CN102068992B - Hydrorefining catalyst for preparing fuel oil from coal tar, preparation method and application method thereof - Google Patents

Abstract

Aiming at the problems existing in the existing coal tar hydrogenation catalysts, the invention proposes a new special hydrogenation refining catalyst for coal tar and its preparation and application method. The hydrorefining catalyst consists of active components, assistants and carriers. The active components of the hydrorefining catalyst are MoO ₃ and NiO or MoO ₃ and CoO, the additives are Bi ₂ O ₃ and K ₂ O, and the carrier is alumina and barium oxide. Calculated in the form of oxides, the active component, auxiliary agent and carrier account for 15-35%, 2-5% and 60-83% of the total mass of the catalyst respectively. The catalyst preparation steps include kneading and milling, extrusion molding, impregnation and catalyst post-treatment, etc. The new technology of ultrasonic impregnation is introduced to strictly control the catalyst preparation conditions. Compared with the prior art, the catalyst of the present invention has excellent surface physical and chemical properties, good heteroatom and gum removal activity, hydrogenation saturation ability, and excellent stability and mechanical strength, effectively improving the quality of hydrogenated product oil and yield.

Description

A kind of producing fuel oil from coal tar Hydrobon catalyst and methods for making and using same thereof

Technical field

The invention belongs to coal tar hydrogenating and produce the fuel oil technical field, be specifically related to a kind of Hydrobon catalyst and methods for making and using same thereof that is used for producing fuel oil from coal tar.

Background technology

At present the Energy Situation of China is " oil starvation, weak breath, a rich coal ", and the energy supply problem has become the outstanding problem that China's economic development and national security face.Under the petroleum resources condition of limited, development Coal Chemical Industry industry, exploitation deep process technology and product obviously have important reality and strategic importance.Utilizing in the approach of coal, the pyrolysis of coal can provide multiple coal-based product, be clean, efficiently and rationally utilize low-order coal resource effective way.Pyrolysis of coal oil or title coal tar are the accessory substances of coal coking, destructive distillation and gasification, and its output in domestic is above 1,000 ten thousand tons.The processing and utilization part of domestic coal tar is used to extract chemicals such as naphthols, but can produce a large amount of sewage; Another part is burnt as low-quality fuel oil after simple process, also can produce atmosphere pollutions such as NOx, SOx.Adopt hydrogenation technique can accomplish desulfurization, denitrogenation, the deoxidation of coal tar raw material, insatiable hunger alkene and aromatic hydrocarbons are saturated, improve raw material H/C ratio, improve its stability, obtain high-grade fuel oil, and reduce environmental pollution.Therefore, be raw material with coal tar, produce fuel oil through the hydrogenation means and can produce tangible economic and social benefit, effectively alleviate China's energy starved present situation.

The research and development of preparing fuel oil with coal oil hydrogenation technology at home and abroad launch, and for example patent CN 1903984A is the coal tar pitch of raw material production gasoline, diesel and upgrading with full cut of high, medium and low temperature coal tar or mixed coal tar.The report of external relevant coal tar hydrogenating is less, and this possibly utilize the strategic choice of aspect relevant with external coal tar.Canada patent CA 312811 in 1931 has described the hydrogenation and the cracking process of coal tar, mineral wet goods raw material, and from cracked gas, obtains the method for required hydrogen feed.The not mentioned hydrogenated products title of this patent, also not mentioned product can be used as fuel oil.Document " from coal tar oils production gasoline " (Harry Clough.Industrialand Engineering Chemistry; 1957; 49 (4): be to be raw material commodity in use catalyst 5058,6434 and 231 673-678) with the creasote that coal tar extracts; Produce gasoline through two-step method, its raw material is not a coal tar.Document " hydrogenation of Yallourn lignite tar continously hydrogen adding " (Peter C.Wailesa; Alan P.Bella; Etc.Fuel, 1980,59 (2): 128-132) introduced the method that coal tar hydrogenating obtains the oil refinery raw material; Hydrogenation products is raw material but not the fuel oil of oil refinery, and catalyst system therefor is the commercial catalyst of BASF AG.

