CN106479564A - Circulating solvent and preparation method thereof - Google Patents
Circulating solvent and preparation method thereof Download PDFInfo
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- CN106479564A CN106479564A CN201610839921.6A CN201610839921A CN106479564A CN 106479564 A CN106479564 A CN 106479564A CN 201610839921 A CN201610839921 A CN 201610839921A CN 106479564 A CN106479564 A CN 106479564A
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- 239000002904 solvent Substances 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 131
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003245 coal Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000005194 fractionation Methods 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000004508 fractional distillation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 178
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 14
- 238000000926 separation method Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003250 coal slurry Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910003296 Ni-Mo Inorganic materials 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000005619 boric acid group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical group [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of circulating solvent and preparation method thereof.The preparation method of this circulating solvent includes for DCL/Direct coal liquefaction full distillate oil carrying out the first fractional distillation process, obtains middle temperature oil and high temperature oil, the distillate for 200～320 DEG C for the wherein middle temperature oil, high temperature oil is the distillate more than 320 DEG C；Middle temperature oil is carried out the first hydrogenation reaction, obtains the first stabilized hydrogenation oil；High temperature oil is carried out the second hydrogenation reaction, obtains the second stabilized hydrogenation oil；After-fractionating process is carried out to the mixture of the first stabilized hydrogenation oil and the second stabilized hydrogenation oil, obtains middle temperature solvent and high-temperature solvent, middle temperature solvent is 200～320 DEG C of distillate, high-temperature solvent is 320～500 DEG C of distillate；And circulating solvent will be obtained after partly middle temperature solvent is mixed with high-temperature solvent.The preparation method of the circulating solvent that the application provides has the advantages that hydrogen consumes gentle low yield and circulating solvent hydrogen supply performance is high.
Description
Technical Field
The invention relates to the field of coal chemical industry, in particular to a circulating solvent and a preparation method thereof.
Background
The direct coal liquefaction process includes the steps of preparing coal slurry with a certain concentration from coal powder, solvent oil, a catalyst and the like, mixing the coal slurry with hydrogen, sequentially entering a coal slurry preheater and a coal liquefaction reactor to react under certain conditions (the reaction temperature is 400-.
In the existing direct coal liquefaction process, the solvent not only fluidizes solid coal powder slurry in the direct coal liquefaction reaction process so as to improve the physical actions of the material conveying performance, thermodynamic property, coal-dissolving pyrolysis products and the like, but also has important chemical actions of providing hydrogen to the coal pyrolysis products, stabilizing the pyrolyzed low-molecular-weight products and the like. The direct coal liquefaction solvent not only has the function of a common solvent, but also has good functions of hydrogen supply and hydrogen transfer. Therefore, the hydrogen-donating performance of the solvent has very important relation to the moderation of reaction conditions and the improvement of the yield of the coal direct liquefaction oil.
In the continuous operation process of the direct coal liquefaction device, the used solvent is mixed oil prepared by medium-temperature oil and high-temperature oil generated by direct coal liquefaction according to a certain proportion, is called as a circulating solvent, and mainly comprises 2-4 ring aromatic hydrocarbons and hydrogenated aromatic hydrocarbons. Since the recycle solvent prepared by liquefying crude oil has a low hydrogen content, a high aromatic carbon rate and a poor hydrogen-supplying property, it is common to subject the recycle solvent to a proper depth of hydrotreatment in order to improve the hydrogen-supplying ability of the solvent oil.
Therefore, in order to obtain a circulating solvent with good hydrogen supply performance for direct coal liquefaction, many researches are made by technicians. The processing characteristic of the circulating solvent of the Japan NEDOL technology is that the distilled part of the coal liquefaction oil produced by the coal liquefaction unit is used as the feeding material of a hydrogenation device, and the hydrogenation device uses a Ni-Mo catalyst. The processing characteristic of the circulating solvent of China Shenhua coal direct liquefaction process (with the authorization notice number of CN1257252C) is that the full-fraction coal liquefaction oil produced by a coal liquefaction unit is used as the feeding material of a hydrogenation device, and the heavy distillate oil cut by fractionation is used as the circulating solvent hydrogenation device and uses a Ni-Mo catalyst. The Chinese patent application with the publication number of CN1844318A discloses a hydrogenation process of a circulating solvent by direct liquefaction of lignite, provides a catalyst grading technology of a hydrogenation process of full distillate oil by direct liquefaction of coal, and obtains the circulating solvent for hydrogen supply under appropriate chemical reaction conditions. The patent with publication number CN 104194830 discloses a method for preparing a recycled solvent for direct coal liquefaction, which comprises fractionating a direct coal liquefaction oil, selectively cutting heavy oil fractions, and then subjecting the heavy oil with a narrow fraction to hydrogenation stabilization, thereby obtaining a recycled solvent for direct coal liquefaction with superior hydrogen supply performance.
