CN102069004A - Hydrocracking catalyst for preparing fuel oil from coal tar and preparation and application methods thereof - Google Patents
Hydrocracking catalyst for preparing fuel oil from coal tar and preparation and application methods thereof Download PDFInfo
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Abstract
The invention provides a novel hydrocracking catalyst special for coal tar and a preparation method and an application method thereof aiming at the problems of the conventional coal tar hydrocracking catalyst. The hydrocracking catalyst consists of active ingredients, an aid and a carrier, wherein the active ingredients of the hydrocracking catalyst consist of WO3 and NiO, the aid is ReO, and the carrier consists of activated alumina, zeolite and BaO; and the active ingredients and the aid respectively account for 14 to 34 percent and 0.4 to 1.2 percent of the total mass of the catalyst based on an oxide form. The method for preparing the catalyst comprises the following steps of: preparing the carrier, pretreating the carrier, impregnating, performing catalyst post-treatment and the like; and the catalyst preparation conditions are strictly controlled by introducing novel ultrasonic impregnation technology. Compared with the prior art, the catalyst is excellent in surface physicochemical properties, has good aromatic hydrocarbon saturated activity and proper cracking activity, and excellent high-temperature resistance and compression resistance, and effectively improves the quality and yield of hydrotreated product oil.
Description
Technical field
The invention belongs to coal tar hydrogenating and produce the fuel oil technical field, be specifically related to a kind of hydrocracking catalyst and methods for making and using same thereof that is used for producing fuel oil from coal tar.
Background technology
" oil starvation, weak breath, rich coal " is the Energy Situation of present China, and the energy supply problem has developed into the outstanding problem that China's economic development and national security face.Under the petroleum resources condition of limited, development Coal Chemical Industry industry development deep process technology and product have important reality and strategic importance.Coal tar is the accessory substance 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, or burns as low-quality fuel oil after the simple process, produces a large amount of sewage or atmosphere pollutions such as NOx, SOx.Heteroatomic deep removal, insatiable hunger alkene and aromatic hydrocarbons such as sulphur nitrogen oxygen that the employing hydrogenation technique can be finished coal tar raw material are saturated, to improve coal tar 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 by hydrogenation technique and can produce tangible economic and social benefit, effectively alleviate China's energy-intensive present situation.
The research and development of preparing fuel oil with coal oil hydrogenation technology at home and abroad launch, document " research of coalite tar electrolytic hydrogenation performance " (Liu Xuguang for example, Zhou Dongmei, Wang Zhizhong. the chemistry of fuel journal, 1996,24 (6): 504-508) organic electrolytic hydrogenation technology is applied to the hydrogenation of coalite tar, though mild condition, but the hydrogenation effect is very limited, and the gained oil product can't be used on market.Patent CN 1903984A is the coal tar pitch that raw material is produced 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 may utilize the strategic choice of aspect relevant with external coal tar.Document " from coal tar oils production gasoline " (Harry Clough.Industrial and 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 by two-step method, its raw material is not a coal tar.U.S. patent US3253202 in 1969 has introduced the method that coal tar hydrogenating obtains the oil refinery raw material, and hydrogenation products is the raw material of oil refinery but not fuel oil.
