal direct liquefaction oil treatment system comprises:
a direct coal liquefaction tank 110 for storing direct coal liquefaction oil;
the first hydrogenation reactor 130 is configured to perform a first hydrogenation reaction on the direct coal liquefaction oil from the direct coal liquefaction oil tank to obtain a first hydrogenation product;
the first separation system is used for separating the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil;
the first fractionating tower 180 is used for fractionating the coal liquefied hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c;
the coal tar treatment system comprises:
a coal tar tank 210 for storing coal direct liquefaction oil;
the second hydrogenation reactor 230 is configured to perform a second hydrogenation reaction on the coal direct liquefaction oil from the coal tar tank to obtain a second hydrogenation product;
the second separation system is used for separating the second hydrogenation product to obtain coal tar hydrogenation stabilized oil;
the second fractionating tower 280 is used for fractionating the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
and the mixing system is used for mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal direct liquefaction circulating solvent.
In order to improve the hydrogen supply capacity and stability of the circulating solvent, it is preferable that the first separation system comprises: a first thermal high separator 140, configured to perform first thermal high separation on the first hydrogenation product to obtain a first thermal high separation gas and a first thermal high separation liquid;
the first cold high separator 160 is configured to perform a first cold high separation on the first hot high separation gas to obtain a first hydrogen-containing gas and a first cold low separation liquid.
Preferably, the second separation system comprises:
a second thermal high separator 240, configured to perform second thermal high separation on the second hydrogenation product to obtain a second thermal high separation gas and a second thermal high separation liquid;
and the second cold high separator 260 is used for performing second cold high separation on the second hot high separation gas to obtain a second hydrogen-containing gas and a second cold low separation liquid.
In the invention, partial saturation and heteroatom removal reactions of aromatic hydrocarbon mainly occur in the hydrogenation reaction process, the hydrocracking reaction is avoided as much as possible, and the over-saturation of hydrogenation can cause the excessive increase of the content of saturated hydrocarbon in the circulating solvent if the hydrogenation supersaturation and insufficient hydrogenation depth are prevented; the hydrogenation depth is insufficient, the aromatic hydrocarbon is not fully and partially saturated, and the active hydrogen content is low; both of which lead to insufficient hydrogen donating ability of the recycled solvent. Preferably, the first hydrogenation reactor and the second hydrogenation reactor are respectively and independently selected from a fixed bed reactor, an expanded bed reactor, a slurry bed reactor or a forced internal circulation fluidized bed reactor, more preferably, the first hydrogenation reactor and the second hydrogenation reactor are both forced internal circulation fluidized bed reactors, the forced internal circulation fluidized bed reactors have strong adaptability to raw materials, the online replacement of a catalyst can be realized, the activity of the catalyst is stable, the reaction temperature is controlled more uniformly, the property of hydrogenated oil is relatively stable, and the property of a circulating solvent is also relatively stable.
In the present invention, there is no special requirement on the type of the mixing system, as long as the mixing of the heavy distillate oil c, the heavy distillate oil e and the medium distillate oil b can be achieved, and the mixing system can be known to those skilled in the art, and can be, for example, a pipeline.
The present invention will be described in detail below by way of examples.
In the following examples, the properties of the feedstock are shown in Table 1, and the distillation range of the feedstock was measured according to ASTM D1160-2015.
The carrier of the hydrogenation catalyst A is aluminum silicate, the active ingredients are Mo and Ni, calculated by oxide, the Mo2O3The weight content of NiO is 20.6wt percent, and the weight content of NiO is 4.6wt percent;
the carrier of the hydrogenation catalyst B is aluminum silicate, the active ingredients are Mo and Co, calculated by oxide, Mo2O320.6 wt% of Co2O3Is 4.6 wt%;
the carrier of the hydrogenation catalyst C is aluminum silicate, the active ingredients are Mo, Co and Ni, calculated by oxide, the Mo2O320 wt%, NiO 3 wt%, Co2O3The content of (B) is 2 wt%.