However, the recycling solvent for direct coal liquefaction obtained by the above processing method has technical problems of high hydrogen consumption, severe process conditions and insufficient hydrogen supply capacity, and thus, there is still a need for improvement of the existing processing method of the recycling solvent.
Disclosure of Invention
The invention mainly aims to provide a circulating solvent and a preparation method thereof, and aims to solve the problems of high hydrogen consumption, harsh process conditions and insufficient hydrogen supply capacity of the conventional direct coal liquefaction hydrogen supply solvent.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method of preparing a recycled solvent, the method comprising: performing a first fractionation process on coal direct liquefaction full distillate oil to obtain medium-temperature oil and high-temperature oil, wherein the medium-temperature oil is distillate oil at the temperature of 200-320 ℃, and the high-temperature oil is distillate oil at the temperature of more than 320 ℃; carrying out a first hydrogenation reaction on the medium temperature oil to obtain first hydrogenation stabilized oil; carrying out a second hydrogenation reaction on the high-temperature oil to obtain second hydrogenation stabilized oil; performing a second fractionation process on a mixture of the first hydrogenation stabilized oil and the second hydrogenation stabilized oil to obtain a medium-temperature solvent and a high-temperature solvent, wherein the medium-temperature solvent is distillate oil at the temperature of 200-320 ℃, and the high-temperature solvent is distillate oil at the temperature of 320-500 ℃; and mixing part of the medium-temperature solvent and the high-temperature solvent to obtain a circulating solvent.
Further, in the second fractionation process, the medium-temperature solvent is distillate oil at 200-300 ℃, and the high-temperature solvent is distillate oil at 300-480 ℃.
Further, the weight ratio of the high-temperature solvent to the medium-temperature solvent is 2: 4-1: 5, preferably 2: 6-1: 4.
Further, the first hydrogenation process comprises the step of carrying out a first hydrogenation reaction on the medium-temperature oil and hydrogen under the action of a first catalyst; wherein the temperature of the first hydrogenation reaction is 300-380 ℃, and preferably 320-360 ℃; the reaction pressure of the first hydrogenation reaction is 10-21 MPa, preferably 16-20 MPa.
Further, the volume ratio of the hydrogen to the medium-temperature oil in the first hydrogenation reaction process is 100-1500, preferably 500-1000; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1。
Further, the second hydrogenation process comprises the step of carrying out second hydrogenation reaction on the high-temperature oil and hydrogen under the action of a second catalyst; wherein the temperature of the second hydrogenation reaction is 320-420 ℃, and preferably 360-400 ℃; the reaction pressure of the second hydrogenation reaction is 10-21 MPa, preferably 16-20 MPa.
Further, the volume ratio of the hydrogen to the high-temperature oil in the second hydrogenation reaction process is 100-1500, and preferably 300-800; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1。
Further, the first catalyst comprises a first active component and a first carrier; the second catalyst comprises a second active component and a second carrier, wherein the first active component and the second active component are respectively and independently selected from one or more of metals corresponding to elements Co, Ni, Mo and W and/or oxides of the metals; preferably the first support and the second support are each independently selected from one or more of the group consisting of alumina, silica and molecular sieves.
Furthermore, an auxiliary agent is added during the first hydrogenation reaction and/or the second hydrogenation reaction, and the auxiliary agent is a substance containing one or more of the elements Si, P and B.
In order to achieve the above object, the present invention further provides a recycled solvent, which is prepared by the above preparation method.
Furthermore, the content of total aromatic hydrocarbon in the circulating solvent is 70-86 wt%, the content of total monocyclic aromatic hydrocarbon is 45-70 wt%, the content of total bicyclic aromatic hydrocarbon is 16-28 wt%, and the hydrogen supply index is 21.5-24.5 mg/g.