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, the catalyst of use mainly comprises following several at present: the hydrogenation protecting agent, and the removal of ccr by hydrotreating agent, Hydrobon catalyst, hydrocracking catalyst etc., its core is Hydrobon catalyst and hydrocracking catalyst.Mainly there are three problems in the coal tar hydrogenation catalyst aspect at present.One, 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, it forms complicated, contain more unsaturated heavy hydrocarbon, the acidity height, the viscosity height, density is big, especially sulphur, nitrogen, carbon residue, colloid, asphalt content are higher, and therefore developing the special-purpose catalyst that is fit to coal tar hydrogenating is pressing for of coal tar hydrogenating industrial development.Its two, existing patent mainly is simply to include (for example patent CN 1903984A) at catalyst activity composition and carrier components, the especially detailed preparation condition of the concrete preparation method of catalyst that is fit to 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 hydrocracking 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 Hydrobon catalyst were united use when this hydrocracking 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 at the existence of existing coal tar hydrogenation catalyst aspect, propose special-purpose hydrocracking 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 hydrocracking catalyst by strictness control catalyst preparation process condition.Hydrogenation cracking activity and hydrothermal stability were general when catalyst of the present invention had overcome existing petrochemical industry commodity hydrocracking catalyst and is used to handle coal tar or handles secondary coal tar raw material after hydrofinishing, resistance to elevated temperatures is not strong, deficiencies such as easy inactivation, it has the high-ratio surface that is fit to handle the coal tar component, the aperture of thickness combination, higher pore volume and suitable activated centre, active component distributes uniformly, simultaneously, it possesses good mechanical strength, hydro-thermal performance and coal tar hydrocracking activity, uniting use with the upstream Hydrobon catalyst can effectively be converted into high-quality fuel oil with coal tar or coal tar fraction.
Coal tar hydrocracking catalyst of the present invention is by active component, and auxiliary agent and carrier are formed.Active component is by WO in the described hydrocracking catalyst
3Form with NiO, calculate the 14-34% that accounts for the catalyst gross mass with oxide form.Wherein, WO
3Account for the 12-28% of catalyst gross mass, NiO accounts for the 2-6% of catalyst gross mass.The auxiliary agent of described hydrocracking catalyst is made up of ReO, and ReO accounts for the 0.4-1.2% of catalyst gross mass.The carrier of described hydrocracking catalyst is made up of activated alumina, zeolite and BaO, and wherein, activated alumina accounts for the 68-88% of carrier gross mass, and zeolite accounts for the 6-20% of carrier gross mass, and BaO accounts for the 6-12% of carrier gross mass.
Zeolite component in the described carrier of hydrocracking catalyst can be modenite, erionite, the HY zeolite of modification, the combination of one or more in H β zeolite, HZSM-5 zeolite, the SAPO-n zeolite.
The preparation method of described hydrocracking catalyst comprises:
(1) preparation of carrier
Under the room temperature condition, the preparation ammonium nitrate solution.The solution compound method is to add 6.4-16g ammonium nitrate in every 100g deionized water.Then the molecular sieve before the modification is added this solution, the adding method is the molecular sieve that adds 50-140g in every 100ml solution.Stir, 70-95 ℃ water-bath 5-12 hour.Slurries filtration, filter cake 100-130 ℃ oven dry, 500-600 ℃ of following constant temperature 4-12 hour roasting in the air atmosphere that contains 10-45% molar concentration steam then, gas agent volume ratio is 500-1200: 1, obtain molecular sieve after the modification, wear into fine powder after the fragmentation.
Commercially available SB aluminum hydroxide solid elastomer powder mixes the dichloro-benzenes that accounts for its quality 0.6-2.0%, and pouring into then is aluminum hydroxide solid elastomer opaque amount 0.5-1.5 aqueous hydrochloric acid solution doubly, and the aqueous hydrochloric acid solution mass concentration is 0.2-4%.Stir evenly to glue, filter, 120 ℃ of dryings, roasting 5 hours in the dry air promptly obtains the active oxidation aluminium powder under 500 ℃ of conditions.
With molecular sieve after the above-mentioned modification and active oxidation aluminium powder mixing, add the polyvinyl alcohol or the sesbania powder that account for mixed-powder gross mass 1-4%, tartaric acid or the citric acid of 1.5-5% stir evenly, and kneading is pushed for several times on the screw rod banded extruder to plastic shape repeatedly, is extruded into special-shaped bar.Extrusion diameter 1.1-3mm, length 3-6mm.
(2) preliminary treatment of carrier
The abnormity bar is positioned in the sealing tube furnace under the 10-40Kpa vacuum condition, under the 90-130 ℃ of condition dry 4-16 hour, then then under vacuum condition the heating rate with 5-15 ℃/minute be heated to 400-650 ℃ of constant temperature calcining 2-6h.Roasting naturally cools to room temperature after finishing, and the aqueous citric acid solution of putting into 10% mass concentration then carries out pre-preg to be handled 0.5-3 hour, and the mass ratio of catalyst and aqueous citric acid solution is 1: 3-10, and the surplus water of draining, cold wind dries up.