The target of coal tar hydrogenating technology is the petrol and diesel oil fuel of production high-quality and improves the oil product yield as far as possible that its core is catalyst.The final effect that coal tar hydrogenating is produced fuel oil depends on catalyst performance, and the composition of catalyst (active component, auxiliary agent and carrier), preparation method and condition (condition of molding, sintering temperature, roasting medium etc.) have determined the performance of catalyst.The catalyst that chemical composition is identical; If the preparation method is different with condition; Then the microscopic property of catalyst (as active material grain size, catalyst aperture distribute and active component at the dispersing uniformity of catalyst surface etc.) difference, thereby cause the performance of catalyst that very big-difference is arranged.

In the research of coal tar hydrogenating, mainly there is following problem in the catalyst aspect at present.One of which, catalyst system therefor are mainly the commercial catalyst of petroleum chemical industry, and for example Chinese patent CN 101126034A adopts petrochemical industry commodity hydrogenation protecting, hydrofinishing and hydrocracking catalyst.Compare with oil, coal tar is by himself unique composition and character, and it forms complicated; Contain more unsaturated heavy hydrocarbon; Acidity is high, and viscosity is high, and density is big; Especially sulphur, nitrogen, carbon residue, colloid, asphalt content are higher, therefore press for to develop the special-purpose catalyst that is fit to coal tar hydrogenating.Its two, existing patent mainly is simply to include (for example patent CN 1903984A) to catalyst activity composition and carrier components, the especially detailed preparation condition of the concrete preparation method of catalyst of suitable coal tar hydrogenating is not deeply groped.

Be directed to the problem of above-mentioned existence, this patent proposes a kind of new coal tar hydrorefining catalyst and methods for making and using same thereof.This catalyst aims at coal tar hydrogenating and designs; Strict control catalyst preparation process condition in the catalyst preparation process; General and self-control or commodity hydrocracking catalyst were united use when this Hydrobon catalyst was used, and had effectively improved the quality and the productive rate of product fuel oil.

Summary of the invention

The objective of the invention is to; Problem to the existence of existing coal tar hydrogenation catalyst aspect; Propose special-purpose Hydrobon catalyst of a kind of new coal tar and methods for making and using same thereof, reach the purpose of preparation high activity and high stability coal tar hydrogenation catalyst through strictness control catalyst preparation process condition.Active general, hydrothermal stability and resistance to elevated temperatures were not strong when catalyst of the present invention had overcome existing goods petroleum distillate Hydrobon catalyst and is used for coal tar hydrogenating; Be prone to deficiencies such as inactivation, it has the high-ratio surface that is fit to handle the coal tar component, the gross porosity footpath; Higher pore volume and suitable activated centre; Simultaneously, it possesses good mechanical strength and hydro-thermal performance, and uniting use with the downstream hydrocracking catalyst can effectively be converted into high-quality fuel oil with coal tar or coal tar fraction.

Coal tar hydrorefining catalyst of the present invention is by active component, and auxiliary agent and carrier are formed.Active component is MoO in the said Hydrobon catalyst ₃With NiO or MoO ₃And CoO, calculate the 15-35% that accounts for the catalyst gross mass with oxide form.If active component is by MoO ₃When forming with NiO, MoO then ₃Account for the 13-25% of catalyst gross mass, NiO accounts for the 2-10% of catalyst gross mass; If active component is by MoO ₃When forming with CoO, MoO then ₃Account for the 12-28% of catalyst gross mass, CoO accounts for the 3-7% of catalyst gross mass.The auxiliary agent of catalyst is Bi ₂O ₃And K ₂O calculates the 2-5% that accounts for the catalyst gross mass, wherein Bi with oxide form ₂O ₃Account for the 1.8-3.5% of catalyst gross mass, K ₂O accounts for the 0.2-1.5% of catalyst gross mass.The carrier of catalyst is active A l ₂O ₃And BaO, account for the 60-83% of catalyst gross mass, wherein active A l ₂O ₃Account for the 80-95% of carrier gross mass, BaO accounts for the 5-20% of carrier gross mass.

