CN112029527A - Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof - Google Patents

Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof Download PDF

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CN112029527A
CN112029527A CN202010820988.1A CN202010820988A CN112029527A CN 112029527 A CN112029527 A CN 112029527A CN 202010820988 A CN202010820988 A CN 202010820988A CN 112029527 A CN112029527 A CN 112029527A
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coal
direct
extraction
liquefaction
oil
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CN112029527B (en
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王洪学
谢晶
李导
舒歌平
杨葛灵
单贤根
程时富
向柠
吴剑平
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China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
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China Shenhua Coal to Liquid Chemical Co Ltd
Shanghai Research Institute of China Shenhua Coal to Liquid Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, 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
    • 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
    • C10G1/045—Separation of insoluble materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/322—Coal-oil suspensions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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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 the field of direct coal liquefaction, and discloses a method for treating direct coal liquefaction residues, a direct coal liquefaction method and application thereof. The method for treating the coal direct liquefaction residues comprises the following steps: 1) extracting the direct coal liquefaction residues with an extraction solvent; 2) carrying out solid-liquid separation on the extraction product obtained in the step 1) to obtain an extraction liquid and an extraction residue; 3) mixing the extract obtained in the step 2) with a catalyst and a hydrogen donor solvent to prepare coal slurry. The method for treating the coal direct liquefaction residues is low in cost and strong in treatment capacity, can be continuously operated on a large scale for a long period, and can be used for remarkably improving the oil yield when the treated product is prepared into coal slurry and recycled to the coal direct liquefaction reaction.

Description

Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof
Technical Field
The invention relates to the field of direct coal liquefaction, in particular to a method for treating direct coal liquefaction residues, a direct coal liquefaction method and application thereof.
Background
The technology for producing the liquid fuel by directly liquefying the coal is an effective means for cleanly and efficiently utilizing the coal and is beneficial to make up for the shortage of petroleum resources. The oil product prepared by direct coal liquefaction has low sulfur, low nitrogen, high heat value and high naphthenic hydrocarbon component, and can be used as an important source of special oil products for aviation, aerospace and the like. The coal direct liquefaction residue is a heavy product of direct coal liquefaction, accounts for about 30 wt% of coal feeding amount, is a high-ash and high-sulfur substance, and mainly comprises heavy liquefied oil (soluble in n-hexane), asphalt substances (insoluble in n-hexane and soluble in tetrahydrofuran), unconverted coal and inorganic substances. Wherein the heavy liquefied oil accounts for about 20 wt% of the total amount of the coal direct liquefaction residue, and the main components of the heavy liquefied oil are 2-4 ring aromatic hydrocarbons and partially hydrogenated aromatic hydrocarbons. The content of asphalt substances accounts for about 30 wt% of the total amount of the coal direct liquefaction residues, the asphalt substances mainly comprise polycyclic condensed aromatic hydrocarbons, and the aromatic degree and the carbon content are high.
Since the 70 s of the 20 th century, development and utilization of direct coal liquefaction residues are receiving wide attention, but related research at home and abroad mainly focuses on the aspects of component analysis, pyrolysis characteristics, combustion characteristics and the like of direct coal liquefaction residues. The traditional utilization technologies of the coal direct liquefaction residues are mainly combustion, coking and hydro-gasification, but the methods do not fully utilize the value of the coal direct liquefaction residues, and particularly the high added values of heavy liquefied oil and asphalt substances in the coal direct liquefaction residues are not fully utilized. Therefore, CN101962560A, CN103275744A, CN104845652A and other patents disclose methods for extracting heavy liquefied oil and asphaltic substances from coal liquefaction residues, and CN103756703A, CN101580729A, CN106986340A, CN105720233A and other patents further disclose methods for preparing high value-added products by using coal direct liquefaction residues, but the amount of coal direct liquefaction residues required for the direction of these high value-added products is not large, a large amount of coal liquefaction residues cannot be completely consumed, and the methods do not play a beneficial role in the coal direct liquefaction production itself.
CN101885976A develops a method for extracting heavy liquefied oil and mesophase pitch substances from coal direct liquefaction residues, in which the extracted heavy liquefied oil is hydrogenated and then recycled to a coal direct liquefaction device to be used as a recycling solvent, the pitch substances are used for preparing carbon materials, CN102010741A is to send the extracted heavy liquefied oil and pitch substances to a suspension bed hydrogenation reactor and crack the substances into hydrogenated medium oil and heavy oil through hydrogenation reaction, wherein the hydrogenated medium oil is output as a product, and the hydrogenated heavy oil is used as a recycling solvent and enters a coal liquefaction system. The two patent applications both achieve the purpose of applying a large amount of coal liquefaction residues, and particularly the second patent application greatly improves the yield of coal liquefaction oil, but an additional suspension bed hydrogenation reactor is needed, and simultaneously, two problems exist, namely firstly, the hydrogenation reaction conditions for heavy raw materials containing asphalt substances of which the weight is up to 60 percent in the hydrogenation reactor are very harsh, the reactor is easy to coke, and long-period operation is difficult to realize; secondly, the ash in the raw material can be enriched in the heavy component of the hydrogenation product, and when the hydrogenation product is used as a coal direct liquefaction circulating solvent, the oil yield is reduced when the ash in the heavy component exceeds that in the coal, so that very high requirements are provided for residue extraction and solid-liquid separation thereof, the requirement of the content of the ash in the component can be met by the combination of multiple filtering modes, the operation is complex during industrial production, and the efficiency is too low.