(3) ultrasonic wave dipping and catalyst post processing
Ammonium metatungstate, the nickel nitrate mixed solution of preparation scheduled volume.The ammonium perrhenate of scheduled volume is dissolved in deionized water and is made into rhenium-containing solution.Under the normal temperature condition, the carrier impregnation of under 20-80KHZ ultrasonic wave condition step (2) being handled was in ammonium metatungstate, nickel nitrate mixed solution 4-12 hour, and the mass ratio of solution and carrier is 1.0-1.6: 1, and 100-140 ℃ of drying, 450-580 ℃ of roasting.Under 20-80KHZ ultrasonic wave condition, flooded rhenium-containing solution 2-12 hour then.After finishing, takes out dipping, the agent of dry air atmosphere gas is than for 600-1400: under 1 condition with 100-140 ℃ of drying 4 hours, be heated to 300-350 ℃ of constant temperature 3 hours with 5-10 ℃/minute heating rate then, be warmed up to 460-550 ℃ of constant temperature 4-8 hour with 20-40 ℃/hour speed again.450-600 ℃ of reductase 12-12 hour in pure hydrogen atmosphere finally made hydrocracking catalyst afterwards.
According to the prepared hydrocracking catalyst of the inventive method, its profile can be spherical, microspheroidal, bar shaped, annular, wheel shape, cylinder, clover, bunge bedstraw herb, butterfly, sheet.Preferred clover, bunge bedstraw herb or butterfly.
The application process of hydrocracking catalyst of the present invention comprises:
Loading the self-control Hydrobon catalyst in first section fixed bed reactors (is active component with Mo and Ni for example, contain a little auxiliary, aluminium oxide and barium monoxide be carrier from controlling catalyst) or commodity Hydrobon catalyst (for example commodity 3822 type catalyst), on the Hydrobon catalyst bed, can load the natural crystal of the shallow degree cracking of having of a certain amount of natural montmorillonite or other acidity function, or the natural crystal that diluted with heat-resisting inert materials such as quartz sands etc., or heat-resisting inert material such as quartz sand, can not load yet.In second section fixed bed reactors, load hydrocracking catalyst.The hydrocracking reaction condition is reaction temperature 360-420 ℃, feedstock oil liquid volume air speed 0.3-2.0h
-1, Hydrogen Vapor Pressure 6-15Mpa, the volume ratio 600-2000 of hydrogen and feedstock oil: 1.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 by first section and second section fixed bed reactors.Before the raw material coal tar, Hydrobon catalyst and hydrocracking catalyst all need to use the vulcanizing agent presulfurization.
The application process that hydrocracking catalyst of the present invention is general is to unite use with self-control or commodity Hydrobon catalyst, also can be applied to the hydrogenation reaction of coal tar, dead oil or coal tar extract separately.
The manageable feed coal tar of hydrocracking catalyst of the present invention comprises the high temperature without any processing, the full cut of middle gentle coalite tar; Any cut section of various coal tar; The mixture of any light fraction section of coal tar and the full cut of coal tar; The various coal tar that simple filtration or processed are crossed.
A kind of common process flow process of using hydrocracking catalyst of the present invention is: feedstock oil mountain high-pressure pump is squeezed into reaction unit by setting flow, successively by 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.
The use of hydrocracking catalyst of the present invention is not limited to above-mentioned conventional coal tar hydrogenation process flow process and fixed bed reactors, also can be applied to the reactor (for example fluid bed, moving bed etc.) of other coal tar hydrogenation process flow processs and other types.