By applying the technical scheme of the invention, after fraction cutting is carried out on the coal direct liquefaction full distillate oil at a specific cutting temperature, the medium-temperature oil and the high-temperature oil are obtained, and then only the medium-temperature oil and the high-temperature oil of the specific fraction section are hydrogenated. The adoption of the process of respectively hydrogenating the medium-temperature oil and the high-temperature oil is beneficial to inhibiting the medium-temperature oil from robbing hydrogen with the high-temperature oil in the hydrogenation process, thereby causing the results of excessive hydrogenation of the medium-temperature oil and insufficient hydrogenation of the high-temperature oil. In addition, the part with weak hydrogen supply capacity is removed through the second fractionation process, and only the medium-temperature solvent and the high-temperature solvent are mixed to be used as the circulating solvent, so that the content of saturated aromatic hydrocarbon is reduced, the content of unsaturated aromatic hydrocarbon is increased, and the hydrogen supply capacity of the circulating solvent is further improved. In conclusion, the preparation method of the circulating solvent provided by the application has the advantages of low hydrogen consumption and gas yield, high hydrogen supply performance of the circulating solvent and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic view showing a configuration of an apparatus for preparing a recycled solvent according to an exemplary embodiment of the present invention;
fig. 2 shows a schematic configuration diagram of an apparatus for preparing a recycled solvent provided in comparative example 2.
Wherein the figures include the following reference numerals:
10. a first fractionation column; 20. a first buffer tank; 30. a first hydrogenation reactor; 40. a second buffer tank; 50. a second hydrogenation reactor; 60. a recycle hydrogen compressor; 70. a thermal high-pressure separator; 80. a cold high-pressure separator; 90. a second fractionation column;
10', a hydrogenation reactor; 20', a recycle hydrogen compressor; 30', a thermal high-temperature separator; 40', a cold high-pressure separator; 50' fractionating tower.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background art, the existing coal direct liquefaction circulating solvent has the problems of high hydrogen consumption, harsh process conditions and insufficient hydrogen supply capacity. In order to solve the technical problems, the invention provides a preparation method of a circulating solvent, which comprises the steps of carrying out a first fractionation process on coal direct liquefaction full distillate oil to obtain medium-temperature oil and high-temperature oil, wherein the medium-temperature oil is distillate oil with the temperature of 200-320 ℃, and the high-temperature oil is distillate oil with the temperature of more than 320 ℃; carrying out a first hydrogenation reaction on the medium temperature oil to obtain first hydrogenation stabilized oil; carrying out a second hydrogenation reaction on the high-temperature oil to obtain second hydrogenation stabilized oil; performing a second fractionation process on a mixture of the first hydrogenation stabilized oil and the second hydrogenation stabilized oil to obtain a medium-temperature solvent and a high-temperature solvent, wherein the medium-temperature solvent is distillate oil at the temperature of 200-320 ℃, and the high-temperature solvent is distillate oil at the temperature of 320-500 ℃; and mixing part of the medium-temperature solvent and the high-temperature solvent to obtain a circulating solvent.
Compared with the prior art that the direct coal liquefaction full distillate oil is directly hydrogenated, the hydrogenation process is beneficial to greatly reducing the hydrogen consumption and the gas yield in the hydrogenation process. The adoption of the process of respectively hydrogenating the medium-temperature oil and the high-temperature oil is beneficial to inhibiting the medium-temperature oil from robbing hydrogen with the high-temperature oil in the hydrogenation process, so that the result that the medium-temperature oil is excessively hydrogenated and the high-temperature oil is insufficiently hydrogenated is caused. In addition, the part with weak hydrogen supply capacity is removed through the second fractionation process, and only the medium-temperature solvent and the high-temperature solvent are mixed to be used as the circulating solvent, so that the content of saturated aromatic hydrocarbon is reduced, the content of unsaturated aromatic hydrocarbon is increased, and the hydrogen supply capacity of the circulating solvent is further improved. In summary, the preparation method of the recycle solvent provided by the application has the advantages of low hydrogen consumption and gas yield, high hydrogen supply performance of the recycle solvent and the like.
In the process of preparing the circulating solvent, only part of products (medium-temperature oil and high-temperature oil) are selected as raw materials, low-temperature oil with the temperature lower than 200 ℃ can be obtained in the first fractionation process and the second fractionation process in the actual preparation process, and the part of low-temperature oil can be used as raw material oil of a hydro-upgrading process after being mixed with the residual medium-temperature oil for preparing the circulating solvent. In the second fractionation process, the low-temperature oil, the medium-temperature solvent and the high-temperature solvent are removed, and the remaining component is heavy oil, which has a weak hydrogen donating property (compared with the medium-temperature solvent and the high-temperature solvent).
The preparation method is beneficial to reducing the hydrogen consumption and the gas yield, and simultaneously, the circulating solvent with higher circulating hydrogen supply capacity is prepared. In a preferred embodiment, the medium-temperature solvent is distillate oil with the temperature of 200-300 ℃, and the high-temperature solvent is distillate oil with the temperature of 300-480 ℃. The further limitation of the distillation sections of the medium-temperature solvent and the high-temperature solvent is beneficial to reducing the content of the components with weaker hydrogen supply capability in the circulating solvent, thereby being beneficial to further improving the hydrogen supply capability of the circulating solvent.
