CN112251252A - Direct coal liquefaction catalyst and direct coal liquefaction method - Google Patents
Direct coal liquefaction catalyst and direct coal liquefaction method Download PDFInfo
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- CN112251252A CN112251252A CN202011027345.8A CN202011027345A CN112251252A CN 112251252 A CN112251252 A CN 112251252A CN 202011027345 A CN202011027345 A CN 202011027345A CN 112251252 A CN112251252 A CN 112251252A
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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
- C10G1/008—Controlling or regulating of liquefaction processes
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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
- C10G1/06—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
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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
- C10G1/086—Characterised by the catalyst used
Abstract
The invention relates to the technical field of direct coal liquefaction, in particular to a direct coal liquefaction catalyst and a direct coal liquefaction method, wherein the direct coal liquefaction catalyst comprises carrier coal and active metal elements loaded on the carrier coal, the vitrinite content of the carrier coal is more than or equal to 70 wt%, and the active metal elements contain iron. The direct coal liquefaction catalyst provided by the invention adopts high vitrinite and low-ash coal as carrier coal, vitrinite structural units are easy to break in the direct coal liquefaction process to generate small-fragment free radicals, and the active components of the catalyst loaded on the carrier coal are uniformly dispersed in a coal liquefaction system along with the cracking of the carrier coal, so that good catalytic conditions are provided for hydrogen activation, coal pyrolysis free radical fragment hydrogenation and coal free radical cracking hydrogenation to oil, and the coal liquefaction conversion rate and the oil yield can be effectively improved.
Description
Technical Field
The invention relates to the technical field of direct coal liquefaction, in particular to a direct coal liquefaction catalyst and a direct coal liquefaction method.
Background
The direct coal liquefaction is a novel coal chemical clean coal technology for converting coal into liquid products by thermochemical reaction and catalytic reaction of the coal under the double actions of a hydrogen supply solvent and a catalyst under the condition of high temperature and high pressure hydrogen. The coal direct liquefaction oil product produced by the technology has high density, high heat capacity, high heat stability, high heat value, low condensation point, low sulfur, low nitrogen, low aromatic hydrocarbon and high naphthenic hydrocarbon, has unique physical properties different from the conventional petroleum-based oil product, and can provide a new source for military oil and special fuel in the aerospace field. Therefore, the direct coal liquefaction technology is always a great concern in the coal clean and efficient conversion and utilization industry. The direct coal liquefaction process involves complex physical and chemical processes, and has a plurality of influencing factors, mainly including: the type and nature of the coal, the reactor form, the catalyst, the hydrogen donor solvent, the reaction operating conditions, and the like. The direct coal liquefaction catalyst can promote coal pyrolysis and accelerate pyrolysis macromolecule hydrocracking, stabilize coal pyrolysis free radicals, improve liquefied oil yield and improve oil quality, and how to effectively utilize the catalyst hydrogenation liquefaction activity is always a hotspot of direct coal liquefaction research.
The catalyst active component iron can react with hydrogen sulfide to produce Fe under the condition of coal liquefaction1-xAnd S has good coal liquefaction catalytic activity, is low in price and can be discarded, and is always used as a priority of a direct coal liquefaction catalyst. CN1579623A discloses a high-dispersion iron-based direct coal liquefaction catalyst, the carrier of the catalyst is Shendong complement tower coal, the highest inert group content is 59.29%, the lowest inert group content is 27.75%, the average content is 43.72%, the quantity of bridge bonds among structural units of the inert group is the least, the structural units are mainly connected through saturated rings, the condensation degree of the structural units of the inert group is higher, the saturated rings are relatively difficult to break in the pyrolysis process, and the generated free radical fragments are larger. In the reaction process, the catalyst particles are inevitably combined with mineral substances after releasing coal free radicals and coal free radicals which do not obtain hydrogen polymerization cokes in time, the catalyst is wrapped, and the active site of the catalyst is annihilated, so that the catalytic activity is insufficient, the direct coal liquefaction reaction activity is reduced, and the coal conversion rate and the oil yield are reduced.