Compare with existing hydrocracking catalyst, coal tar hydrocracking catalyst of the present invention has following several advantage: (1) specific surface height, and pore capacities is big, the effective combination in thickness aperture, active component and auxiliary agent are evenly distributed; (2) the full active and suitable cracking activity of good aromatic hydrocarbons has effectively improved quality, stability and the yield of hydrogenated products petrol and diesel oils; (3) good operational stability, the good temperature resistance energy, the higher compression mechanical strength, the catalyst long service life satisfies long-time industrialization service requirement.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and Comparative Examples.In embodiment and the Comparative Examples: catalyst L1 and L2 are for using the prepared hydrocracking catalyst of the present invention; Catalyst J is the self-control Hydrobon catalyst, and active component is Mo and Ni, contains a little auxiliary, and carrier is aluminium oxide and barium monoxide; Catalyst FC-22 and 3824 is a petrochemical industry convenience goods hydrocracking catalyst, and catalyst FF-16 is a petrochemical industry convenience goods Hydrobon catalyst, catalyst FC-22,3824 and the composition of FF-16 can in corresponding patent or document, find easily.
Embodiment 1
Hydrocracking catalyst L1 is prepared as follows:
Under the room temperature, add 2.4g ammonium nitrate wiring solution-forming in the 20g deionized water.The modenite that adds 15g then.Stir 95 ℃ of water-baths 12 hours.Slurries filtration, 130 ℃ of oven dry of filter cake, 600 ℃ of constant temperature roasting in 4 hours in the air atmosphere that contains 40% molar concentration steam then, gas agent volume ratio is 1200, obtains zeolite after the modification, it is standby to wear into fine powder after the fragmentation.Commercially available SB aluminum hydroxide solid elastomer powder 100g mixes the 2g dichloro-benzenes, pours the 100g aqueous hydrochloric acid solution then into, and the aqueous hydrochloric acid solution mass concentration is 1.8%.Stir evenly to glue, filter, 120 ℃ of dryings, roasting 5 hours in the dry air promptly obtains the active oxidation aluminium powder under 500 ℃ of conditions.With molecular sieve after the above-mentioned modification and active oxidation aluminium powder mixing, add the 3g polyvinyl alcohol, the 5g citric acid, kneading adopts butterfly to squeeze the orifice plate extruded moulding on the screw rod banded extruder to plastic shape.Extrusion diameter 1.1mm, length 3mm.
Wet bar is positioned under the sealing tube furnace 15Kpa vacuum condition, 100 ℃ of dry 14h down, then then under vacuum condition the heating rate with 6 ℃/minute be heated to 500 ℃ of constant temperature calcining 2h.Naturally cool to room temperature after roasting finishes, put into the 300g aqueous solution pre-preg 2 hours that contains the 30g citric acid, the surplus water of draining, cold wind dries up, and obtains the moulding bar of pre-preg.
Preparation contains the mixed solution 160g of 46.5g ammonium metatungstate, 34g Nickelous nitrate hexahydrate.3.2g ammonium perrhenate be dissolved in the 160g deionized water and be made into rhenium-containing solution.Frequency is under the ultrasonic wave condition of 70KHz the moulding bar of pre-preg to be put into ammonium metatungstate, nickel nitrate mixed solution dipping 12 hours.Take out 100 ℃ of dryings, 500 ℃ of roastings 4 hours.Under 70KHz ultrasonic wave condition, flood rhenium-containing solution then.Take out the dipping back that finishes, in the dry air gas agent ratio be under 1200: 1 conditions with 120 ℃ of dryings 4 hours, the heating rate with 5 ℃ of per minutes was heated to 300 ℃ of constant temperature 3 hours then, was warmed up to 500 ℃ of constant temperature 4 hours with 20 ℃/hour speed again.Afterwards in hydrogen atmosphere 550 ℃ the reduction 4 hours, make hydrocracking catalyst L1.