Disclosure of Invention
The invention aims to overcome the problem of difficult utilization of a large amount of coal direct liquefaction residues in the prior art, and provides a method for treating the coal direct liquefaction residues, which has the advantages of low cost, strong treatment capacity and large-scale and long-period continuous operation, and can remarkably improve the oil yield when the treated product is prepared into coal slurry and recycled to the coal direct liquefaction reaction.
The inventor of the present invention finds, through mass production practices and research, that the oil yield of the current coal direct liquefaction device is about 50%, and the main reasons affecting the oil yield are that a part of heavy liquefied oil converted from coal enters the residue and cannot be distilled out, and more asphalt substances are formed, and if the heavy liquefied oil and the asphalt substances in the coal direct liquefaction residue can be further converted into oil which can be distilled, the oil yield of the coal direct liquefaction is greatly improved.
Accordingly, in order to achieve the above object, a first aspect of the present invention provides a method for treating a coal direct liquefaction residue, the method comprising the steps of:
1) extracting the direct coal liquefaction residues with an extraction solvent;
2) carrying out solid-liquid separation on the extraction product obtained in the step 1) to obtain an extraction liquid and an extraction residue;
3) mixing the extract obtained in the step 2) with a catalyst and a hydrogen donor solvent to prepare coal slurry.
Preferably, in the step 1), the extraction solvent is one or more of coal direct liquefaction hydrogenation stabilized oil, coal high-temperature coking decrystallization washing oil and coal direct liquefaction crude oil; more preferably, the extraction solvent is a coal direct liquefaction hydro-stabilized oil.
Preferably, in step 1), the extraction conditions include: the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1:1-10, the extraction temperature is 80-220 ℃, and the extraction time is 0.5-5 h; more preferably, the weight ratio of the coal direct liquefaction residue to the extraction solvent is 1:1.5-5, the extraction temperature is 100-200 ℃, and the extraction time is 1-3 h.
Preferably, in the step 2), the solid-liquid separation is performed by centrifugation, filtration, sedimentation and the like; more preferably, in the step 2), the solid-liquid separation is performed by using a screw centrifuge; further preferably, when the solid-liquid separation is carried out, the separation linear speed of the horizontal screw centrifuge is 20-180m/s, and the separation temperature is 90-200 ℃; particularly preferably, when the solid-liquid separation is carried out, the separation linear speed of the horizontal screw centrifuge is 30-150m/s, and the separation temperature is 100-180 ℃.
Preferably, in the step 3), the hydrogen donor solvent is one or more of coal high-temperature coking decrystallized anthracene oil, coal high-temperature coking decrystallized washing oil, petroleum heavy oil catalytic cracking recycle oil, petroleum heavy oil catalytic cracking clarified oil hydrogenated oil and coal direct liquefaction hydrogenation stabilized oil; more preferably, the hydrogen donating solvent is a coal direct liquefaction hydrogenation stabilized oil.
Preferably, in the step 3), the concentration of the coal slurry is 40-55 wt%.
Preferably, the active component of the catalyst is selected from one or more of iron, molybdenum, nickel, cobalt and tungsten; more preferably, the catalyst is one or more of an iron-based catalyst, a molybdenum-based catalyst, a nickel-based catalyst, a cobalt-based catalyst, and a tungsten-based catalyst; further preferably, the catalyst is an iron-based catalyst.
Preferably, the addition amount of the catalyst is 0.2-3 wt% of the total weight of the heavy liquefied oil and the asphaltic substances in the extraction liquid based on the active ingredients.
Preferably, in the step 3), coal powder is further used when preparing the coal slurry.
Preferably, the addition amount of the catalyst is 0.2-3 wt% of the total weight of the heavy liquefied oil, the asphaltic substances and the coal dust in the extraction liquid based on the active ingredients.
Preferably, the method further comprises: recovering the extraction solvent in the raffinate obtained in the step 2).
In a second aspect, the invention provides a direct coal liquefaction method, wherein the direct coal liquefaction reaction is carried out by using the coal slurry obtained by the treatment method as a raw material.
Preferably, the conditions of the direct coal liquefaction reaction include: the reaction temperature is 440-460 ℃, the reaction time is 60-120min, and the reaction hydrogen pressure is 12-20 MPa.
In a third aspect, the invention provides a use of the above direct coal liquefaction method in direct coal liquefaction.
Through the technical scheme, the coal direct liquefaction residue can be effectively utilized, the heavy liquefaction oil and the asphalt substances in the coal direct liquefaction residue are prepared into coal slurry and recycled to the coal direct liquefaction reaction again, the utilization rate of carbon is maximized, the oil yield can be obviously improved, the extraction solvent can be recycled, the coal direct liquefaction residue is fully and environmentally utilized, the total oil yield and the economic benefit of the coal direct liquefaction are greatly improved, the process is simple, the cost is low, and the method is suitable for large-scale long-period continuous operation.
Drawings
FIG. 1 is a schematic process flow diagram of a preferred embodiment of the present invention.
Description of the reference numerals
1: extraction tank
2: extraction product delivery pump
3: horizontal screw centrifugal machine
4: extract liquid delivery pump
5: raffinate transfer pump
6: paddle dryer
7: coal slurry preparation tank
8: coal slurry booster pump
A: direct coal liquefaction residue
B: extraction solvent
C: catalyst and process for preparing same
D: pulverized coal
H: hydrogen donor solvent
F: waste material
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 treating coal direct liquefaction residues, which comprises the following steps:
1) extracting the direct coal liquefaction residues with an extraction solvent;
2) carrying out solid-liquid separation on the extraction product obtained in the step 1) to obtain an extraction liquid and an extraction residue;
3) mixing the extract obtained in the step 2) with a catalyst and a hydrogen donor solvent to prepare coal slurry.