The preparation method of said Hydrobon catalyst comprises:

(1) mixed pinching milled

Commercially available SB aluminum hydroxide solid elastomer powder adds the barium nitrate fine powder account for its quality 8-27% (preferred 10-16%), accounts for the peptizing agent and the binding agent that accounts for its quality 0.1-3.0% (preferred 0.5-1.5%) of its quality 0.1-5.0% (preferred 0.5-3%), the furnishing glue cake that wets.Wet glue cake places on the kneading machine; Constantly be sprinkled into the Ammonium Molybdate Tetrahydrate fine powder that accounts for aluminum hydroxide solid elastomer powder 15-32% (preferred 18-24%) quality; The Nickelous nitrate hexahydrate or the cabaltous nitrate hexahydrate fine powder of 7-28% (preferred 12-18%) quality; The cellulose of 0.1-2.0% (preferred 0.6-1.2%) quality mixes and pinches evenly.Under the 100-140 ℃ of condition in drying equipment dry 2-16h, be milled into fine powder.

(2) extruded moulding

Add the extrusion aid that accounts for its quality 1.2-5.5% in the fine powder, and small amount of deionized water, extruding is adopted the crowded orifice plate extruded moulding of cloverleaf pattern or other shapes for several times on the screw rod banded extruder.Extrusion diameter 1.1-3.0mm, length 3-8mm.Washed the moulding bar 2-10 minute with acetate.100-140 ℃ of dry 2-16h in drying equipment, in the air atmosphere that contains 15-40% molar concentration steam, gas agent volume ratio is 400-1400 then: under 1 condition, under the 450-550 ℃ of constant temperature in roasting apparatus roasting 4-15 hour.

(3) dipping and catalyst post processing

Under the normal temperature condition, quantitative in advance potassium nitrate and bismuth nitrate are made into mixed solution.Step (2) gained moulding bar impregnated in potassium nitrate and bismuth nitrate mixed solution 4-24 hour.Dipping is under the conventional no ultrasonic wave condition of 20-80KHz ultrasonic wave conditioned disjunction, to carry out.The gained catalyst places roasting apparatus; In the dry air atmosphere; Be heated to and removed adsorbed water in 200 ℃ of constant temperature 1-2 hours; Be heated to 5-10 ℃/minute heating rate and removed constitution water in 350-380 ℃ of constant temperature 2-3 hour, be warmed up to 420-550 ℃ of constant temperature 4-8 hour with 10-35 ℃/hour speed again.

Employed peptizing agent can be one or more the mixture in the aliphatic acid, bromine hydracid, ammoniacal liquor of nitric acid, hydrochloric acid, acetic acid, the water miscible 4-22 of a containing carbon among the Hydrobon catalyst preparation method as stated.

Employed binding agent can be one or more the mixture in sesbania powder, sodium carboxymethylcellulose, palm wax, paraffin, animal glue, starch, dextrin, molasses, the polyvinyl alcohol etc. among the Hydrobon catalyst preparation method as stated.

Employed extrusion aid can be one or more the mixture in sesbania powder, tartaric acid, graphite powder, the citric acid etc. among the Hydrobon catalyst preparation method as stated.

According to the prepared Hydrobon catalyst of the inventive method, its profile can be spherical, microspheroidal, bar shaped, annular, wheel shape, cylinder, clover, bunge bedstraw herb, butterfly or sheet.Preferential clover, bunge bedstraw herb or the butterfly selected.

The said drying equipment that is used for Preparation of Catalyst can be vacuum drying chamber, air dry oven, rotary dryer, spray dryer, crawler type drier, the film drier of using always or take off formula drier etc.

The said roasting apparatus that is used for Preparation of Catalyst can be vertical continuous roasting furnace, drum calciner or the kiln formula roaster of using always etc.

The application process of Hydrobon catalyst of the present invention comprises:

In first section fixed bed reactors, load Hydrobon catalyst, reaction condition is reaction temperature 320-380 ℃, feedstock oil liquid volume air speed 0.3-2.0h ^-1Hydrogen Vapor Pressure 6-15Mpa; The volume ratio 600-1800 of hydrogen and feedstock oil: 1, on the Hydrobon catalyst bed, can load the natural montmorillonite that accounts for Hydrobon catalyst 5-30% quality or other acid natural crystals with shallow degree cracking function, or the natural crystal that diluted with heat-resisting inert materials such as quartz sands; Or heat-resisting inert material such as quartz sand, can not load yet.In second section fixed bed reactors, load the self-control hydrocracking catalyst (for example: with W, Ni, Co etc. is active component, with aluminium oxide and molecular sieve be carrier from controlling catalyst) or the commodity hydrocracking catalyst (for example: commodity FC-28 type catalyst).Feed coal tar carries out hydrofinishing (the comprising nitrogen and desulfurization deoxidation etc.) reaction and the hydrocracking lighting reaction of feed coal tar respectively successively through first section and second section fixed bed reactors.Before the raw material coal tar, Hydrobon catalyst and hydrocracking catalyst all need use vulcanizing agent (for example: carbon disulfide or dimethyl disulfide etc.) to carry out presulfurization.