The application process of hydrocracking catalyst L1 is as follows:
Load 50g self-control Hydrobon catalyst J in first section fixed bed reactors, reaction condition is 360 ℃ of reaction temperatures, feedstock oil liquid volume air speed 0.5h
-1, Hydrogen Vapor Pressure 12MPa, the volume ratio of hydrogen and feedstock oil 1400: 1 is added the natural montmorillonite of 15g on the Hydrobon catalyst bed.Load 50g self-control hydrocracking catalyst L1 in second section fixed bed reactors, reaction condition is 390 ℃ of reaction temperatures, reaction oil liquid volume air speed 0.5h
-1, Hydrogen Vapor Pressure 12MPa, the volume ratio of hydrogen and oil 1600: 1.After catalyst fills, adopt the aviation kerosine that contains 2.2% (mass concentration) dimethyl disulfide catalyst to be carried out presulfurization as sulfurized oil.Conditions of vulcanization is 250 ℃ 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 self-control Hydrobon catalyst J, on the Hydrobon catalyst bed, add the natural montmorillonite of 15g; In second section fixed bed reactors, load 50g commodity FC-22 type hydrocracking catalyst.Experiment reaction condition and embodiment 1 are identical.
Embodiment 2
Hydrocracking catalyst L2 is prepared as follows:
Under the room temperature, add 3g ammonium nitrate wiring solution-forming in the 20g deionized water.The H β zeolite that adds 14g then.Stir 90 ℃ of water-baths 6 hours.Slurries filtration, 110 ℃ of oven dry of filter cake, 600 ℃ of constant temperature roasting in 4 hours in the air atmosphere that contains 30% molar concentration steam then, gas agent volume ratio is 600, obtains zeolite after the modification, it is standby to wear into fine powder after the fragmentation.Commercially available SB aluminum hydroxide solid elastomer powder 100g mixes the 1.8g dichloro-benzenes, pours the 100g aqueous hydrochloric acid solution then into, and the aqueous hydrochloric acid solution mass concentration is 3%.Stir evenly to glue, filter, 120 ℃ of dryings, roasting 5 hours in the dry air promptly obtains the active oxidation aluminium powder under 500 ℃ of conditions.With molecular sieve after the above-mentioned modification and active oxidation aluminium powder mixing, add 4g sesbania powder, 4.5g tartaric acid, kneading adopts cloverleaf pattern to squeeze the orifice plate extruded moulding on the twin-screw banded extruder to plastic shape.Extrusion diameter 1.2mm, length 3mm.
Wet bar is positioned under the sealing tube furnace 20Kpa vacuum condition, 100 ℃ of dry 8h down, then then under vacuum condition the heating rate with 15 ℃/minute be heated to 6000 ℃ of constant temperature calcining 2h.Naturally cool to room temperature after roasting finishes, put into the 300g aqueous solution pre-preg 2 hours that contains the 30g citric acid, the surplus water of draining, cold wind dries up, and obtains the moulding bar of pre-preg.
Preparation contains the mixed solution 160g of 22g ammonium metatungstate, 15g Nickelous nitrate hexahydrate.1.8g ammonium perrhenate be dissolved in the 150g deionized water and be made into rhenium-containing solution.Frequency is under the ultrasonic wave condition of 30KHz the moulding bar of pre-preg to be put into ammonium metatungstate, nickel nitrate mixed solution dipping 12 hours.Take out 100 ℃ of dryings, 450 ℃ of roastings 4 hours.Under 30KHz ultrasonic wave condition, flood rhenium-containing solution then.Take out the dipping back that finishes, in the dry air gas agent ratio be under 1200: 1 conditions with 120 ℃ of dryings 4 hours, the heating rate with 10 ℃ of per minutes was heated to 300 ℃ of constant temperature 3 hours then, was warmed up to 550 ℃ of constant temperature 4 hours with 40 ℃/hour speed again.Afterwards in hydrogen atmosphere 500 ℃ the reduction 4 hours, make hydrocracking catalyst L2.
The application process of hydrocracking catalyst L2 is as follows:
Load 50g commodity Hydrobon catalyst FF-16 in first section fixed bed reactors, reaction condition is 340 ℃ of reaction temperatures, feedstock oil liquid volume air speed 0.7h
-1, Hydrogen Vapor Pressure 10.5MPa, the volume ratio of hydrogen and feedstock oil 1300: 1.Load 50g hydrocracking catalyst L2 in second section fixed bed reactors, reaction condition is 370 ℃ of reaction temperatures, reaction oil liquid volume air speed 0.7h
-1, Hydrogen Vapor Pressure 10.5MPa, the volume ratio of hydrogen and oil 1600: 1.After catalyst fills, adopt the aviation kerosine that contains 2.5% (mass concentration) dimethyl disulfide catalyst to be carried out presulfurization as sulfurized oil.Conditions of vulcanization is 250 ℃ 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 FF-16 type Hydrobon catalyst; In second section fixed bed reactors, load 50g commodity 3824 type hydrocracking catalysts.Experiment reaction condition and embodiment 2 are identical.