TABLE 1
Example 1
A method for preparing a coal direct liquefaction circulating solvent comprises the following steps:
s1, introducing the coal direct liquefaction full distillate oil 1 into a coal direct liquefaction oil tank 110, boosting the pressure of the coal direct liquefaction oil by a first high-pressure raw material pump 101, mixing the coal direct liquefaction oil with hydrogen 3 to obtain a mixture flow, heating the mixture flow by a first heating furnace 120, introducing the heated mixture flow into a first hydrogenation reactor 130 (fluidized bed reactor) containing a hydrogenation catalyst A to perform a first hydrogenation reaction, realizing partial saturation of aromatic hydrocarbons and heteroatom removal reaction, and obtaining a first hydrogenation product, wherein a first forced circulation pump 102 is arranged at the bottom of the first hydrogenation reactor 130.
The first hydrogenation product enters a first hot high-pressure separator 140 for first hot high separation after heat exchange and cooling to obtain a first hot high separation gas and a first hot high separation liquid, and the conditions of the first hot high separation are as follows: the temperature is 250 ℃, and the pressure is 15 MPa; the first hot high separation gas is cooled by the first high pressure heat exchanger 150 and then enters the first cold high pressure separator 160 to perform first cold high separation, so as to obtain a first hydrogen-containing gas and a first cold low separation liquid, wherein the first cold high separation conditions are as follows: the temperature is 54 ℃, and the pressure is 15 MPa;
part of the first hydrogen-containing gas serving as recycle hydrogen 4 is subjected to pressure increase by the first recycle hydrogen compressor 103 and then is circulated to the inlet of the first heating furnace 120 to be mixed with the coal direct liquefaction oil 1, and the rest part of the first hydrogen-containing gas serving as tail gas 5 is discharged; and mixing the first hot high separation liquid after pressure reduction with the first cold low separation liquid to obtain the coal liquefaction hydrogenation stable oil.
Introducing coal tar 2 (with distillation range less than 500 ℃) into a coal tar tank 210, boosting the pressure by a second high-pressure raw material pump 201, and mixing with hydrogen 3 to obtain a mixed material flow; the mixture is heated by the second heating furnace 220 and then introduced into the second hydrogenation reactor 230 (ebullated bed reactor) containing the hydrogenation catalyst a to perform a second hydrogenation reaction, so as to achieve partial saturation of aromatic hydrocarbons and a heteroatom removal reaction, thereby obtaining a second hydrogenation product, and the bottom of the second hydrogenation reactor 230 is provided with the second forced circulation pump 202.
The second hydrogenation product enters a second hot high-pressure separator 240 after heat exchange and cooling to perform second hot high separation, so as to obtain a second hot high separation gas and a second hot high separation liquid, wherein the conditions of the second hot high separation are as follows: the temperature is 250 ℃, and the pressure is 15 MPa; the second hot high separation gas is cooled by the second high pressure heat exchanger 250 and then enters the second cold high pressure separator 260 to perform second cold high separation, so as to obtain a second hydrogen-containing gas and a second cold low separation liquid, wherein the conditions of the second cold high separation are as follows: the temperature is 54 ℃, and the pressure is 15 MPa;
part of the second hydrogen-containing gas is used as recycle hydrogen 4, is subjected to pressure increase by the second recycle hydrogen compressor 203 and then is recycled to the inlet of the second heating furnace 220 to be mixed with the coal tar 2, and the rest part of the second hydrogen-containing gas is used as tail gas 5 to be discharged; and mixing the second hot high separation liquid and the second cold low separation liquid after pressure reduction to obtain the coal tar hydrogenation stabilized oil.