The manageable feed coal tar of Hydrobon catalyst of the present invention comprises the high temperature without any processing, the full cut of middle gentle coalite tar; Simple process is crossed the various coal tar of (for example: filtration or electric desalting and dewatering etc.); Any cut section of various coal tar; Any light fraction between coal tar 350-500 ℃ and the mixture of the full cut of coal tar; Extract the coal tar after one or more chemical substances, extraction of substance is like naphthalene, anthracene, phenols etc.

The application process that Hydrobon catalyst according to the invention is general is to unite use with self-control or commodity hydrocracking catalyst, also can be applied to the hydrogenation of coal tar, dead oil or coal tar extract under some situation separately.

A kind of common process flow process of using Hydrobon catalyst of the present invention is: feedstock oil is squeezed into reaction unit by high-pressure pump by setting flow, successively through the fuel oil preheating device, and first section fixed bed reactors; Second section fixed bed reactors; Hot high score device, cold high score device, condenser etc.Second section fixed bed reactors can be provided with the bypass hydrogen make-up.Learn final hydrogenation reaction effect through analyzing the product oil that receives in the condenser: product petrol and diesel oil total recovery is not less than 91%; Desulfurization degree is not less than 98%; Denitrification percent is not less than 97%; Take off the carbon residue rate and be not less than 97%, the gasoline fraction octane number is not less than 85 in the product, and the diesel oil distillate Cetane number is not less than 38.

The technological process of using Hydrobon catalyst according to the invention is not limited to above-mentioned conventional coal tar hydrogenation process flow process, also can be other coal tar hydrogenation process flow processs; The reactor of filling Hydrobon catalyst and hydrocracking catalyst is not limited to fixed bed reactors, also can be the reactor of other types, fluid bed for example, moving bed etc.

Compared with prior art; Coal tar hydrorefining catalyst of the present invention has following several advantage: (1) specific surface is high, and pore capacities is big, and the aperture is thick and distribute concentrated; Active component and auxiliary agent distribute very evenly, and possess good desulfurization, denitrogenation, deoxidation, demetalization, the matter of coming unstuck activity; (2) good alkene, alkadienes, aromatic hydrocarbons saturability improved quality, stability and the yield of hydrogenated products oil, and the octane number of gasoline fraction can improve 5-11 unit in the product, diesel oil distillate to Cetane number can improve 3-9 unit; (3) catalyst and technology of preparing adaptability thereof are strong, and prepared catalyst can be used for handling the various coal tar of different regions different manufacturers; (4) possess good operational stability and anti-pressure and abrasion-proof mechanical strength, the catalyst long service life satisfies the requirement of industrialization long-play.

The specific embodiment

Below in conjunction with embodiment and Comparative Examples the present invention is made further detailed description.In embodiment and the Comparative Examples: catalyst F1 and F2 are for using the prepared Hydrobon catalyst of the present invention; Catalyst C is the self-control hydrocracking catalyst, and active component is W and Ni, contains little auxiliary, and carrier is aluminium oxide and mordenite molecular sieve mixture; Catalyst FF-16 and 3822 is a petrochemical industry convenience goods Hydrobon catalyst, and catalyst FC-28 is a petrochemical industry convenience goods hydrocracking catalyst, catalyst FF-16,3822 and the composition of FC-28 can in corresponding patent or document, find easily.

Embodiment 1

The preparation of Hydrobon catalyst F1 is following:

Commercially available SB aluminum hydroxide solid elastomer powder 100g adds 8.4g barium nitrate fine powder, 1.1g nitric acid, and the 1.8g citric acid reconciles into wet glue cake.Wet glue cake places on the kneading machine, constantly is sprinkled into 21.7g Ammonium Molybdate Tetrahydrate fine powder, 22.9g cabaltous nitrate hexahydrate fine powder, and the 1.2g cellulose mixes and pinches evenly.Dry 14h under 120 ℃ of conditions is milled into fine powder.