Disclosure of Invention
The invention aims to solve the problem that the catalytic activity is reduced due to the fact that a catalyst is wrapped in the pyrolysis process in the prior art, and provides a direct coal liquefaction catalyst and a direct coal liquefaction method.
In order to achieve the above object, a first aspect of the present invention provides a direct coal liquefaction catalyst, which includes carrier coal and an active metal element supported on the carrier coal, wherein a vitrinite content of the carrier coal is equal to or greater than 70 wt%, and the active metal element contains iron.
In a second aspect, the present invention provides a direct coal liquefaction method, comprising the steps of: and mixing the direct coal liquefaction catalyst, the raw material coal and the solvent oil to prepare coal oil slurry, introducing the coal oil slurry into a reaction system, and sequentially carrying out liquefaction reaction in a first-stage reactor and a second-stage reactor.
According to the technical scheme, the direct coal liquefaction catalyst provided by the invention adopts high vitrinite and low-ash coal as carrier coal, vitrinite structural units are easy to break in the direct coal liquefaction process to generate small-fragment free radicals, and the active ingredients of the catalyst loaded on the carrier coal are uniformly dispersed in a coal liquefaction system along with the cracking of the carrier coal, so that good catalytic conditions are provided for hydrogen activation, coal pyrolysis free radical fragment hydrogenation and coal free radical cracking hydrogenation to oil, and the coal liquefaction conversion rate and the oil yield can be effectively improved.
Drawings
Fig. 1 is a process flow diagram of a direct coal liquefaction process according to an embodiment of the present invention.
Description of the reference numerals
1. Catalyst slurry oil homogenizing tank 2 and slurry oil preparation tank
3. Coal oil slurry preheater 4 and first-stage reactor
5. Static mixer 6, two-stage reactor
7. Solvent naphtha 8, direct coal liquefaction catalyst
9. Raw coal 10, steam
11. Condensed water 12, hydrogen-containing gas
13. Liquefied product
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a direct coal liquefaction catalyst which comprises carrier coal and active metal elements loaded on the carrier coal, wherein the vitrinite content of the carrier coal is more than or equal to 70 wt%, and the active metal elements contain iron.
In the invention, vitrinite-rich coal is introduced into a direct coal liquefaction catalyst as carrier coal, vitrinite structural units in the vitrinite-rich coal are mainly monocyclic aromatic hydrocarbon and are rich in weak chemical bonds such as ether bonds, methylene bonds and the like, and can be completely cracked into radical fragments with different sizes according to different liquefaction reaction conditions in the direct coal liquefaction process, and catalyst active components loaded on the carrier coal are uniformly dispersed in a coal liquefaction system along with the cracking of the carrier coal, so that the effective collision of liquefied coal radical fragments and hydrogen is increased, good catalytic conditions are provided for the reactions of hydrogen activation, the re-hydrogenation of coal pyrolysis large radical fragments and the conversion of coal radical cracking hydrogenation into oil and the like in the direct coal liquefaction process, coal radicals are converted into oil products by obtaining active hydrogen, and the coal liquefaction conversion rate and the oil yield are effectively improved. Under the preferred condition, the vitrinite content of the carrier coal is more than or equal to 80wt percent, and more preferably more than or equal to 90wt percent.
According to the invention, the lower the ash content of the directly liquefied carrier coal is, the higher the vitrinite content is, the higher the conversion rate of small free radical fragments is under the direct liquefaction reaction condition, and in a liquefaction reaction system, the more uniformly the active components in the catalyst are dispersed, the smaller the granularity is, the lower the aggregation possibility is, the effective collision probability of the active components and reactants can be increased, namely, the higher the catalytic activity is. Therefore, in order to improve the activity of the coal direct liquefaction catalyst, it is preferable that the ash content a of the support coal is under a condition thatd5 wt% or less, more preferably 2.5 wt% or less, most preferably 1 wt% or less; volatile component V of the carrier coaldafNot less than 35 wt%, more preferably not less than 40 wt%.