In the invention, the direct coal liquefaction residue refers to solid residue which can be formed after the direct hydrogenation liquefaction reaction of the coal and the separation of liquefied crude oil, and finally liquid substances are discharged from the bottom of the pressure reduction tower and cooled.
In the present invention, the direct coal liquefaction residue in the present invention is preferably liquid direct coal liquefaction residue for easy transportation, and may be discharged from the vacuum tower and directly extracted with an extraction solvent.
In the invention, the heavy liquefied oil is a heavy oil which is generated by direct coal liquefaction reaction and has the molecular weight of 300-400 and can be dissolved in normal hexane.
In the invention, the asphalt substances refer to asphaltene and preasphaltene which are generated after coal is subjected to direct liquefaction reaction, are hydrocarbons with molecular weight of 400-2000 and containing trace heteroatoms, are insoluble in n-hexane and soluble in tetrahydrofuran solvent.
In the invention, the solid content refers to the ash content of heavy liquefied oil and asphaltic substances in the extraction liquid.
In the invention, the high-temperature coking decrystallization washing oil of coal refers to decrystallization washing oil generated in the high-temperature coking process of coal.
In the invention, the high-temperature coking and decrystallization anthracene oil of coal refers to decrystallization anthracene oil generated in the high-temperature coking process of coal.
In the invention, the petroleum heavy oil catalytic cracking cycle oil refers to cycle oil produced in the aromatic hydrocarbon extraction and generation process of the petroleum heavy oil catalytic cracking cycle oil.
In the invention, the hydrogenated oil of the petroleum heavy oil catalytic cracking clarified oil is solvent oil obtained by carrying out one or more times of hydrogenation treatment on the coal high-temperature coking and decrystallizing anthracene oil, the coal high-temperature coking and decrystallizing washing oil and the catalytic cracking clarified oil.
In the invention, the direct coal liquefaction crude oil refers to direct coal liquefaction crude oil separated by a direct coal liquefaction process.
In the invention, when the coal slurry consists of an extraction liquid, a catalyst and a hydrogen supply solvent, the concentration of the coal slurry refers to the percentage of the total mass of heavy liquefied oil and asphalt substances in the extraction liquid to the total mass of the coal slurry; when the coal slurry consists of the extraction liquid, the coal powder, the catalyst and the hydrogen supply solvent, the concentration of the coal slurry refers to the percentage of the total mass of the heavy liquefied oil, the asphalt substances and the coal powder in the extraction liquid to the total mass of the coal slurry.
According to the invention, preferably, the extraction solvent can be one or more of coal direct liquefaction hydrogenation stabilized oil, coal high-temperature coking decrystallization washing oil and coal direct liquefaction crude oil.
In the invention, more preferably, the extraction solvent is coal direct liquefaction hydrogenation stabilized oil, when the coal direct liquefaction hydrogenation stabilized oil is adopted as the extraction solvent, no external solvent is needed, no subsequent separation is needed, not only can the cost be saved, but also when the extraction liquid is further prepared into coal slurry and returns to a coal direct liquefaction system, no other substance is introduced, and other negative effects on the coal direct liquefaction system are avoided. More preferably, the extraction solvent is coal direct liquefaction hydrogenation stabilized oil with the distillation range of more than 200 ℃; further preferably, the extraction solvent is coal direct liquefaction hydrogenation stabilized oil with distillation range of 220-350 ℃; particularly preferably, the extraction solvent is coal direct liquefaction hydrogenation stabilized oil with the distillation range of 260-320 ℃. The coal direct liquefaction hydrogenation stabilized oil in the distillation range is mainly hydrogenated aromatic hydrocarbons with 2-4 rings, is similar to the molecular structures of heavy liquefied oil and asphalt substances in residues, and has good dissolving capacity for the heavy liquefied oil and the asphalt substances according to the principle of similarity and intermiscibility, so the extraction condition is mild, and the extraction rate for the heavy liquefied oil and the asphalt substances is high.
According to the invention, the weight ratio of the coal direct liquefaction residue to the extraction solvent during extraction can vary within a wide range, for example, can be 1: 1-10; preferably, the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1: 1.5-5. When the weight ratio of the coal direct liquefaction residue to the extraction solvent is within the above range, the extraction efficiency of the coal direct liquefaction residue can be improved, and when the amount of the extraction solvent is less than the above range, the extraction time is prolonged, and the extraction rate is decreased; increasing the amount of the extraction solvent can increase the extraction speed and the extraction rate, but when the amount of the extraction solvent exceeds the above range, the increase of the extraction rate is limited, and the utilization degree of the extraction device is reduced and the energy consumption is increased due to excessive extraction solvent.
According to the invention, the extraction temperature is 80-220 ℃, and the extraction time is 0.5-5 h; preferably, the temperature of the extraction is 100-200 ℃, and the time of the extraction is 1-3 h. The extraction rate can be improved by increasing the extraction temperature and the extraction time within a certain range, but the energy consumption is increased due to the overhigh extraction temperature, and the evaporation of the solvent is accelerated; on the other hand, the effect of further prolonging the extraction time on the improvement of the extraction rate is not large, and the utilization efficiency of the extraction device is reduced.
In the present invention, the extraction atmosphere and pressure may be those which are generally used in the art for extraction, and are not particularly limited, and for example, the extraction atmosphere may be nitrogen, and the extraction pressure may be 0.1 to 0.2 MPa.