The main physico-chemical property of hydrocracking catalyst L1 of the present invention and L2 sees Table one among above-mentioned three embodiment, and raw material, reaction condition, hydrogenation effect and product oil nature see Table two.
The main physico-chemical property of each embodiment catalyst of table one
Raw material, reaction condition, hydrogenation effect and product oil nature in table two embodiment and the Comparative Examples
Claims (6)
1. hydrocracking catalyst that is used for producing fuel oil from coal tar is characterized in that: described hydrocracking catalyst catalyst is by active component, and auxiliary agent and carrier are formed; Active component is by WO in the described hydrocracking catalyst
3Form with NiO, calculate the 14-34% that accounts for the catalyst gross mass with oxide form; Wherein, WO
3Account for the 12-28% of catalyst gross mass, NiO accounts for the 2-6% of catalyst gross mass; The auxiliary agent of described hydrocracking catalyst is made up of ReO, and ReO accounts for the 0.4-1.2% of catalyst gross mass; The carrier of described hydrocracking catalyst is made up of activated alumina, zeolite and BaO, and wherein, activated alumina accounts for the 68-88% of carrier gross mass, and zeolite accounts for the 6-20% of carrier gross mass, and BaO accounts for the 6-12% of carrier gross mass.
2. hydrocracking catalyst according to claim 1, it is characterized in that: the zeolite component in the carrier can be modenite, erionite, the HY zeolite of modification, the combination of one or more in H β zeolite, HZSM-5 zeolite, the SAPO-n zeolite.
3. the preparation method of hydrocracking catalyst comprises the steps: according to claim 1
(1) preparation of carrier
Under the room temperature condition, the preparation ammonium nitrate solution, the solution compound method is to add 6.4-16g ammonium nitrate in every 100g deionized water, then the molecular sieve before the modification is added this solution, the adding method is the molecular sieve that adds 50-140g in every 100ml solution, stir, 70-95 ℃ water-bath 5-12 hour, slurries filtration, filter cake 100-130 ℃ oven dry, 500-600 ℃ of following constant temperature 4-12 hour roasting in the air atmosphere that contains 10-45% molar concentration steam then, gas agent volume ratio is 500-1200: 1, obtain molecular sieve after the modification, wear into fine powder after the fragmentation;
Commercially available SB aluminum hydroxide solid elastomer powder, mix the dichloro-benzenes that accounts for its quality 0.6-2.0%, pouring into then is aluminum hydroxide solid elastomer opaque amount 0.5-1.5 aqueous hydrochloric acid solution doubly, the aqueous hydrochloric acid solution mass concentration is 0.2-4%, stir evenly to glue, filter 120 ℃ of dryings, roasting 5 hours in the dry air promptly obtains the active oxidation aluminium powder under 500 ℃ of conditions;
With molecular sieve after the above-mentioned modification and active oxidation aluminium powder mixing, add the polyvinyl alcohol or the sesbania powder that account for mixed-powder gross mass 1-4%, tartaric acid or the citric acid of 1.5-5% stir evenly, kneading is pushed for several times on the screw rod banded extruder to plastic shape repeatedly, be extruded into different in nature bar, extrusion diameter 1.1-3mm, length 3-6mm;
(2) preliminary treatment of carrier
Wet bar is positioned in the sealing tube furnace under the 10-40Kpa vacuum condition, under the 90-130 ℃ of condition dry 4-16 hour, then then under vacuum condition the heating rate with 5-15 ℃/minute be heated to 400-650 ℃ of constant temperature calcining 2-6h, roasting naturally cools to room temperature after finishing, the aqueous citric acid solution of putting into 10% mass concentration then carries out pre-preg to be handled 0.5-3 hour, the mass ratio of catalyst and aqueous citric acid solution is 1: 3-10, and the surplus water of draining, cold wind dries up;
(3) dipping and catalyst post processing