In the above preparation method, the weight ratio of the medium temperature solvent to the high temperature solvent can be adjusted by those skilled in the art. In a preferred embodiment, the weight ratio of the high-temperature solvent to the medium-temperature solvent is 2:4 to 1: 5. The weight ratio of the medium-temperature solvent to the high-temperature solvent includes, but is not limited to, the above-mentioned ratio range, but it is preferable to limit the weight ratio to the above-mentioned range to improve the overall performance of the circulating solvent. Preferably 2:6 to 1: 4.
In the preparation method provided by the invention, a person skilled in the art can select specific process conditions in the first hydrogenation process. In a preferred embodiment, the first hydrogenation process comprises the step of carrying out a first hydrogenation reaction on the medium-temperature oil and hydrogen under the action of a first catalyst; wherein the temperature of the first hydrogenation reaction is 300-380 ℃, and preferably 320-360 ℃; the reaction pressure of the first hydrogenation reaction is 10-21 MPa, preferably 16-20 MPa. Limiting the temperature and pressure of the first hydrogenation process within the above ranges is advantageous for improving the hydrogenation effect of the medium temperature oil.
In a preferred embodiment, the volume ratio of the hydrogen to the medium temperature oil in the first hydrogenation reaction process is 100 to 1500, preferably 500 to 1000; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1. Limiting the volume ratio of hydrogen to the medium temperature oil and the volume space velocity within the above ranges facilitates adjustment of the degree of hydrogenation of the medium temperature oil. The process condition of moderate hydrogenation for the medium temperature oil not only ensures the hydrogen supply performance, but also ensures the hydrogen supply performanceThe medium temperature oil contains certain element content such as S, N, O. S is an important auxiliary agent in the direct coal liquefaction process, so moderate hydrogenation of medium-temperature oil is beneficial to reducing the addition amount of sulfur when coal slurry is prepared, and polar compounds such as N, O are beneficial to improving the direct coal liquefaction reaction activity, thereby improving the conversion rate of coal and the yield of oil.
In the preparation method provided by the invention, a person skilled in the art can select specific process conditions in the second hydrogenation process. In a preferred embodiment, the second hydrogenation process comprises the step of carrying out a second hydrogenation reaction on the high-temperature oil and hydrogen under the action of a second catalyst; wherein the temperature of the second hydrogenation reaction is 320-420 ℃, and preferably 360-400 ℃; the reaction pressure of the second hydrogenation reaction is 10-21 MPa, preferably 16-20 MPa. Limiting the temperature and pressure of the second hydrogenation process within the above ranges is advantageous for improving the hydrogenation effect of the high-temperature oil.
In a preferred embodiment, the volume ratio of the hydrogen to the high-temperature oil in the second hydrogenation reaction process is 100 to 150, preferably 300 to 800; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1. Limiting the volume ratio of hydrogen to the high temperature oil and the volume space velocity in the above ranges is favorable for adjusting the hydrogenation degree of the high temperature oil so as to properly hydrogenate the high temperature oil.
It is worth to be noted that, in the invention, different hydrogenation processes are respectively adopted for medium-temperature oil and high-temperature oil, which is equivalent to different process conditions for raw materials with different distillation ranges and properties, thereby being beneficial to further improving the hydrogenation effect and realizing the further optimization of the hydrogen supply performance of the circulating solvent.
The reactor used for the hydrogenation reaction can be selected from an ebullating bed reactor, a slurry bed reactor, an expanded bed reactor or a fixed bed reactor. Preferably, a fixed bed reactor or an expanded bed reactor is used for hydrogenation of the medium-temperature oil in the first hydrogenation reaction, and an ebullated bed reactor or a slurry bed reactor is used for hydrogenation of the high-temperature oil in the second hydrogenation reaction.
In the preparation method provided by the invention, the catalytic hydrogenation process can be carried out by adopting a catalyst commonly used in the hydrogenation process of the direct coal liquefaction oil by a person skilled in the art. In a preferred embodiment, the first catalyst comprises a first active component and a first support; the second catalyst comprises a second active component and a second carrier, wherein the first active component and the second active component are respectively and independently selected from one or more of metals corresponding to elements Co, Ni, Mo and W and/or oxides of the metals; preferably the first support and the second support are each independently selected from one or more of the group consisting of alumina, silica and molecular sieves. The catalyst with the composition is beneficial to improving the catalytic activity of the first hydrogenation reaction and the second hydrogenation reaction.