In order to further improve the catalytic efficiency of the coal direct liquefaction catalyst, the content of the active metal element is preferably 1.2 to 7.2 wt% (for example, 1.2 wt%, 2.5 wt%, 5 wt%, 6 wt%, 7.2 wt%, or any value in a range formed by any two of the above values) based on the total amount of the coal direct liquefaction catalyst; the content of the carrier coal is 85 wt% or more (for example, 85 wt%, 87.5 wt%, 90 wt%, 95 wt%, or any value in a range of any two of the above values).
In the present invention, the active metal element exists in the form of metal hydroxide, for example, the iron element exists in the form of FeOOH, and may be at least one of α -FeOOH, β -FeOOH, and γ -FeOOH, and further, the content of the metal hydroxide may be calculated according to the content of the active metal element.
In order to further improve the catalytic efficiency of the coal direct liquefaction catalyst, the active metal element further contains at least one of Cr, Mo, W, Sg, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Hs, Mt and Ds under the preferable conditions; preferably, the active metal element is selected from at least one of Mo, W, Co and Ni.
In the invention, the preparation method of the coal direct liquefaction catalyst can be obtained by selecting a proper route according to a known preparation method of the coal liquefaction catalyst, and for example, a dipping method, a spray drying method and the like can be adopted.
For example, the preparation method of the coal liquefaction catalyst can be as follows:
(1) in the presence of a water-containing solvent, uniformly stirring an iron source and carrier coal, adding an alkaline solution, and adjusting the pH of the system to 6-12 to obtain coal slurry;
(2) oxidizing the coal slurry;
(4) and carrying out centrifugal filtration or pressure filtration on the oxidized coal slurry.
The invention also provides a direct coal liquefaction method, which comprises the following steps: and mixing the direct coal liquefaction catalyst, the raw material coal and the solvent oil to prepare the coal oil slurry, and sequentially carrying out a first-stage liquefaction reaction and a second-stage liquefaction reaction on the coal oil slurry.
In the invention, the raw material coal can be young bituminous coal and old lignite, and the anhydrous and ashless volatile component V of the raw material coal is preferably selecteddaf≥35wt％，Ad≤10wt％。
Because coal inert component liquefaction conditions are harsh, thermal cracking is mostly large radical fragments, and a large radical fragment polycondensate which does not effectively capture active hydrogen, unreacted raw material coal and inorganic mineral substances in the raw material coal are mutually fused and solidified to wrap annihilation catalysts, so that the liquefaction activity of the catalysts loaded on the reaction system is influenced, in order to fully liquefy the raw material coal, the reaction system comprises a first-stage reactor and a second-stage reactor, and preferably, the reaction conditions of the first-stage reaction carried out in the first-stage reactor comprise: the reaction temperature is 445-460 ℃, and the reaction pressure is 12-20 MPa; further preferably, the reaction conditions of the secondary reaction carried out in the secondary reactor comprise: the reaction temperature is 445 ℃ and 460 ℃, and the reaction pressure is 12-20 MPa.
In the present invention, the kind of the first-stage reactor and the second-stage reactor may be those shown by those skilled in the art, for example, the first-stage reactor and the second-stage reactor are each independently selected from one of a bubbling bed, an ebullating bed, a fully back-mixed suspended bed, and an internal and external loop reactor.
In the invention, the coal direct liquefaction catalyst can be introduced into the reaction system at one time through the first-stage reactor, and can also be introduced into the reaction system at two times according to the hydrogen consumption of the reaction in the first-stage reactor and the second-stage reactor.
In the direct coal liquefaction reaction process, the hydrogen consumption of the liquefaction reactant in the first-stage reaction accounts for about 70% of the total hydrogen consumption, the hydrogen consumption in the second-stage reactor accounts for about 30% of the total hydrogen consumption, the first-stage reactant is easy-to-convert coal, the second-stage reactant is difficult-to-react, and longer conversion time is needed, so that fresh catalyst is added into the second-stage reactor, the conversion efficiency of raw material coal can be improved, and under the optimal condition, the direct coal liquefaction catalyst is introduced into the second-stage reactor twice, wherein 60-80 wt% of the direct coal liquefaction catalyst is added into the first-stage liquefaction reaction, and 20-40 wt% of the direct coal liquefaction catalyst is added into the second-stage liquefaction reaction.