S2, heating the coal liquefaction hydrogenation stabilized oil by a third heating furnace 170, introducing the heated coal liquefaction hydrogenation stabilized oil into a first fractionating tower 180 for first fractionating under the first fractionating condition of 300 ℃ and 0.1MPa to obtain light distillate oil a 6 with the distillation range of less than 200 ℃, medium distillate oil b 7 with the distillation range of 200 ℃ and 350 ℃ and heavy distillate oil c 8 with the distillation range of more than 350 ℃;
heating the coal tar hydrogenation stabilized oil by a fourth heating furnace 270, introducing the coal tar hydrogenation stabilized oil into a second fractionating tower 280 for second fractionation, wherein the second fractionation condition is 300 ℃ and 0.1MPa, and obtaining light distillate oil d 9 with the distillation range of less than 200 ℃ and heavy distillate oil e 10 with the distillation range of more than 200 ℃;
and S3, mixing the heavy distillate oil c, the heavy distillate oil e and part of the medium distillate oil b in a pipeline to obtain a coal liquefaction circulating solvent, wherein the heavy distillate oil e accounts for 30 wt% of the circulating solvent.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 2
The procedure of example 1 is followed except that the heavy fraction e represents 65% by weight of the total amount of recycled solvent.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 3
The process of example 1 was followed except that the feed oil of the direct coal liquefaction oil was coal liquefaction oil B having a boiling range of greater than 200 ℃.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 4
The method of example 1 is followed except that the raw oil of the coal direct liquefaction oil is coal liquefaction oil C with distillation range of 220-.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 5
The method of example 1 was followed except that the coal tar feedstock oil was coal tar B having a distillation range of 220-;
the types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 6
The process of example 1 was followed except that the coal tar feedstock oil was coal tar C having a distillation range of 220 ℃. times.400 ℃ and the heavy distillate oil e accounted for 45 wt% of the amount of circulating solvent.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 7
The process of example 1 was followed except that the coal tar base oil was wash oil and the heavy distillate e accounted for 45 wt% of the recycle solvent amount.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 8
The process of example 1 was followed except that the coal tar base oil was anthracene oil and the heavy distillate e accounted for 45 wt% of the recycle solvent amount.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 9
According to the method of example 1, except that the first hydrogenation reactor and the second hydrogenation reactor are both fixed bed reactors, and the conditions of the first fractionation and the second fractionation are different from those of example 1, the following steps are specifically performed:
s1, introducing the coal direct liquefaction full distillate oil 1 into a coal direct liquefaction oil tank 110, boosting the pressure of the coal direct liquefaction oil by a first high-pressure raw material pump 101, mixing the coal direct liquefaction oil with hydrogen 3 to obtain a mixture flow, heating the mixture flow by a first heating furnace 120, introducing the heated mixture flow into a first hydrogenation reactor 130 (a fixed bed reactor) containing a hydrogenation catalyst A to perform a first hydrogenation reaction, realizing partial saturation of aromatic hydrocarbon and heteroatom removal reaction, and obtaining a first hydrogenation product, wherein a first forced circulation pump 102 is arranged at the bottom in the first hydrogenation reactor 130.
The first hydrogenation product enters a first hot high-pressure separator 140 for first hot high separation after heat exchange and cooling to obtain a first hot high separation gas and a first hot high separation liquid, and the conditions of the first hot high separation are as follows: the temperature is 250 ℃, and the pressure is 15 MPa; the first hot high separation gas is cooled by the first high pressure heat exchanger 150 and then enters the first cold high pressure separator 160 to perform first cold high separation, so as to obtain a first hydrogen-containing gas and a first cold low separation liquid, wherein the first cold high separation conditions are as follows: the temperature is 54 ℃, and the pressure is 15 MPa;
part of the first hydrogen-containing gas serving as recycle hydrogen 4 is subjected to pressure increase by the first recycle hydrogen compressor 103 and then is circulated to the inlet of the first heating furnace 120 to be mixed with the coal direct liquefaction oil 1, and the rest part of the first hydrogen-containing gas serving as tail gas 5 is discharged; and mixing the first hot high separation liquid after pressure reduction with the first cold low separation liquid to obtain the coal liquefaction hydrogenation stable oil.
Introducing coal tar 2 (with distillation range less than 500 ℃) into a coal tar tank 210, boosting the pressure by a second high-pressure raw material pump 201, and mixing with hydrogen 3 to obtain a mixed material flow; the mixture is heated by the second heating furnace 220 and then introduced into the second hydrogenation reactor 230 (fixed bed reactor) containing the hydrogenation catalyst a to perform a second hydrogenation reaction, so as to achieve partial saturation of aromatic hydrocarbon and heteroatom removal reaction, thereby obtaining a second hydrogenation product, and the bottom of the second hydrogenation reactor 230 is provided with the second forced circulation pump 202.
The second hydrogenation product enters a second hot high-pressure separator 240 after heat exchange and cooling to perform second hot high separation, so as to obtain a second hot high separation gas and a second hot high separation liquid, wherein the conditions of the second hot high separation are as follows: the temperature is 250 ℃, and the pressure is 15 MPa; the second hot high separation gas is cooled by the second high pressure heat exchanger 250 and then enters the second cold high pressure separator 260 to perform second cold high separation, so as to obtain a second hydrogen-containing gas and a second cold low separation liquid, wherein the conditions of the second cold high separation are as follows: the temperature is 54 ℃, and the pressure is 15 MPa;
part of the second hydrogen-containing gas is used as recycle hydrogen 4, is subjected to pressure increase by the second recycle hydrogen compressor 203 and then is recycled to the inlet of the second heating furnace 220 to be mixed with the coal tar 2, and the rest part of the second hydrogen-containing gas is used as tail gas 5 to be discharged; and mixing the second hot high separation liquid and the second cold low separation liquid after pressure reduction to obtain the coal tar hydrogenation stabilized oil.