Add 4g sesbania powder and small amount of deionized water in the fine powder, on the screw rod banded extruder, adopt cloverleaf pattern orifice plate extruded moulding.Extrusion diameter 1.2mm, length 3mm.Washed the moulding bar 6 minutes with acetate.110 ℃ of dry 2h, then in the air atmosphere that contains 35% molar concentration steam, gas agent volume ratio is that roasting is 12 hours under 490 ℃ of constant temperature, to improve hydrothermal stability under 1200: 1 conditions.

Under the normal temperature condition, preparation is dissolved with 3.2g potassium nitrate and 6.1g five nitric hydrate bismuth mixed aqueous solution 150g.Frequency is under the ultrasonic wave condition of 60KHz above-mentioned moulding bar to be impregnated in potassium nitrate and bismuth nitrate mixed solution 18 hours.The moulding bar places dry air atmosphere, is heated to 200 ℃ of constant temperature and removes adsorbed water in 3 hours, is heated to 350 ℃ of constant temperature with 6 ℃/minute heating rates and removes constitution water in 2 hours, is warmed up to 520 ℃ of constant temperature 6 hours with 12 ℃/hour speed again.Promptly obtain Hydrobon catalyst F1.

The application process of Hydrobon catalyst F1 is following:

In first section fixed bed reactors, load 50g Hydrobon catalyst F1, reaction condition is 360 ℃ of reaction temperatures, feedstock oil liquid volume air speed 0.5h ^-1, Hydrogen Vapor Pressure 10MPa, the volume ratio of hydrogen and feedstock oil 1400: 1, the 20-30 order quartz sand of interpolation 15g on Hydrobon catalyst F1 bed.In second section fixed bed reactors, load 40g commodity FC-28 type hydrocracking catalyst, reaction condition is 390 ℃ of reaction temperatures, reaction oil liquid volume air speed 0.6h ^-1, Hydrogen Vapor Pressure 10MPa, the volume ratio of hydrogen and reaction oil 1600: 1.After catalyst fills, adopt the aviation kerosine that contains 3% (mass concentration) dimethyl disulfide catalyst to be carried out presulfurization as sulfurized oil.Conditions of vulcanization is 270 ℃ of curing temperatures, sulfurized oil liquid volume air speed 1.0h ^-1, Hydrogen Vapor Pressure 6MPa, the volume ratio of hydrogen and sulfurized oil 1000: 1, cure time is 24 hours.

Comparative Examples 1

In first section fixed bed reactors, load 50g commodity FF-16 type Hydrobon catalyst, on the Hydrobon catalyst bed, add the 20-30 order quartz sand of 15g; In second section fixed bed reactors, load 40g commodity FC-28 type hydrocracking catalyst.Experiment reaction condition and embodiment 1 are identical.

Embodiment 2

The preparation of Hydrobon catalyst F2 is following:

Commercially available SB aluminum hydroxide solid elastomer powder 100g adds 10g barium nitrate fine powder, 1g nitric acid, and 1.2g acetic acid, the 2g citric acid reconciles into wet glue cake.Wet glue cake places on the kneading machine, constantly is sprinkled into 27.5g Ammonium Molybdate Tetrahydrate fine powder, 15.9g Nickelous nitrate hexahydrate fine powder, and the 1g cellulose mixes and pinches evenly.Dry 15h under 120 ℃ of conditions is milled into fine powder.

Add 3.2g sesbania powder and small amount of deionized water in the fine powder, on the screw rod banded extruder, adopt cloverleaf pattern orifice plate extruded moulding.Extrusion diameter 1.5mm, length 3mm.Washed the moulding bar 8 minutes with acetate.110 ℃ of dry 15h, then in the air atmosphere that contains 40% molar concentration steam, gas agent volume ratio is that roasting is 12 hours under 480 ℃ of constant temperature under 1200: 1 conditions.