According to the invention, under the preferred conditions, the amount of the coal direct liquefaction catalyst is 0.2-1.2 wt% calculated by active metal elements contained in the coal direct liquefaction catalyst based on the total amount of dry coal; the dry coal includes feed coal and carrier coal from the coal direct liquefaction catalyst.
In order to improve the catalytic activity of the coal direct liquefaction catalyst, under the preferable condition, the oil coal slurry also contains a sulfur auxiliary agent; further preferably, the molar ratio of the sulfur element contained in the sulfur auxiliary agent to the iron element contained in the catalyst is 1.5-3: 1.
According to the invention, under the preferable conditions, the solid content of the oil coal slurry is 40-60 wt%.
Fig. 1 is a process flow diagram of a direct coal liquefaction method according to an embodiment of the present invention, and as shown in fig. 1, the present invention provides a direct coal liquefaction method including the steps of:
uniformly mixing a part of coal direct liquefaction catalyst 8, a sulfur auxiliary agent and solvent oil 7 in a catalyst oil slurry homogenizing tank 1 to obtain a material flow 1, introducing the material flow 1, raw material coal 9 and steam 10 into an oil coal slurry preparation tank 2 to obtain a mixed system, heating the mixed system to 80-200 ℃ under the action of the steam 10, simultaneously converting the steam 10 into condensed water 11 to be led out of the system, and fully mixing and swelling to obtain oil coal slurry; preheating the oil-coal slurry by an oil-coal slurry preheater 3, introducing the preheated oil-coal slurry and a hydrogen-containing gas 12 into a first-stage reactor 4 together for a first liquefaction reaction to obtain a first liquefied product;
and then mixing the residual part of the direct coal liquefaction catalyst, the first liquefied product and the hydrogen-containing gas 12 together in a static mixer 5, introducing the mixed material into a secondary reactor 6 for a second liquefaction reaction to obtain a second liquefied product, and introducing the second liquefied product into a downstream separation system for product separation.
Wherein the hydrogen-containing gas 12 is recycled hydrogen and/or fresh hydrogen from the system.
The solvent oil is at least one selected from coal high-temperature coking decrystallized anthracene oil, washing oil, petroleum heavy oil catalytic cracking cycle oil, clarified oil hydrogenated oil and coal direct liquefaction self-production cycle solvent oil.
The present invention will be described in detail below by way of examples.
In the following examples, physical properties of the coal samples are shown in table 1.
TABLE 1 physical Properties of coal samples
Wherein the coal sample 4 consists of a coal sample 1 and a coal sample 2 according to the weight ratio of 5: 1; the coal sample 5 is composed of a coal sample 1 and a coal sample 3 according to a weight ratio of 5: 1.
Example 1
Preparation of a direct coal liquefaction catalyst:
5.7 parts by weight of FeSO4·7H2Dissolving O in 46.88 parts by weight of water to obtain FeSO4Solution in FeSO4Adding 15.78 parts by weight of carrier coal (coal sample 2) into the solution, and uniformly stirring to obtain FeSO4Coal slurry; and
diluting 1.27 parts by weight of strong ammonia water with 17.38 parts by weight of water to obtain an ammonia water solution;
adding the aqueous ammonia solution to the FeSO under stirring4Adjusting pH to 7.8 in coal slurry, continuing stirring for 10s after adding, and then enabling the reaction product to be at 40 ℃ and 3m3Oxidizing for 100min under the air flow/h, and carrying out centrifugal filtration and drying on an oxidation product to obtain the coal direct liquefaction catalyst A1, wherein the physical parameters are shown in Table 2.