According to the invention, after extraction is finished, solid-liquid separation is carried out on the obtained extraction product to obtain extraction liquid and raffinate.
In the present invention, the solid-liquid separation may be performed using various apparatuses commonly used in the art for solid-liquid separation of extraction products of direct coal liquefaction residues, and is not particularly limited. For example, the extraction product can be separated by various means such as centrifugation, filtration through a filter element, and sedimentation.
In the invention, the requirement on solid content in the extract liquor is not high, so that the requirement on solid-liquid separation is reduced, and therefore, the solid-liquid separation in the invention is preferably carried out by adopting a centrifugal mode, and when the solid-liquid separation is carried out by adopting the centrifugal mode, a horizontal screw centrifuge is preferably adopted, because the horizontal screw centrifuge is very suitable for large-scale and long-period continuous operation.
The inventor of the invention discovers through mass production experiments that a certain relation exists between the separation linear speed and the separation temperature of the horizontal screw centrifuge and the extraction rate and the solid content in the extraction liquid, the separation efficiency of the extraction liquid and the raffinate can be improved by improving the linear speed and the separation temperature of the centrifuge, the solid content in the extraction liquid is reduced, but the energy consumption is increased due to overhigh linear speed of the centrifuge, the equipment cost is increased, and the energy consumption is increased due to overhigh separation temperature. Therefore, in the invention, the separation linear speed of the horizontal screw centrifuge is preferably 20-180m/s, and the separation temperature is preferably 90-200 ℃; more preferably, the separation linear speed of the horizontal screw centrifuge is 30-150m/s, and the separation temperature is preferably 100-180 ℃.
In the invention, the extraction liquid obtained by solid-liquid separation contains an extraction solvent and heavy liquefied oil with higher content and asphaltic substances, and the solid content in the extraction liquid is less than 10 percent by weight through solid-liquid separation; preferably, solid-liquid separation is carried out, so that the solid content in the extract is less than 5 wt%; when the coal powder is further used when preparing the coal slurry, more preferably, the solid content in the extract liquid is consistent with the ash content in the feed coal. When the solid content in the extraction liquid is too high, more ash content can be brought into the direct coal liquefaction system by the extraction liquid, and the efficiency of the direct coal liquefaction reactor is reduced.
The inventor of the invention also finds that the heavy liquefied oil and the asphalt substances have good re-hydrocracking capability, can generate light oil products, are easier to be further hydrocracked due to one-time direct coal liquefaction reaction, can generate more liquefied oil, and can greatly improve the total oil yield of direct coal liquefaction when being prepared into coal slurry and further subjected to the direct coal liquefaction reaction.
On the other hand, the heavy liquefied oil and the asphalt substances in the extract liquid have good compatibility with the coal dust, and when the heavy liquefied oil and the asphalt substances are mixed with the coal dust to further prepare coal slurry, the properties of the coal slurry can be improved, and the transportability of the coal slurry is improved. In addition, the heavy liquefied oil and the asphalt substances are fed together with the coal powder, so that the oil yield of the direct coal liquefied oil can be improved.
Next, a process of preparing coal slurry by mixing the extract obtained by solid-liquid separation with a catalyst and a hydrogen donor solvent will be described, and the addition or non-addition of pulverized coal can be flexibly determined according to actual production requirements when coal slurry is prepared. For example, when there is sufficient extraction liquid in the actual production, the extraction liquid, the catalyst and the hydrogen donor solvent can be used only to prepare coal slurry, and the coal direct liquefaction reaction is carried out separately; when the amount of the extraction liquid is not enough to carry out the direct coal liquefaction reaction for one time independently or the extraction liquid is required to be added to improve the yield and the effect of the direct coal liquefaction reaction, the coal powder can also be added and mixed with the extraction liquid, the hydrogen supply solvent and the catalyst to prepare the coal slurry. That is, whether to add the pulverized coal to prepare the coal slurry may be determined according to the purpose and demand of actual production.
In the present invention, the ratio of the pulverized coal to the extraction liquid is not particularly limited, and may vary within a wide range as long as the finally prepared coal slurry has a concentration of 40 to 55 wt%, preferably 45 to 50 wt%. When the coal slurry concentration is in the range, the viscosity of the coal slurry is proper, so that pumping pipe conveying is facilitated, and if the coal slurry concentration is higher than the range, the viscosity of the coal slurry is increased, so that pumping pipe conveying is not facilitated; if the coal slurry concentration is lower than the above range, the coal liquefaction processing amount becomes small, the economy is poor, and the prepared coal slurry is deposited, which is also not favorable for pumping pipe transportation.
The hydrogen donor solvent in preparing the coal slurry according to the present invention may be various hydrogen donor solvents commonly used in the art for preparing coal slurry, and is not particularly limited. For example, the hydrogen donor solvent can be one or more of coal high-temperature coking decrystallized anthracene oil, coal high-temperature coking decrystallized washing oil, petroleum heavy oil catalytic cracking recycle oil, petroleum heavy oil catalytic cracking clarified oil hydrogenated oil and coal direct liquefaction hydrogenation stabilized oil; preferably, the hydrogen donor solvent is coal direct liquefaction hydrogenation stabilized oil, and when the coal direct liquefaction hydrogenation stabilized oil is used as the hydrogen donor solvent, the quality of the hydrogen donor solvent can be ensured, and the hydrogen donor solvent is better in compatibility when the coal slurry is prepared because the hydrogen donor solvent is produced by a coal liquefaction process; the purchased hydrogen donor solvent is limited in quality and quantity and can be used as the hydrogen donor solvent after being processed for many times.