In a preferred embodiment, an auxiliary agent is further added during the first hydrogenation reaction and/or the second hydrogenation reaction, and the auxiliary agent is a substance containing one or more of the elements Si, P and B. The addition of the auxiliary agent is beneficial to further improving the catalytic activity of the first hydrogenation reaction and the second hydrogenation reaction. Preferably phosphoric acid and/or boric acid.
The invention also provides a circulating solvent, and the circulating solvent is prepared by the preparation method.
The circulating solvent prepared by the method has good hydrogen supply performance, is beneficial to improving the conversion rate of coal and the yield of product oil in the direct coal liquefaction reaction process, reducing hydrogen consumption and material emission, and is also beneficial to improving the utilization level of raw material coal.
In a preferred embodiment, the circulating solvent contains 70-86 wt% of total aromatic hydrocarbons, 45-70 wt% of total monocyclic aromatic hydrocarbons, 16-28 wt% of total bicyclic aromatic hydrocarbons and 21.5-24.5 mg/g of hydrogen donor index. Limiting the components in the circulating solvent within the above ranges is advantageous for further improving the hydrogen donating performance of the circulating solvent.
Example 1
As shown in fig. 1, a first fractionation process is performed on coal direct liquefaction whole distillate oil in a first fractionation tower 10 under a pressure of 0.05MPa to obtain low temperature oil, medium temperature oil and high temperature oil, wherein the low temperature oil is the distillate oil with a temperature of less than 200 ℃, the medium temperature oil is the distillate oil with a temperature of 200-300 ℃, and the high temperature oil is the distillate oil with a temperature of more than 300 ℃.
The medium temperature oil enters a first hydrogenation reactor 30 (fixed bed reactor) after being stabilized by a first buffer tank 20 and then enters Ni-Mo/Al2O3(Ni-MOIs an active component, Al2O3Is a carrier) to obtain first hydrogenation stable oil, wherein the pressure of the first hydrogenation process is 16MPa, the temperature is 320 ℃, the hydrogen-oil ratio is 800v/v, and the reaction space velocity is 1.5h-1。
The high temperature oil enters a second hydrogenation reactor 50 (boiling bed reactor) after being stabilized by a second buffer tank 40 and then enters Ni-W/Al2O3(Ni-W is an active component, Al)2O3Is a carrier) to obtain second hydrogenation stable oil, wherein the pressure of the second hydrogenation process is 16MPa, the temperature is 360 ℃, and the hydrogen-oil ratio is 300 v/v; the reaction space velocity is 1.5h-1. The hydrogen in the first hydrogenation reactor 30 and the second hydrogenation reactor 50 is provided by a recycle hydrogen compressor 60.
The first hydrogenation stabilized oil and the second hydrogenation stabilized oil enter a thermal high-temperature separator 70 for separation to obtain a light component and a heavy component, the separation pressure is 16MPa, and the separation temperature is 250 ℃.
The light components at the top of the hot high-molecular separator 70 enter the cold high-molecular separator 80 for separation to obtain a gas-phase product and a liquid-phase product, the separation pressure is 16MPa, and the temperature is 20 ℃.
The liquid phase product produced from the bottom of the cold high-temperature separator 80 and the heavy component produced from the bottom of the hot high-temperature separator 70 enter a second fractionating tower 90 to be subjected to a second fractionating process, so as to obtain low-temperature oil, a medium-temperature solvent and a high-temperature solvent, wherein the low-temperature oil is distillate oil with the temperature of less than 200 ℃, the low-temperature oil is produced from the top of the second fractionating tower 90, the medium-temperature solvent is distillate oil with the temperature of 200-.
Mixing a high-temperature solvent and a medium-temperature solvent according to a weight ratio of 2: 7 mixing to obtain the coal direct liquefaction circulating solvent.
Example 2
The pressure of the first hydrogenation reaction and the second hydrogenation reaction was 20MPa, and the other conditions were the same as in example 1.
Example 3
The temperature of the first hydrogenation reaction is 360 ℃, and the temperature of the second hydrogenation reaction is 400 ℃; mixing a high-temperature solvent and a medium-temperature solvent according to a weight ratio of 1:4 to obtain a coal direct liquefaction recycle solvent, and the other conditions are the same as in example 1.
Example 4
The temperature of the first hydrogenation reaction is 360 ℃, and the reaction space velocity is changed to 0.8h-1The temperature of the second hydrogenation reaction is 400 ℃, and the reaction space velocity is changed to 0.8h-1The high-temperature solvent and the medium-temperature solvent are mixed according to the weight ratio of 2:6 to obtain a coal-directly liquefied recycle solvent, and the other conditions were the same as in example 1.