Direct coal liquefaction reaction:
taking Shendong coal as raw material coal, and carrying out direct coal liquefaction reaction on a direct coal liquefaction (BSU) device of 180kg/d, wherein the dosage of the raw material coal (coal sample 1) is 5 times of that of the carrier coal, and the method comprises the following steps:
uniformly mixing 70 wt% of coal direct liquefaction catalyst A1, sulfur powder (the molar ratio of sulfur element in the sulfur powder to iron element in catalyst A1 is 2:1) and solvent oil 7 (a self-produced hydrogen supply solvent with a distillation range of 220-; preheating the oil-coal slurry to the reaction starting temperature by an oil-coal slurry preheater 3, and introducing the oil-coal slurry and a hydrogen-containing gas into a first-stage reactor 4 together for a first liquefaction reaction to obtain a first liquefied product; the conditions of the first liquefaction reaction are: the reaction temperature is 455 ℃ and the reaction pressure is 19 MPa;
then mixing the residual 30 wt% of coal direct liquefaction catalyst, the first liquefaction product and hydrogen-containing gas together in a static mixer 5, introducing the mixed material into a secondary reactor 6 for a second liquefaction reaction to obtain a second liquefaction product, and introducing the second liquefaction product into a downstream separation system for product separation analysis, wherein the conditions of the second liquefaction reaction are as follows: 455 ℃ and the reaction pressure is 19 MPa.
The results of the analysis of the direct coal liquefaction product are shown in table 3:
the composition of the gaseous substances (namely gas phase products) is analyzed by a gas chromatograph; the liquid-solid mixture (i.e. liquid-solid phase product) is subjected to Soxhlet extraction separation by using n-hexane and tetrahydrofuran in sequence, wherein n-hexane soluble substances are defined as oil, n-hexane insoluble substances and tetrahydrofuran soluble substances are defined as asphaltene, and tetrahydrofuran insoluble substances are defined as unreacted coal and ash, the yield is calculated by taking coal dry ashless coal (daf coal) as a reference, and various yields are defined as follows:
oil yield: n-hexane solubles/daf coal × 100%;
water yield: produced water/daf coal × 100%;
gas yield: tail gas does not contain H2The non-condensable gas/daf coal is multiplied by 100 percent;
hydrogen consumption: (fresh H)2H in the offgas2) Daf coal × 100%;
coal conversion: 1- (residue THF insoluble-residue unoxidized ash)/daf coal x 100%, wherein residue unoxidized ash refers to the weight of ash in the coal added in terms of the actual weight of iron, sulfur and other inorganics entering the coal slurry;
asphaltene yield: (insoluble in n-hexane-insoluble in tetrahydrofuran) in the residue)/daf coal X100%.
Comparative example 1
The process of example 1 was followed except that: adopting a coal sample 4 as carrier coal to obtain a direct coal liquefaction catalyst B1, wherein the physical parameters are shown in Table 2;
the coal sample 4 is adopted as the raw material coal, and the direct coal liquefaction reaction method is the same as the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 2
The process of example 1 was followed except that: adopting a coal sample 3 as carrier coal to obtain a direct coal liquefaction catalyst A2, wherein the physical parameters are shown in Table 2;
the coal sample 1 is adopted as the raw material coal, and the direct coal liquefaction reaction method is the same as the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 2
The process of example 1 was followed except that: adopting a coal sample 5 as carrier coal to obtain a direct coal liquefaction catalyst B2, wherein the physical parameters are shown in Table 2;
the coal sample 5 is adopted as raw material coal, and the direct coal liquefaction reaction method is the same as that of the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 3
According to the method of the embodiment 1, except that ammonium molybdate is added in the preparation process of the direct coal liquefaction catalyst, the specific steps are as follows:
5.7 parts by weight of FeSO4·7H2Dissolving the O and the water in 46.88 parts by weight to obtain a mixed solution, adding 15.78 parts by weight of carrier coal (coal sample 2) into the mixed solution, and uniformly stirring to obtain coal slurry;
diluting 1.27 parts by weight of strong ammonia water with 17.38 parts by weight of water to obtain an ammonia water solution;