S2, heating the coal liquefaction hydrogenation stabilized oil by a third heating furnace 170, introducing the heated coal liquefaction hydrogenation stabilized oil into a first fractionating tower 180 for first fractionation, wherein the first fractionating condition is 300 ℃ and 0.1MPa, and obtaining light distillate oil a 6 with the distillation range of less than 220 ℃, medium distillate oil b 7 with the distillation range of 220 ℃ and 350 ℃ and heavy distillate oil c 8 with the distillation range of more than 350 ℃;
heating the coal tar hydrogenation stabilized oil by a fourth heating furnace 270, introducing the coal tar hydrogenation stabilized oil into a second fractionating tower 280 for second fractionation, wherein the second fractionation condition is 300 ℃ and 0.1MPa, and obtaining light distillate oil d 9 with the distillation range of less than 220 ℃ and heavy distillate oil e 10 with the distillation range of more than 220 ℃;
and S3, mixing the heavy distillate oil c, the heavy distillate oil e and part of the medium distillate oil b in a pipeline to obtain a coal liquefaction circulating solvent, wherein the heavy distillate oil e accounts for 30 wt% of the circulating solvent.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 10
The process of example 9 was followed except that the first hydrogenation catalyst and the second hydrogenation catalyst were both hydrogenation catalyst B.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Example 11
The process of example 9 was followed except that the first hydrogenation catalyst and the second hydrogenation catalyst were both hydrogenation catalyst C.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
Comparative example 1
The process of example 1 was followed except that: the coal liquefaction circulating solvent is a coal direct liquefaction self-production solvent and comprises the following components: 75 wt% of middle distillate oil b (distillation range of 220-350 ℃) and 25 wt% of heavy distillate oil c (distillation range of more than 350 ℃) are mixed to be used as the circulating solvent.
The types of raw materials for preparing the coal liquefaction cycle solvent and the composition of the coal liquefaction cycle solvent in this example are shown in table 2.
The process parameters of the steps in this example are shown in table 3, and the basic properties of the obtained coal liquefaction cycle solvent are shown in table 4.
TABLE 2
TABLE 3
TABLE 4
TABLE 4 continuation
Examples of the experiments
Evaluation of coal liquefaction performance of circulating solvent:
the direct coal liquefaction reaction was carried out using a 0.2t/d direct coal liquefaction experimental apparatus, and the performance of direct coal liquefaction by the recycled solvent obtained in examples 1 to 11 and comparative example 1 was examined.
The experimental conditions were: the reaction temperature is 455 ℃, and the reaction pressure is 19 MPa; the analytical data of the coal sample used in the experiment are shown in Table 5, and the results of the liquefaction reaction are shown in Table 6.
TABLE 5
TABLE 6
It can be seen from tables 4 and 6 that mixing the coal tar hydrogenation product with the coal direct liquefaction self-production solvent can increase the content of part of saturated aromatic hydrocarbons in the coal direct liquefaction circulating solvent, reduce the content of saturated chain hydrocarbons, and thus increase the hydrogen supply capacity of the coal direct liquefaction circulating solvent.
By improving and optimizing the composition of the coal direct liquefaction circulating solvent, the conversion rate of the coal is facilitated in the coal direct liquefaction reaction process, and the yield of coal liquefied oil is improved.
As is clear from comparison of the data of example 1 and example 2, the recycled solvent of example 2 does not contain the middle distillate b, but the performance of direct coal liquefaction of the recycled solvent can be improved by optimizing the conditions of the first hydrogenation reaction and the second hydrogenation reaction.
It can be seen from comparison of the data of example 1 and examples 10 to 11 that the direct coal liquefaction performance of the recycle solvent can be improved by simultaneously optimizing the type of hydrogenation catalyst, the hydrogenation reaction conditions, and the composition of the recycle solvent.