Under the normal temperature condition, preparation is dissolved with 2.6g potassium nitrate and 6.4g five nitric hydrate bismuth mixed aqueous solution 140g.Be under the ultrasonic wave condition of 60KHz above-mentioned moulding bar to be impregnated in potassium nitrate and bismuth nitrate mixed solution 24 hours in frequency.The moulding bar places dry air atmosphere, is heated to 200 ℃ of constant temperature and removes adsorbed water in 2 hours, is heated to 350 ℃ of constant temperature with the heating rate of 6 ℃ of per minutes and removes constitution water in 2 hours, is warmed up to 500 ℃ of constant temperature 4 hours with 12 ℃/hour speed again.Promptly obtain Hydrobon catalyst F2.

The application process of Hydrobon catalyst F2 is following:

In first section fixed bed reactors, load 50g Hydrobon catalyst F2, reaction condition is 370 ℃ of reaction temperatures, feedstock oil liquid volume air speed 0.6h ^-1, Hydrogen Vapor Pressure 12MPa, the volume ratio of hydrogen and feedstock oil 1500: 1, the natural montmorillonite of 20-30 order of interpolation 12g on hydrofinishing F2 beds.In second section fixed bed reactors, load 40g self-control hydrocracking catalyst C, reaction condition is 400 ℃ of reaction temperatures, reaction oil liquid volume air speed 0.7h ^-1, Hydrogen Vapor Pressure 12MPa, the volume ratio of hydrogen and reaction oil 1800: 1.After catalyst fills, adopt the aviation kerosine that contains 2% (mass concentration) dimethyl disulfide catalyst to be carried out presulfurization as sulfurized oil.Conditions of vulcanization is 270 ℃ of curing temperatures, sulfurized oil liquid volume air speed 1.0h ^-1, Hydrogen Vapor Pressure 6MPa, the volume ratio of hydrogen and sulfurized oil 1000: 1, cure time is 24 hours.

Comparative Examples 2

In first section fixed bed reactors, load 50g commodity 3822 type Hydrobon catalysts, on the Hydrobon catalyst bed, add the natural montmorillonite of 20-30 order of 12g; In second section fixed bed reactors, load 40g self-control hydrocracking catalyst C.Experiment reaction condition and embodiment 2 are identical.

The main physico-chemical property of Hydrobon catalyst F1 of the present invention and F2 is seen table one in the foregoing description, and raw material, reaction condition, hydrogenation effect and product oiliness matter are seen table two in embodiment and the Comparative Examples.Can know through table two, compare, use Hydrobon catalyst of the present invention, can significantly improve the reaction effect of coal tar hydrogenating, for example improve yield, octane number and the diesel cetane-number etc. of gasoline, diesel product with the commodity Hydrobon catalyst.

The main physico-chemical property of Hydrobon catalyst of the present invention among table one embodiment

Raw material, reaction condition, hydrogenation effect and product oiliness matter in table two embodiment and the Comparative Examples

Claims (8)