adding the aqueous ammonia solution to the FeSO under stirring4Adjusting pH to 7.8 in coal slurry, continuing stirring for 10s after adding, and then enabling the reaction product to be at 40 ℃ and 3m3Oxidizing for 100min at/h air flow, centrifuging, filtering, and soaking in 2.5 weight parts of 15% (NH)4)6Mo7O24Drying the aqueous solution to obtain a coal direct liquefaction catalyst A3, wherein the physical parameters are shown in Table 2;
the direct coal liquefaction reaction method is the same as that of example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 3
The preparation method of the direct coal liquefaction catalyst is the same as that of example 1, except that in the direct coal liquefaction reaction process, the direct coal liquefaction catalyst A1 is introduced into the reaction system through the first-stage reactor at one time;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 4
The direct coal liquefaction catalyst was prepared in the same manner as in example 1, except that the direct coal liquefaction catalyst a1 was introduced into the reaction system in two times during the direct coal liquefaction reaction, wherein 50 wt% of the direct coal liquefaction catalyst a1 was introduced into the reaction system through the first-stage reactor, and 50 wt% of the direct coal liquefaction catalyst a1 was introduced into the reaction system through the second-stage reactor;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 5
The preparation method of the direct coal liquefaction catalyst is the same as that in example 1, except that in the direct coal liquefaction reaction process, the reaction conditions of the first liquefaction reaction and the second liquefaction reaction are as follows: the reaction temperature is 480 ℃ and the reaction pressure is 25 MPa;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 4
The direct coal liquefaction catalyst was prepared in the same manner as in example 1, except that the amount of the raw material coal (coal sample 1) was 29 times the amount of the carrier coal (coal sample 2) during the direct coal liquefaction reaction.
The analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 5
The preparation method of the direct coal liquefaction catalyst is the same as that of example 1, except that the amount of the raw material coal (coal sample 1) is 9 times that of the carrier coal (coal sample 2) in the direct coal liquefaction reaction process.
The analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 6
The preparation method of the direct coal liquefaction catalyst is the same as that of example 1, except that the amount of the raw material coal (coal sample 1) is 3 times that of the carrier coal (coal sample 2) in the direct coal liquefaction reaction process.
The analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 6
The direct coal liquefaction catalyst was prepared as in example 1 except that FeSO was used4·7H2The amount of O added was 1.2 parts by weight, whereby catalyst A4 was obtained.
The coal sample 2 is adopted as the raw material coal, and the direct coal liquefaction reaction method is the same as the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Example 7
The direct coal liquefaction catalyst was prepared as in example 1 except that FeSO was used4·7H2The amount of O added was 2.5 parts by weight, whereby catalyst A5 was obtained.
The coal sample 2 is adopted as the raw material coal, and the direct coal liquefaction reaction method is the same as the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Comparative example 7
The direct coal liquefaction catalyst was prepared as in example 1 except that FeSO was used4·7H2The amount of O added was 6.8 parts by weight, whereby catalyst B3 was obtained.
The coal sample 2 is adopted as the raw material coal, and the direct coal liquefaction reaction method is the same as the example 1;
the analysis method of the direct coal liquefaction product was the same as in example 1, and the results are shown in Table 3.
Table 2: physical parameters of catalysts A1-A3 and catalysts B1-B3
TABLE 3 analysis of direct coal liquefaction products in examples 1-4 and comparative examples 1-5
Wherein, the dosage of the catalyst is equal to the total weight of the active metal elements/(the total weight of the raw material coal and the carrier coal) multiplied by 100 percent.
As can be seen from Table 3, it can be seen from the comparison between examples 1-2 and comparative examples 1-2 that the higher the vitrinite content in the supported coal of the catalyst, the higher the activity of the catalyst, and the higher the coal conversion rate and oil yield in the coal liquefaction reaction.
As can be seen by comparing example 1 with comparative example 4, the conversion rate and oil yield of coal can be improved by introducing the coal direct liquefaction catalyst into the reaction system in several times.