Example 5
In the first fractionation process, the low-temperature oil is distillate oil with the temperature of less than 200 ℃, the medium-temperature oil is distillate oil with the temperature of 200-340 ℃, and the high-temperature oil is distillate oil with the temperature of more than 340 ℃; the pressure of the first hydrogenation process is 16MPa, the temperature is 320 ℃, the hydrogen-oil ratio is 500v/v, and the reaction space velocity is 1h-1The auxiliary agent is phosphoric acid; the pressure of the second hydrogenation process is 16MPa, the temperature is 360 ℃, and the hydrogen oilThe ratio is 300 v/v; the reaction space velocity is 1h-1The auxiliary agent is phosphoric acid; mixing a high-temperature solvent and a medium-temperature solvent according to a weight ratio of 1:5 mixing to obtain the coal direct liquefaction circulating solvent, and the other conditions are the same as the example 1.
Example 6
In the first fractionation process, the low-temperature oil is distillate oil with the temperature of less than 220 ℃, the medium-temperature oil is distillate oil with the temperature of 220-320 ℃, and the high-temperature oil is distillate oil with the temperature of more than 320 ℃; the pressure of the first hydrogenation process is 16MPa, the temperature is 330 ℃, the hydrogen-oil ratio is 500v/v, and the reaction space velocity is 1h-1The auxiliary agent is phosphoric acid; the pressure of the second hydrogenation process is 16MPa, the temperature is 370 ℃, and the hydrogen-oil ratio is 300 v/v; the reaction space velocity is 1h-1The auxiliary agent is phosphoric acid; the high-temperature solvent and the medium-temperature solvent are mixed according to the weight ratio of 2: 7 to obtain a coal direct liquefaction recycle solvent, and the other conditions are the same as in example 1.
Example 7
In the first fractionation process, the low-temperature oil is distillate oil with the temperature of less than 200 ℃, the medium-temperature oil is distillate oil with the temperature of 200-320 ℃, and the high-temperature oil is distillate oil with the temperature of more than 320 ℃; the pressure of the first hydrogenation process is 16MPa, the temperature is 340 ℃, the hydrogen-oil ratio is 800v/v, and the reaction space velocity is 1.25h-1The auxiliary agent is boric acid; the pressure of the second hydrogenation process is 16MPa, the temperature is 380 ℃, and the hydrogen-oil ratio is 500 v/v; the reaction space velocity is 1.25h-1The auxiliary agent is boric acid; mixing a high-temperature solvent and a medium-temperature solvent according to a weight ratio of 1:5 mixing to obtain the coal direct liquefaction circulating solvent, and the other conditions are the same as the example 1.
Example 8
In the first fractionation process, the low-temperature oil is distillate oil with the temperature of less than 220 ℃, the medium-temperature oil is distillate oil with the temperature of 220-340 ℃, and the high-temperature oil is distillate oil with the temperature of more than 340 ℃; the pressure of the first hydrogenation process is 20MPa, the temperature is 350 ℃, and the hydrogen-oil ratio is1000v/v, reaction space velocity of 1.5h-1The auxiliary agent is phosphoric acid; the pressure of the second hydrogenation process is 20MPa, the temperature is 390 ℃, the hydrogen-oil ratio is 800v/v, and the reaction space velocity is 1.5h-1The auxiliary agent is phosphoric acid; the high-temperature solvent and the medium-temperature solvent are mixed according to the weight ratio of 2:6 to obtain a coal-directly liquefied recycle solvent, and the other conditions were the same as in example 1.
Example 9
On the basis of example 1, the pressure in the first hydrogenation process is 10MPa, the temperature is 380 ℃, the hydrogen-oil ratio is 100v/v, and the reaction space velocity is 4.5h-1(ii) a The reaction pressure of the second hydrogenation process is 10MPa, the temperature is 420 ℃, the hydrogen-oil ratio is 100v/v, and the reaction space velocity is 4.5h-1Other conditions were the same as in example 1.
Example 10
On the basis of example 1, the reaction pressure of the first hydrogenation process is 8MPa, the temperature is 280 ℃, the hydrogen-oil ratio is 80v/v, and the reaction space velocity is 5h-1(ii) a The reaction pressure of the second hydrogenation process is 8MPa, the temperature is 300 ℃, the hydrogen-oil ratio is 50v/v, and the reaction space velocity is 5h-1Other conditions were the same as in example 1.
Example 11
On the basis of the embodiment 1, the high-temperature solvent is distillate oil with the temperature of 300-500 ℃, and other conditions are the same as the embodiment 1.
Example 12
The weight ratio of the high-temperature solvent to the low-temperature solvent was 1:1 in example 1, and the other conditions were the same as in example 1.