1. A hydrofinishing catalyst for coal tar fuel oil, characterized in that: the hydrofinishing catalyst is made up of active components, auxiliary agents and carriers; the hydrofining catalyst active component is MoO ₃ and NiO or MoO ₃ and CoO, calculated in the form of oxides account for 15-35% of the total mass of the catalyst; if the active component is composed of MoO ₃ and NiO, then MoO ₃ accounts for 13-25% of the total mass of the catalyst, and NiO accounts for 10% of the total mass of the catalyst 2-10%; if the active component is composed of MoO ₃ and CoO, then MoO ₃ accounts for 12-28% of the total mass of the catalyst, and CoO accounts for 3-7% of the total mass of the catalyst; the additive of the catalyst is Bi ₂ O ₃ and K ₂ O, calculated in the form of oxides account for 2-5% of the total mass of the catalyst, wherein Bi ₂ O ₃ accounts for 1.8-3.5% of the total mass of the catalyst, and K ₂ O accounts for 0.2-1.5% of the total mass of the catalyst; The carrier is active _Al2O3 and BaO, _accounting for _60-83 % of the total mass of the catalyst, wherein the active _Al2O3 accounts for 80-95% of the total mass of the carrier, and BaO accounts for 5-20% of the total mass of the carrier. 2. the preparation method of hydrorefining catalyst as claimed in claim 1, comprises the steps: (1) kneading and grinding Commercially available SB aluminum hydroxide dry rubber powder, adding barium nitrate fine powder accounting for 8-27% of its mass, peptizer accounting for 0.1-5.0% of its mass and binder accounting for 0.1-3.0% of its mass, adjusted to wet The rubber cake, the wet rubber cake is placed on the kneader, and the ammonium molybdate tetrahydrate fine powder accounting for 15-32% of the quality of the dry aluminum hydroxide powder is continuously sprinkled, and the nickel nitrate hexahydrate or cobalt nitrate hexahydrate is continuously sprinkled with 7-28% of the quality Fine powder, 0.1-2.0% cellulose by mass, kneaded evenly, dried in a drying equipment at 100-140°C for 2-16 hours, and ground into fine powder; (2) extrusion molding Add extrusion aid accounting for 1.2-5.5% of the mass of the fine powder, and a small amount of deionized water, extrude several times on the screw extruder, and use clover-shaped or other shapes of extrusion orifice extrusion molding, extrusion diameter 1.1 -3.0mm, length 3-8mm, wash the molded bar with acetic acid for 2-10 minutes, dry in a drying equipment at 100-140°C for 2-16 hours, and then in an air atmosphere containing 15-40% molar concentration of water vapor, aerosol Under the condition that the volume ratio is 400-1400:1, roast in a roasting equipment at a constant temperature of 450-550°C for 4-15 hours; (3) impregnation and catalyst post-treatment Under normal temperature conditions, pre-quantitative potassium nitrate and bismuth nitrate are made into a mixed solution, and the formed strips obtained in step (2) are immersed in the mixed solution of potassium nitrate and bismuth nitrate for 4-24 hours, and the obtained catalyst is placed in a roasting equipment, and dried in air In the atmosphere, heat to 200°C for 1-2 hours to remove adsorbed water, heat to 350-380°C for 2-3 hours at a heating rate of 5-10°C/min to remove structural water, and then heat to 10-35°C/min The speed of the hour is heated to 420-550 ℃ and the temperature is kept constant for 4-8 hours. 3. The method for preparing a hydrorefining catalyst as claimed in claim 2, characterized in that: the impregnation is carried out under 20-80KHz ultrasonic conditions or conventional conditions without ultrasonic waves. 4. as claimed in claim 2, the preparation method of the hydrogenation refining catalyst is characterized in that: the peptizer is one or the other in nitric acid, hydrochloric acid, acetic acid, water-soluble fatty acid containing 4-22 carbons, hydrobromic acid, ammonia A mixture of several. 5. the preparation method of hydrorefining catalyst as claimed in claim 2 is characterized in that: binding agent is safflower powder, sodium carboxymethyl cellulose, palm wax, paraffin, animal glue, starch, dextrin, molasses, polysaccharide One or more mixtures of vinyl alcohols. 6. The preparation method of hydrorefining catalyst as claimed in claim 2, characterized in that: the extrusion aid is one or more mixtures of safflower powder, tartaric acid, graphite powder, and citric acid. 7. the application method of hydrorefining catalyst as claimed in claim 1, is characterized in that: Fill the hydrofinishing catalyst in the first stage fixed-bed reactor, the reaction conditions are reaction temperature 320-380°C, feed oil liquid volume space velocity 0.3-2.0h ^-1 , hydrogen pressure 6-15Mpa, hydrogen and feed oil The volume ratio is 600-1800:1, and the natural montmorillonite or other acidic natural ore with shallow cracking function, which accounts for 5-30% of the mass of the hydrofinishing catalyst, is filled before the hydrofinishing catalyst bed, or quartz sand is used Heat-resistant inert material Diluted natural ore, or quartz sand heat-resistant inert material, or not filled, the second-stage fixed-bed reactor is filled with a commercial hydrocracking catalyst, and the raw coal tar passes through the first and second stages in sequence One-stage fixed-bed reactors are used to carry out the hydrofinishing reaction and hydrocracking lightening reaction of raw coal tar respectively. Before the raw coal tar is fed, both the hydrofinishing catalyst and the hydrocracking catalyst need to be presulfurized with a sulfiding agent. 8. The application method of hydrorefining catalyst as claimed in claim 7, characterized in that: raw material coal tar comprises high temperature without any treatment, medium and low temperature coal tar full fraction; Coal tar; any fraction of various coal tars; a mixture of any light fraction of coal tar between 350-500 °C and the full fraction of coal tar; coal tar after one or several chemical substances are extracted, the extract is: Naphthalene, anthracene, phenol.