As can be seen by comparing example 1 with comparative example 5, as the reaction temperature, pressure increased, the conversion of coal and the gas yield increased, but the oil yield decreased.
As can be seen from comparison of examples 1, 4 to 7 and comparative examples 6 to 7, when the amount of the coal direct liquefaction catalyst is 1.13 wt% in terms of active metal elements contained therein, the activity is high, so that the conversion of coal is as high as 91.09 wt% and the oil yield is as high as 62.26 wt%.
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 (10)
1. The direct coal liquefaction catalyst is characterized by comprising carrier coal and active metal elements loaded on the carrier coal, wherein the vitrinite content of the carrier coal is more than or equal to 70 wt% based on the total amount of the carrier coal, and the active metal elements comprise iron.
2. The direct coal liquefaction catalyst according to claim 1, wherein the vitrinite content of the support coal is equal to or greater than 80 wt%, preferably equal to or greater than 90 wt%, based on the total amount of the support coal.
3. The direct coal liquefaction catalyst according to claim 1 or 2, wherein the ash content a of the support coal is based on the total amount of the support coald5% by weight or less, preferably 2.5% by weight or less;
preferably, the volatile component V of the carrier coal is based on the total amount of the carrier coaldaf35 wt% or more, preferably 40 wt% or more.
4. The coal direct liquefaction catalyst according to any one of claims 1 to 3, wherein the content of the active metal element is 1.2 to 7.2 wt% based on the total amount of the coal direct liquefaction catalyst; the content of the carrier coal is more than or equal to 85 wt%.
5. The coal direct liquefaction catalyst of any one of claims 1 to 4, wherein the active metal element further comprises at least one of Cr, Mo, W, Sg, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Hs, Mt, Ds;
preferably, the active metal element further contains at least one of Mo, W, Co, and Ni.
6. A direct coal liquefaction method is characterized by comprising the following steps: mixing the direct coal liquefaction catalyst of any one of claims 1 to 5, raw coal and solvent oil to prepare coal oil slurry, and sequentially carrying out a first-stage liquefaction reaction and a second-stage liquefaction reaction on the coal oil slurry;
preferably, the conditions of the first stage liquefaction reaction include: the first-stage reaction temperature is 445-460 ℃, and the first-stage reaction pressure is 12-20 MPa;
preferably, the conditions of the secondary liquefaction reaction include: the second-stage reaction temperature is 445-460 ℃, and the second-stage reaction pressure is 12-20 MPa;
preferably, the first-stage liquefaction reaction and the second-stage liquefaction reaction are respectively carried out in a first-stage reactor and a second-stage reactor, and the first-stage reactor and the second-stage reactor are respectively and independently selected from one of a bubbling bed, an ebullating bed, a full-backmixing suspension bed and an internal and external loop reactor.
7. The direct coal liquefaction method of claim 6, wherein the direct coal liquefaction catalyst is introduced at one time by the primary liquefaction reaction; or
The direct coal liquefaction catalyst is introduced by two times, wherein 60-80 wt% of the direct coal liquefaction catalyst is added into the first-stage liquefaction reaction, and 20-40 wt% of the direct coal liquefaction catalyst is added into the second-stage liquefaction reaction.
8. The direct coal liquefaction method according to claim 6 or 7, wherein the amount of the direct coal liquefaction catalyst is 0.2 to 1.2 wt% in terms of active metal elements contained, based on the total amount of dry coal;
wherein the dry coal comprises raw coal and carrier coal from the coal direct liquefaction catalyst;
preferably, the oil coal slurry also contains a sulfur auxiliary agent;
preferably, the molar ratio of the sulfur element contained in the sulfur auxiliary agent to the iron element contained in the catalyst is 1.5-3: 1.
9. The direct coal liquefaction method of any one of claims 6 to 8, wherein the solid content of the coal oil slurry is 40 to 60 wt%.
10. The direct coal liquefaction method according to any one of claims 6 to 9, wherein the volatile matter V of the raw coaldafMore than or equal to 35wt percent; ash content A of the raw material coald≤10wt％。
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