The ammonium metatungstate of preparation scheduled volume, the nickel nitrate mixed solution, the ammonium perrhenate of scheduled volume is dissolved in deionized water and is made into rhenium-containing solution, under the normal temperature condition, the carrier impregnation of under the ultrasonic wave condition step (2) being handled is in ammonium metatungstate, nickel nitrate mixed solution 4-12 hour, the mass ratio of solution and carrier is 1.0-1.6: 1,100-140 ℃ of drying, 450-580 ℃ of roasting, under the ultrasonic wave condition, flooded rhenium-containing solution 2-12 hour then, after finishing, takes out dipping, the agent of dry air atmosphere gas is than for 600-1400: under 1 condition with 100-140 ℃ of drying 4 hours, be heated to 300-350 ℃ of constant temperature 3 hours with 5-10 ℃/minute heating rate then, be warmed up to 460-550 ℃ of constant temperature 4-8 hour with 20-40 ℃/hour speed again, 450-600 ℃ of reductase 12-12 hour in pure hydrogen atmosphere finally made hydrocracking catalyst afterwards.
4. hydrocracking catalyst preparation method as claimed in claim 3 is characterized in that: dipping is to carry out under the conventional no ultrasonic wave condition of 20-80KHz ultrasonic wave conditioned disjunction.
5. the application process of hydrocracking catalyst according to claim 1 is characterized in that:
In first section fixed bed reactors, load self-control or commodity Hydrobon catalyst, on the Hydrobon catalyst bed, can load the natural crystal of the shallow degree cracking of having of a certain amount of natural montmorillonite or other acidity function, or the natural crystal that diluted with heat-resisting inert materials such as quartz sands etc., or heat-resisting inert material such as quartz sand, also can not load; Load hydrocracking catalyst in second section fixed bed reactors, the hydrocracking reaction condition is reaction temperature 360-420 ℃, feedstock oil liquid volume air speed 0.3-2.0h
-1, Hydrogen Vapor Pressure 6-15Mpa, the volume ratio 600-2000 of hydrogen and feedstock oil: 1.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 by first section and second section fixed bed reactors.Before the raw material coal tar, Hydrobon catalyst and hydrocracking catalyst all need to carry out presulfurization with vulcanizing agent.
6. the application process of hydrocracking catalyst as claimed in claim 5, it is characterized in that: feed coal tar comprises the high temperature without any processing, the full cut of middle gentle coalite tar; Any cut section of various coal tar; The mixture of any light fraction section of coal tar and the full cut of coal tar; The various coal tar that simple filtration or processed are crossed.
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| CN103889573B (en) * | 2011-10-24 | 2016-08-24 | 道达尔炼油法国 | For preparing the method for hydrogenation conversion catalyst, thus obtained catalyst and the purposes in hydrogenating conversion process thereof |
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| CN109277102A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Hydrodemetalation catalyst and its preparation method and application |
| CN109575987B (en) * | 2017-09-28 | 2020-12-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil by hydrogenation of tar |
| CN109575986A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | Method for Tar production fuel oil |
| CN109575987A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of hydrogenation of tar made fuel oil |
| CN109575986B (en) * | 2017-09-28 | 2020-12-29 | 中国石油化工股份有限公司 | Method for producing fuel oil from tar |
| CN108940283B (en) * | 2018-08-20 | 2021-02-12 | 嘉兴迪迈科技有限公司 | Supported high-efficiency hydrogenation catalyst and preparation method thereof |
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| CN109529926A (en) * | 2018-12-06 | 2019-03-29 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene is hydrocracked the catalyst and preparation method and application of light aromatics processed |
| CN114231333A (en) * | 2022-01-10 | 2022-03-25 | 安徽海螺投资有限责任公司 | Liquid coal combustion accelerant and preparation method thereof |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
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