According to the present invention, the catalyst may be various catalysts commonly used in the art for direct coal liquefaction reaction, for example, the active component of the catalyst may be selected from one or more of iron, molybdenum, nickel, cobalt, and tungsten, without particular limitation. Preferably, the catalyst is one or more of an iron-based catalyst, a molybdenum-based catalyst, a nickel-based catalyst, a cobalt-based catalyst and a tungsten-based catalyst; more preferably, the catalyst is an iron-based catalyst.
In the invention, the iron-based catalyst can be a supported or non-supported catalyst, the carrier of the supported catalyst is pulverized coal, the active component of the supported catalyst is ferric salt, and can be selected from ferrous salt and/or ferric salt, specifically, the ferrous salt can be ferrous sulfate, ferrous nitrate and ferrous chloride, and the ferric salt can be ferric sulfate, ferric nitrate and ferric chloride; the non-supported catalyst can be one or more of iron ore, iron-containing waste residues, iron oxides, iron salts, pyrite and aluminum-smelting red mud. In the present invention, preferably, the iron-based catalyst is a supported iron-based catalyst using pulverized coal as a carrier.
In the present invention, the amount of the catalyst to be added may vary within a wide range, and is not particularly limited as long as the direct coal liquefaction reaction can be catalyzed. The addition amount of the catalyst can be determined according to the total weight of the heavy liquefied oil, the asphaltic substances and the coal dust in the extraction liquid. Preferably, the addition amount of the catalyst is 0.2-3 wt% of the total weight of the heavy liquefied oil, the asphaltic substances and the coal powder in the extraction liquid based on the active ingredients; more preferably, the amount of the catalyst added is 0.5-1.5 wt% of the total weight of the heavy liquefied oil, the asphaltic substances and the coal dust in the extract (the coal slurry is prepared without adding coal dust, the catalyst content is calculated according to the total weight of the heavy liquefied oil and the asphaltic substances). When the addition amount of the catalyst is in the range, the direct coal liquefaction reaction can be effectively catalyzed, and the waste of production data can not be caused.
In the invention, when the catalyst is an iron catalyst, in order to change the catalyst into an active state, a sulfur auxiliary agent is further added, and the sulfur auxiliary agent can be sulfur powder, liquid sulfur or can be decomposed into H under a vulcanization condition2One or more of the labile sulfides of S.
In the present invention, the amount of the sulfur aid added may be determined according to the amount of the iron-based catalyst, and it is preferable that the molar ratio of the sulfur aid in terms of sulfur element to the catalyst in terms of iron element is 0.8 to 5: 1; more preferably, the molar ratio of the sulfur promoter, calculated as elemental sulfur, to the first catalyst, calculated as elemental iron, is from 1.5 to 2.5: 1.
Therefore, the coal slurry is prepared by mixing the extraction liquid with the catalyst and the hydrogen supply solvent (coal powder can be added or not added), the direct coal liquefaction residues can be recycled to the direct coal liquefaction reaction, a large amount of direct coal liquefaction residues are treated, the subsequent direct coal liquefaction yield and the obtained product quality can be improved, the operation is simple and convenient, convenience and flexibility are realized, and the economic benefit is greatly improved.
Hereinafter, the raffinate obtained after the solid-liquid separation will be further described.
According to the invention, the raffinate obtained by solid-liquid separation contains extraction solvent, coal cinder, ash and other solids. In order to save cost and improve the utilization rate of the extracting agent, the extracting solvent in the raffinate can be further recovered.
In the present invention, the extraction solvent of the raffinate may be recovered by various methods commonly used in the art for the recovery of extraction solvents, without particular limitation, and for example, the extraction solvent of the raffinate may be distilled off by a distillation method.
According to the present invention, when the extraction solvent is recovered by a distillation method, the raffinate may be dried by various apparatuses commonly used in the art, as long as the purpose of recovering the extraction solvent can be achieved, and is not particularly limited. For example, the drying can be carried out by a spray dryer, a vacuum paddle dryer, a drum dryer, or the like. Preferably, the recovery of the extraction solvent is performed using a vacuum paddle drying device and/or a drum drying device. The recovery conditions may be: the drying temperature is 150-; preferably, the drying temperature is 200-300 ℃, and the drying time is 2-8 h. Both increased drying temperature and increased drying time can increase the recovery of the extraction solvent, but both excessive temperatures and excessive time can increase energy consumption; too low a temperature and too short a time are disadvantageous for recovery of the extraction solvent, and the recovery rate of the extraction solvent is lowered.
According to the invention, the recovered extraction solvent can be further recycled for continuous extraction. Therefore, the cost can be saved, and the cyclic utilization of resources can be realized.
In a second aspect of the present invention, there is provided a direct coal liquefaction method, wherein the direct coal liquefaction raw material is the coal slurry prepared by the above method.
The direct coal liquefaction method of the present invention may be performed by various methods for performing direct coal liquefaction in the art, and is not particularly limited, and for example, a direct coal liquefaction reaction may be performed by a fluidized bed liquefaction process, a suspension bed liquefaction process, an internal and external circulation liquefaction process, or the like.
In the present invention, the coal direct liquefaction reactor may be any of various reactors commonly used in the art for direct coal liquefaction, and is not particularly limited, and may be any of various reactors capable of providing a place for direct coal liquefaction, such as a bubbling bed, a fully-backmixed suspension bed, an internal and external loop reactor, and the like.