In addition, when the hydrogen supply effect of the circulating solvent is ensured, the coal tar is introduced as the solvent in the coal liquefaction process, the co-refining of the coal and the coal tar is realized, the processing mode and the processing difficulty of the coal tar are widened, more target products can be produced, and the direct coal liquefaction economic benefit is favorably improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method for preparing a coal direct liquefaction circulating solvent is characterized by comprising the following steps:
s1, in the presence of a hydrogen-containing gas and a first hydrogenation catalyst, carrying out a first hydrogenation reaction on the coal direct liquefaction oil to obtain a first hydrogenation product, and carrying out first separation on the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil; and
performing a second hydrogenation reaction on the coal tar in the presence of a hydrogen-containing gas and a second hydrogenation catalyst to obtain a second hydrogenation product, and performing second separation on the second hydrogenation product to obtain coal tar hydrogenation stable oil;
s2, performing first fractionation on the coal liquefaction hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c; and
performing second fractionation on the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
s3, mixing the heavy distillate oil c, the heavy distillate oil e and an optional part of the medium distillate oil b to obtain the coal liquefaction circulating solvent.
2. The process of claim 1, wherein the coal direct liquefaction oil is a coal direct liquefaction whole distillate or a coal direct liquefaction distillate with a distillation range > 200 ℃;
preferably, the distillation range of the coal direct liquefaction oil is 220-500 ℃.
3. The process as claimed in claim 1 or 2, wherein the distillation range of the coal tar is < 500 ℃, preferably 220-500 ℃, more preferably 220-400 ℃;
preferably, the weight content of aromatics in the coal tar is > 70 wt.%, preferably > 85 wt.%, based on the total amount of the coal tar.
4. A process according to any one of claims 1-3, wherein the light fraction a has a distillation range of < 220 ℃, preferably < 200 ℃;
preferably, the distillation range of the middle distillate oil b is 200-350 ℃, preferably 220-350 ℃;
preferably, the distillation range of the heavy distillate oil c is more than 200 ℃;
preferably, the distillation range of the heavy distillate oil e is more than 220 ℃, preferably more than 350 ℃;
preferably, the weight content of aromatics in the heavy fraction oil e is greater than 80 wt%, based on the total amount of the heavy fraction oil e.
5. The process of any one of claims 1 to 3, wherein the weight content of the heavy fraction oil c is 20 to 35 wt%, the weight content of the heavy fraction oil e is not higher than 80 wt%, and the weight content of the medium fraction oil b is 0 to 80 wt%, based on the total amount of the coal direct liquefaction cycle solvent;
preferably, the weight content of the heavy distillate oil c is 25-35%, the weight content of the heavy distillate oil e is 30-65%, and the weight content of the medium distillate oil b is 0-45%.
6. The process of any of claims 1-5, wherein the first hydrogenation catalyst comprises a first support and a first active component supported on the first support, and the second hydrogenation catalyst comprises a second support and a second active component supported on the second support;
the first active component and the second active component are respectively and independently selected from at least one of VIB group metals and/or VIII group metals;
preferably, the group VIB metal is selected from molybdenum and/or tungsten; the group VIII metal is selected from cobalt and/or nickel;
preferably, the weight content of the first active component in terms of oxide is 10-40 wt% based on the total amount of the first hydrogenation catalyst;
preferably, the second active component is present in an amount of 10 to 40 wt% on an oxide basis, based on the total amount of the second hydrogenation catalyst.
7. The process of any one of claims 1-6, wherein the first hydrogenation reaction conditions are at least: the reaction temperature is 320-400 ℃, and preferably 350-390 ℃; reaction pressureThe force is 8-22MPa, preferably 12-19 MPa; the hydrogen-oil ratio is 300-1000 and the volume space velocity is 0.5-2.0h-1；
Preferably, the second hydrogenation reaction is performed under conditions at least satisfying: the reaction temperature is 320-400 ℃, and preferably 350-390 ℃; the reaction pressure is 8-22MPa, preferably 12-19 MPa; the hydrogen-oil ratio is 300-1000 and the volume space velocity is 0.5-2.0h-1。
8. The method according to any one of claims 1-7, wherein in step S1, the first separating comprises: carrying out first hot high separation on the first hydrogenation product to obtain first hot high separation gas and first hot high separation liquid, and then carrying out first cold high separation on the first hot high separation gas to obtain first hydrogen-containing gas and first cold low separation liquid;
mixing the first hot high separation liquid and the first cold low separation liquid to obtain coal liquefaction hydrogenation stabilized oil;
the first thermal high separation condition at least satisfies: the temperature is 230 ℃ and 350 ℃, and the pressure is 8-22 MPa;
the first cold-high separation condition at least satisfies: the temperature is 45-54 deg.C, and the pressure is 8-22 MPa.