Example 13
The weight ratio of the high-temperature solvent to the low-temperature solvent was 2:4 in example 1, and the other conditions were the same as in example 1.
Comparative example 1
The coal direct liquefaction full distillate oil is used as a coal direct liquefaction circulating solvent.
Comparative example 2
As shown in figure 2, the coal direct liquefaction full distillate oil is subjected to hydrogenation reaction in a hydrogenation reactor 10' (boiling bed reactor) to obtain hydrogenation stabilized oil, wherein the hydrogenation condition is that a catalyst is a tungsten-nickel catalyst RDA-1402, the pressure is 19MPa, the temperature is 390 ℃, the hydrogen-oil ratio is 300v/v, and the reaction space velocity is 1.5h-1. Hydrogen is supplied from the recycle hydrogen compressor 20'.
Separating the hydrogenated stabilized oil in a thermal high-temperature separator 30 'to obtain high-temperature oil, and discharging the high-temperature oil from the top of the thermal high-temperature separator 30', wherein the separation conditions are that the pressure is 19MPa and the separation temperature is 400 ℃.
And (3) entering a cold high-temperature separator 40 'with the pressure of 19MPa and the temperature of 20 ℃, and separating the high-temperature oil in the cold high-temperature separator 40' to obtain a gas-phase product and a liquid-phase product.
And introducing the liquid-phase product and the high-temperature oil into a fractionating tower 50' for fractionating, controlling the pressure of the fractionating tower to be 0.05MPa, and separating low-temperature oil at the temperature of less than 200 ℃, medium-temperature oil at the temperature of 200-350 ℃ and high-temperature oil at the temperature of more than 350 ℃.
Mixing high-temperature oil and medium-temperature oil according to the weight ratio of 2: 7 mixing to obtain the coal direct liquefaction circulating solvent. Mixing the residual medium-temperature oil and low-temperature oil to obtain the raw oil for hydrogenation modification process.
The properties of the circulating solvents obtained in examples 1 to 13 and comparative examples 1 to 2 are shown in tables 1 and 2.
TABLE 1
TABLE 2
In the application, mg-Hn beta/g-H refers to the proportion of beta hydrogen in all hydrogen elements, and PDQI refers to the hydrogen supply capacity of the circulating solvent.
The recycled solvents prepared in examples 1 to 13 and comparative examples 1 to 2 were used to perform the direct coal liquefaction test. A0.5L stirring type autoclave is adopted, the amount of coal entering the autoclave is 28g (dry coal), the weight ratio of a circulating solvent to the coal is 2:1, the initial pressure of hydrogen is 10.0MPa, a catalyst is an iron catalyst (the catalyst is a coal-based supported FeOOH type catalyst and is prepared by the method in the embodiment 1 in the prior patent ZL 01153377.9), the addition amount of Fe is 1 wt% of the dry coal, an auxiliary agent is sulfur, and n (S)/n (Fe) is 2. The autoclave was then brought to a reaction temperature of 455 ℃ and thermostated for 60min to obtain a gas-phase product and a liquid-solid mixture.
And (3) analyzing the composition of the gas phase product by adopting a gas chromatograph, and sequentially carrying out Soxhlet extraction separation on the liquid-solid phase product by using normal hexane and tetrahydrofuran. Wherein n-hexane soluble material is defined as oil, n-hexane insoluble and tetrahydrofuran soluble material is defined as pre-asphaltene and asphaltene (asphaltene component for short), and tetrahydrofuran insoluble material is defined as unreacted coal. The results of the direct coal liquefaction test are shown in tables 3 and 4.
TABLE 3
TABLE 4
In examples 1 to 13, coal-direct-liquefaction full distillate oil is fractionated, medium-temperature oil and high-temperature oil are respectively hydrogenated, and then a part of medium-temperature solvent and high-temperature solvent are mixed to be used as circulating solvent, in comparative example 1, coal-direct-liquefaction full distillate oil is used as circulating solvent, and in comparative example 2, coal-blending direct liquefaction reaction is performed on circulating solvent obtained by hydrogenating and then fractionating coal-direct-liquefaction full distillate oil. As can be seen from tables 3 and 4, although the hydrogen consumption in the direct coal liquefaction reaction by recycling the solvent provided by the present application is slightly high, the conversion rate of coal and the yield of oil in the direct coal liquefaction reaction are greatly improved, and the yield of the pitch substances and the gas is reduced. Therefore, the preparation method of the circulating solvent provided by the application is beneficial to improving the hydrogen supply performance of the circulating solvent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A method for producing a recycled solvent, comprising:
performing a first fractionation process on coal direct liquefaction full distillate oil to obtain medium-temperature oil and high-temperature oil, wherein the medium-temperature oil is distillate oil with the temperature of 200-320 ℃, and the high-temperature oil is distillate oil with the temperature of more than 320 ℃;
carrying out a first hydrogenation reaction on the medium-temperature oil to obtain first hydrogenation stabilized oil;
carrying out a second hydrogenation reaction on the high-temperature oil to obtain second hydrogenation stabilized oil;
performing a second fractionation process on the mixture of the first hydrogenation stabilized oil and the second hydrogenation stabilized oil to obtain a medium-temperature solvent and a high-temperature solvent, wherein the medium-temperature solvent is distillate oil at the temperature of 200-320 ℃, and the high-temperature solvent is distillate oil at the temperature of 320-500 ℃; and
and mixing part of the medium-temperature solvent and the high-temperature solvent to obtain the circulating solvent.