After the direct coal liquefaction reaction is finished, the direct coal liquefaction reaction product enters a separation system for subsequent separation. The subsequent separation process may be performed according to various methods commonly used for separation of products of a refining reaction, for example, a product after a liquefaction reaction may be first separated into a first gas phase and a liquid-solid mixed phase, the obtained first gas phase is cooled step by step and then separated into a gas and a light oil, and the remaining part of the obtained gas after discharging a part of tail gas is recycled to the direct coal liquefaction reaction; and (3) carrying out step-by-step pressure reduction and normal pressure reduction distillation on the obtained liquid-solid mixed phase to obtain a second gas phase, an oil product and residues, and mixing the oil product with the light oil to obtain liquefied crude oil. The separation of the products after direct coal liquefaction is a well-known technique in the art and will not be described in detail herein.
The process flow of a preferred embodiment of the present invention will be described below with reference to fig. 1.
As shown in fig. 1, firstly, the coal direct liquefaction residue a and the extraction solvent B are extracted in an extraction tank 1, and the extracted product is pumped to a horizontal decanter centrifuge 3 by an extraction product delivery pump 2 for solid-liquid separation. On the one hand, the extract obtained by solid-liquid separation is pumped into a coal slurry preparation tank 7 through an extract delivery pump 4 to prepare coal slurry with the catalyst C, the hydrogen donor solvent H and the coal powder D (with or without addition), and after the coal slurry is prepared, the extract is pumped into a direct coal liquefaction system through a coal slurry booster pump 8 to perform direct coal liquefaction reaction. On the other hand, the raffinate obtained by the solid-liquid separation is sent to a paddle dryer 6 through a raffinate transfer pump 5 to recover the extraction solvent B, and the waste F is discharged out of the system. The recovered extraction solvent can be reused for extracting the direct coal liquefaction residues. Therefore, a large amount of coal direct liquefaction residues can be treated to the maximum extent, the cost is low, the treatment capacity is high, and large-scale and long-period continuous operation can be realized. The extraction solvent can be recycled, and the product obtained by treatment can be further recycled to the direct coal liquefaction reaction, so that the oil yield can be improved.
In a third aspect, the present invention provides the use of the above-described direct coal liquefaction process in the direct coal liquefaction.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, all reagents used were commercially available unless otherwise specified.
In the following examples and comparative examples, various yields were calculated based on dry ashless reactants (reactants including coal fines and/or asphaltenic species in a coal slurry) (as measured according to the national standard of the people's republic of China GB/T212-2008) and the various yields and parameters were defined as follows:
extraction rate: (weight of residue-weight of raffinate)/weight of residue × 100%;
and (3) solvent recovery rate: (amount of solvent recovered/amount of solvent put in the system). times.100%;
conversion rate: 1- (post-reaction tetrahydrofuran insolubles-post-reaction ash)/dry ashless reactant;
hydrogen consumption: (fresh H)2H in the offgas2) Dry ashless reactant;
oil yield: n-hexane solubles/dry ashless reactant;
gas yield: tail gas does not contain H2Non-condensable/dry ashless reactants of (a);
yield of asphalt: (n-hexane insoluble-tetrahydrofuran insoluble in direct coal liquefaction residue)/drying ashless reactant;
water yield: water/dry ashless reactant is produced.
The basic components of the direct coal liquefaction residues used in the following examples and comparative examples are shown in table 1:
TABLE 1
Direct coal liquefactionResidue fraction Heavy liquefied oil Substances of the bituminous type Coal and ash content
Content (wt%) 19.39 32.51 48.1
In the following examples and comparative examples (except comparative example 2), the extraction solvent used was a fraction of coal direct liquefaction hydropbilizate oil, the basic properties of which are shown in table 2:
TABLE 2
Figure BDA0002634403370000141
In the following examples and comparative examples, the coal dust used was raw material coal, and was pulverized and dried to obtain 85% or more of coal dust having a particle size of less than 74 μm and a moisture content of 4.5 wt%; the raw material coal used is Shendong coal, and the basic components are shown in Table 3:
TABLE 3
Figure BDA0002634403370000142
Note: mad is air drying base moisture; ad is ash; vdaf is volatile.
In the following examples and comparative examples, the hydrogen donating solvent used was coal direct liquefaction hydrogenation stabilized oil, the properties of which are shown in table 4:
TABLE 4
Figure BDA0002634403370000151
Note: IBP is the initial boiling point;
50% refers to the temperature at which 50% by weight of the oil is distilled off;
90% refers to the temperature at which 90% by weight of the oil is distilled off.
In the following examples and comparative examples, the preparation of the catalyst was carried out according to the method described in CN 1579623A:
1) 5.7kg of industrial FeSO is taken4·7H2Dissolving O in 46.88kg of water, adding the O into 15.78kg of coal powder, and uniformly stirring to obtain FeSO4Coal slurry;
2) adding 1.27kg of ammonia water into 17.38kg of water, and adding the obtained ammonia water into the FeSO obtained in the step 1)4Coal slurry is stirred for 10 seconds;
3) the product obtained in the step 2) is heated at 40 ℃ for 3m3Oxidizing for 100 minutes under the air flow;
4) and (4) carrying out centrifugal filtration on the oxidation product to obtain a filter cake, namely the first catalyst.
Example 1
1) Mixing the direct coal liquefaction residue with an extraction solvent according to the weight ratio of 1: 2, extracting at 130 ℃ for 1h under the condition of nitrogen gas and 0.1 MPa.