9. The method according to any one of claims 1-8, wherein in step S1, the second separating comprises: performing second hot high separation on the second hydrogenation product to obtain second hot high separation gas and second hot high separation liquid, and then performing second cold high separation on the second hot high separation gas to obtain second hydrogen-containing gas and second cold low separation liquid;
mixing the second hot high separation liquid and the second cold low separation liquid to obtain coal tar hydrogenation stabilized oil;
the second thermal high separation condition at least satisfies: the temperature is 230 ℃ and 350 ℃, and the pressure is 8-22 MPa;
the conditions of the second cold-high separation at least meet the following conditions: the temperature is 45-54 deg.C, and the pressure is 8-22 MPa.
10. The process of any one of claims 1-9, wherein the conditions of the first fractionation are at least: the pressure is 0.1-0.2MPa, and the temperature is 300-350 ℃;
preferably, the conditions of the second fractionation are at least: the pressure is 0.1-0.2MPa, and the temperature is 300-350 ℃.
11. A coal direct liquefaction recycle solvent prepared by the method of any one of claims 1 to 10;
preferably, the weight content of saturated aromatic hydrocarbon in the coal direct liquefaction circulating solvent is 80-90 wt%; the weight content of paraffinic hydrocarbons is less than 5 wt%; the content of naphthenes is less than 15 wt%;
preferably, the weight content of saturated aromatic hydrocarbon in the coal direct liquefaction circulating solvent is 81-89 wt%; the weight content of paraffinic hydrocarbons is from 2 to 3 wt%; the weight content of naphthenes is 10.8-13 wt%.
12. A system for preparing a coal direct liquefaction cycle solvent, comprising: the system comprises a mixing system, a coal direct liquefaction oil treatment system and a coal tar treatment system which are respectively communicated with the mixing system;
the coal direct liquefaction oil treatment system comprises:
a direct coal liquefaction tank (110) for storing direct coal liquefaction oil;
the first hydrogenation reactor (130) is used for carrying out a first hydrogenation reaction on the direct coal liquefaction oil from the direct coal liquefaction oil tank to obtain a first hydrogenation product;
the first separation system is used for separating the first hydrogenation product to obtain coal liquefaction hydrogenation stable oil;
the first fractionating tower (180) is used for fractionating the coal liquefied hydrogenation stabilized oil to obtain light distillate oil a, medium distillate oil b and heavy distillate oil c;
the coal tar treatment system comprises:
a coal tar tank (210) for storing the coal direct liquefaction oil;
the second hydrogenation reactor (230) is used for carrying out second hydrogenation reaction on the direct coal liquefaction oil from the coal tar tank to obtain a second hydrogenation product;
the second separation system is used for separating the second hydrogenation product to obtain coal tar hydrogenation stabilized oil;
the second fractionating tower (280) is used for fractionating the coal tar hydrogenation stabilized oil to obtain light distillate oil d and heavy distillate oil e;
and the mixing system is used for mixing the heavy distillate oil c, the heavy distillate oil e and the optional medium distillate oil b to obtain the coal direct liquefaction circulating solvent.
13. The system of claim 12, wherein the first separation system comprises:
a first thermal high separator (140) for performing a first thermal high separation on the first hydrogenation product to obtain a first thermal high separation gas and a first thermal high separation liquid;
a first cold high separator (160) for performing a first cold high separation on the first hot high separated gas to obtain a first hydrogen-containing gas and a first cold low separated liquid;
preferably, the second separation system comprises:
a second thermal high separator (240) for performing a second thermal high separation on the second hydrogenation product to obtain a second thermal high separation gas and a second thermal high separation liquid;
and the second cold high separator (260) is used for carrying out second cold high separation on the second hot high separation gas to obtain a second hydrogen-containing gas and a second cold low separation liquid.
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| CN115491221A (en) * | 2022-10-09 | 2022-12-20 | 国家能源集团宁夏煤业有限责任公司 | Solvent for coal hydrogenation liquefaction and coal hydrogenation liquefaction method |
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