2. The preparation method according to claim 1, wherein in the second fractionation process, the medium-temperature solvent is a distillate oil at 200 to 300 ℃, and the high-temperature solvent is a distillate oil at 300 to 480 ℃.
3. The preparation method according to claim 1 or 2, wherein the weight ratio of the high-temperature solvent to the medium-temperature solvent is 2:4 to 1:5, preferably 2:6 to 1: 4.
4. The preparation method according to claim 3, wherein the first hydrogenation process comprises a step of subjecting the medium-temperature oil and hydrogen to the first hydrogenation reaction under the action of a first catalyst; wherein,
the temperature of the first hydrogenation reaction is 300-380 ℃, and preferably 320-360 ℃;
the reaction pressure of the first hydrogenation reaction is 10-21 MPa, and preferably 16-20 MPa.
5. The preparation method according to claim 4, wherein the volume ratio of the hydrogen to the medium-temperature oil in the first hydrogenation reaction process is 100 to 1500, preferably 500 to 1000; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1。
6. The preparation method according to claim 4 or 5, wherein the second hydrogenation process comprises a step of performing the second hydrogenation reaction on the high-temperature oil and hydrogen under the action of a second catalyst; wherein,
the temperature of the second hydrogenation reaction is 320-420 ℃, and preferably 360-400 ℃;
the reaction pressure of the second hydrogenation reaction is 10-21 MPa, and preferably 16-20 MPa.
7. The preparation method according to claim 6, wherein the volume ratio of the hydrogen to the high-temperature oil in the second hydrogenation reaction process is 100 to 1500, preferably 300 to 800; the space velocity of the reaction volume is 0.5-4.5 h-1Preferably 0.8 to 2.5 hours-1。
8. The production method according to claim 6, wherein the first catalyst comprises a first active component and a first support; the second catalyst comprises a second active component and a second carrier, wherein the first active component and the second active component are respectively and independently selected from one or more of metals corresponding to elements Co, Ni, Mo and W and/or oxides of the metals; preferably, the first support and the second support are each independently selected from one or more of the group consisting of alumina, silica and molecular sieves.
9. The method according to claim 6, wherein an auxiliary agent is further added during the first hydrogenation reaction and/or the second hydrogenation reaction, and the auxiliary agent is a substance containing one or more of the elements Si, P and B.
10. A recycled solvent obtained by the production method according to any one of claims 1 to 9.
11. The circulating solvent of claim 10, wherein the circulating solvent comprises 70-86 wt% of total aromatic hydrocarbons, 45-70 wt% of total monocyclic aromatic hydrocarbons, 16-28 wt% of total bicyclic aromatic hydrocarbons, and 21.5-24.5 mg/g of hydrogen donor index.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116162481A (en) * | 2023-01-09 | 2023-05-26 | 中国神华煤制油化工有限公司 | Direct coal liquefaction circulating hydrogen supply solvent and preparation method and application thereof |
| WO2024148467A1 (en) * | 2023-01-09 | 2024-07-18 | 中国神华煤制油化工有限公司 | Recycled hydrogen-donor solvent for direct coal liquefaction and preparation method therefor and use thereof |
| CN116162481B (en) * | 2023-01-09 | 2024-10-22 | 中国神华煤制油化工有限公司 | Direct coal liquefaction circulating hydrogen supply solvent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116162481A (en) * | 2023-01-09 | 2023-05-26 | 中国神华煤制油化工有限公司 | Direct coal liquefaction circulating hydrogen supply solvent and preparation method and application thereof |
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| CN116162481B (en) * | 2023-01-09 | 2024-10-22 | 中国神华煤制油化工有限公司 | Direct coal liquefaction circulating hydrogen supply solvent and preparation method and application thereof |
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