2) Conveying the extraction product obtained in the step 1) to a horizontal screw centrifuge (German Flottweg230) for solid-liquid separation, wherein the linear velocity of the horizontal screw centrifuge is 60m/s during the solid-liquid separation, and the separation temperature is 130 ℃, so as to obtain extraction liquid and extraction residues;
3) recovering the raffinate obtained in the step 2) in a blade dryer (JG-7.0 of Tianhua chemical machinery and automated research and design institute Co., Ltd.), wherein the drying temperature is 260 ℃ and the drying time is 5 hours to obtain an extraction solvent;
4) mixing the extract obtained in the step 2) with coal dust, a catalyst and a hydrogen supply solvent, wherein the concentration of the obtained coal slurry is 48 wt%, the total addition amount of heavy liquefied oil and asphalt substances in the extract is 12.5 wt% of the coal dust, and the addition amount of the catalyst is 1 wt% of the total weight of the heavy liquefied oil, the asphalt substances and the coal dust in the extract calculated by active component iron; the molar ratio of sulfur powder serving as a sulfur auxiliary agent to a catalyst serving as an iron element is 2, so that coal slurry is prepared;
5) directly liquefying the coal of the coal slurry prepared in the step 4) at 455 ℃ for 90min and 19MPa,
6) the direct coal liquefaction product obtained in step 5) was separated, and the results are shown in table 5.
Example 2
The procedure is as in example 1, except that:
in the step 1), the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1: 4, the extraction temperature is 180 ℃, and the extraction time is 2.5 hours;
in the step 2), the linear velocity of a horizontal screw centrifuge is 90m/s during solid-liquid separation, and the separation temperature is 150 ℃.
The results obtained are shown in Table 5.
Example 3
The procedure is as in example 1, except that:
in the step 1), the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1:1.5, the extraction temperature is 100 ℃, and the extraction time is 1.5 h;
in the step 2), the linear velocity of a horizontal screw centrifuge is 30m/s during solid-liquid separation, and the separation temperature is 100 ℃.
The results obtained are shown in Table 5.
Example 4
The procedure is as in example 1, except that:
in the step 1), the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1: 5, the extraction temperature is 200 ℃, and the extraction time is 3 hours;
in the step 2), the linear velocity of a horizontal screw centrifuge is 150m/s during solid-liquid separation, and the separation temperature is 180 ℃.
The results obtained are shown in Table 5.
Example 5
The procedure is as in example 1, except that:
in the step 4), the coal slurry concentration was 45 wt%.
The results obtained are shown in Table 5.
Example 6
The procedure is as in example 1, except that:
in the step 4), the concentration of the coal slurry is 50 wt%.
The results obtained are shown in Table 5.
Example 7
The procedure is as in example 1, except that:
in the step 4), no coal powder is added, the concentration of the coal slurry is 48 wt%, and the adding amount of the catalyst is 1 wt% of the total weight of the heavy liquefied oil and the asphalt substances in the extraction liquid based on the active component iron.
The results obtained are shown in Table 5.
Example 8
The procedure is as in example 1, except that:
in the step 4), the adding amount of the catalyst is 1.5 wt% of the total weight of the heavy liquefied oil, the asphalt substances and the coal powder in the extraction liquid, calculated by active component iron.
The results obtained are shown in Table 5.
Example 9
The procedure is as in example 1, except that:
in the step 4), the adding amount of the catalyst is 0.5 wt% of the total weight of the heavy liquefied oil, the asphalt substances and the coal powder in the extraction liquid, calculated by active component iron.
The results obtained are shown in Table 5.
Example 10
The procedure is as in example 1, except that:
in the step 3), the drying temperature is 300 ℃, and the drying time is 8 hours.
The results obtained are shown in Table 5.
Example 11
The procedure is as in example 1, except that:
in the step 3), the drying temperature is 200 ℃, and the drying time is 2 h.
The results obtained are shown in Table 5.
Example 12
The procedure is as in example 1, except that:
in the step 1), the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1: 8, the extraction temperature is 80 ℃, and the extraction time is 0.5 h;
in the step 2), the linear velocity of a horizontal screw centrifuge is 20m/s during solid-liquid separation, and the separation temperature is 90 ℃.
In the step 3), the drying temperature is 180 ℃ and the drying time is 1 h.
The results obtained are shown in Table 5.
Comparative example 1
When the coal slurry is prepared, an extraction liquid is not added, and only coal powder, a catalyst and a sulfur auxiliary agent are added, wherein the adding amount of the coal powder enables the concentration of the coal slurry to be 45 wt%, and the adding amount of the catalyst is 1 wt% of the total weight of the coal powder calculated by an active component iron; the molar ratio of sulfur powder, a sulfur auxiliary agent, in terms of sulfur element, to the catalyst, in terms of iron element, was 2 to prepare a coal slurry, and then the direct coal liquefaction reaction was performed under the same conditions as in example 1.
The results obtained are shown in Table 5.
TABLE 5
Figure BDA0002634403370000191
It can be seen from the results in table 5 that, by using the embodiment of the present invention, the extraction solvent can be recovered while extracting the heavy liquefied oil and the asphalt substances in the coal direct liquefaction residue with a high extraction rate, and the solvent recovery rate can reach 98-98%, thereby realizing the recycling of the extraction solvent.
In addition, when the extraction liquid is prepared into coal slurry and recycled to the direct coal liquefaction reaction, compared with the scheme of comparative example 1 without adding the extraction liquid, the oil yield can be improved to 70.2% from 56.8%, and the extraction liquid and the coal powder can be mixed to prepare the coal slurry according to actual needs, so that the effect of remarkably improving the oil yield can be achieved. Not only makes full use of the direct coal liquefaction residue, but also greatly improves the total oil yield and economic benefit of the direct coal liquefaction.
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 (12)

1. A method for treating coal direct liquefaction residues is characterized by comprising the following steps:
1) extracting the direct coal liquefaction residues with an extraction solvent;
2) carrying out solid-liquid separation on the extraction product obtained in the step 1) to obtain an extraction liquid and an extraction residue;
3) mixing the extract obtained in the step 2) with a catalyst and a hydrogen donor solvent to prepare coal slurry.
2. The treatment method according to claim 1, wherein in the step 1), the extraction solvent is one or more of coal direct liquefaction hydrogenation stabilized oil, coal high-temperature coking decrystallization washing oil and coal direct liquefaction crude oil;
preferably, the extraction solvent is a coal direct liquefaction hydrogenation stabilized oil.
3. The process of claim 1 or 2, wherein in step 1), the conditions of the extraction comprise: the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1:1-10, the extraction temperature is 80-220 ℃, and the extraction time is 0.5-5 h;
preferably, the weight ratio of the direct coal liquefaction residue to the extraction solvent is 1:1.5-5, the extraction temperature is 100-200 ℃, and the extraction time is 1-3 h.
4. The treatment method according to any one of claims 1 to 3, wherein in the step 2), the solid-liquid separation is performed by centrifugation, filtration, sedimentation, or the like;
preferably, in the step 2), the solid-liquid separation is performed by using a screw centrifuge;
more preferably, when the solid-liquid separation is carried out, the separation linear speed of the horizontal screw centrifuge is 20-180m/s, and the separation temperature is 90-200 ℃;
further preferably, when the solid-liquid separation is carried out, the separation linear velocity of the horizontal screw centrifuge is 30-150m/s, and the separation temperature is 100-180 ℃.
5. The treatment method according to any one of claims 1 to 3, wherein in the step 3), the hydrogen donor solvent is one or more of coal high-temperature coking decrystallized anthracene oil, coal high-temperature coking decrystallized washing oil, petroleum-based heavy oil catalytic cracking recycle oil, petroleum-based heavy oil catalytic cracking clarified oil hydrogenated oil and coal direct liquefaction hydrogenation stabilized oil;
preferably, the hydrogen donor solvent is coal direct liquefaction hydrogenation stabilized oil.
6. The process of any one of claims 1 to 3, wherein the coal slurry concentration in step 3) is 40 to 55 wt%.
7. The treatment process according to any one of claims 1 to 3, wherein the active component of the catalyst is selected from one or more of iron, molybdenum, nickel, cobalt and tungsten;
preferably, the catalyst is one or more of an iron-based catalyst, a molybdenum-based catalyst, a nickel-based catalyst, a cobalt-based catalyst and a tungsten-based catalyst;
preferably, the catalyst is an iron-based catalyst;
preferably, the amount of the catalyst added is 0.2-3 wt% of the total weight of the heavy liquefied oil and the asphaltic substances in the extraction solution based on the active ingredients.
8. The process according to any one of claims 1 to 3, wherein in the step 3), coal powder is further used in preparing the coal slurry,
preferably, the addition amount of the catalyst is 0.2-3 wt% of the total weight of the heavy liquefied oil, the asphaltic substances and the coal dust in the extraction liquid based on the active ingredients.
9. The processing method according to any one of claims 1 to 3, wherein the method further comprises: recovering the extraction solvent in the raffinate obtained in the step 2).
10. A direct coal liquefaction method characterized by carrying out a direct coal liquefaction reaction using the coal slurry obtained by the treatment method according to any one of claims 1 to 9 as a raw material.
11. The direct coal liquefaction process of claim 10, wherein the conditions of the direct coal liquefaction reaction include: the reaction temperature is 440-460 ℃, the reaction time is 60-120min, and the reaction hydrogen pressure is 12-20 MPa.
12. Use of the direct coal liquefaction process of claim 10 or 11 in the direct coal liquefaction.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113457204A (en) * 2021-06-02 2021-10-01 中国神华煤制油化工有限公司 Method for extracting coal directly to liquefy oil residue by using coking crude benzene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01304182A (en) * 1988-05-31 1989-12-07 Nippon Katsutan Ekika Kk Coal liquefaction technique
CN101885976A (en) * 2010-07-02 2010-11-17 神华集团有限责任公司 Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof
CN102533373A (en) * 2012-01-12 2012-07-04 锡林郭勒盟创源煤化工有限公司 Method for using residue generated by directly liquefying coal
CN103254933A (en) * 2013-05-30 2013-08-21 神华集团有限责任公司 Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01304182A (en) * 1988-05-31 1989-12-07 Nippon Katsutan Ekika Kk Coal liquefaction technique
CN101885976A (en) * 2010-07-02 2010-11-17 神华集团有限责任公司 Method for extracting heavy liquefaction oil and intermediate-phase bitumen matter from coal liquefaction residuals and application thereof
CN102533373A (en) * 2012-01-12 2012-07-04 锡林郭勒盟创源煤化工有限公司 Method for using residue generated by directly liquefying coal
CN103254933A (en) * 2013-05-30 2013-08-21 神华集团有限责任公司 Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113457204A (en) * 2021-06-02 2021-10-01 中国神华煤制油化工有限公司 Method for extracting coal directly to liquefy oil residue by using coking crude benzene
CN113457204B (en) * 2021-06-02 2022-05-31 中国神华煤制油化工有限公司 Method for extracting coal directly to liquefy oil residue by using coking crude benzene

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