CN102068992B - Hydrorefining catalyst for preparing fuel oil from coal tar, preparation method and application method thereof - Google Patents
Hydrorefining catalyst for preparing fuel oil from coal tar, preparation method and application method thereof Download PDFInfo
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Abstract
The invention provides a hydrorefining catalyst special for new coal tar, a preparation method and an application method thereof, which are used for solving problems existing in the conventional hydrogenation catalyst for coal tar. The hydrorefining catalyst consists of active components, aids and carriers, wherein the active components refer to MoO3 and NiO or MoO3 and CoO; the aids refer to Bi2O3 and K2O; and the carriers refer to alumina and barium oxide. According to calculation by the form of an oxide, the active components, the aids and the carriers account for 15 to 35 percent, 2 to 5 percent and 60 to 83 percent of the total mass of the catalyst respectively. The catalyst is prepared by the following steps of: kneading, grinding, extruding into strips, molding, soaking, performing catalyst post-treatment and the like. New ultrasonic soaking technology is introduced, and the preparation condition of the catalyst is controlled strictly. Compared with the prior art, the catalyst has high surface physical and chemical properties, high purified atom degumming activity, high hydrogenation saturation capability, high stability and high mechanical intensity, and the quality and yield of hydrogenation product oil can be enhanced effectively.
Description
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. Hydrobon catalyst that is used for producing fuel oil from coal tar is characterized in that: Hydrobon catalyst is by active component, and auxiliary agent and carrier are formed; The Hydrobon catalyst active component is MoO
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.
2. the preparation method of Hydrobon catalyst as claimed in claim 1 comprises the steps:
(1) mixed pinching milled
Commercially available SB aluminum hydroxide solid elastomer powder adds the barium nitrate fine powder that accounts for its quality 8-27%, accounts for the peptizing agent and the binding agent that accounts for its quality 0.1-3.0% of its quality 0.1-5.0%; The furnishing glue cake that wets; Wet glue cake places on the kneading machine, constantly is sprinkled into the Ammonium Molybdate Tetrahydrate fine powder that accounts for aluminum hydroxide solid elastomer powder 15-32% quality, the Nickelous nitrate hexahydrate of 7-28% quality or cabaltous nitrate hexahydrate fine powder; The cellulose of 0.1-2.0% quality; Mix and to pinch 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 for several times on the screw rod banded extruder; Adopt the crowded orifice plate extruded moulding of cloverleaf pattern or other shapes; 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, and 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; The gained catalyst places roasting apparatus, in the dry air atmosphere, is heated to and removes 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.
3. like the said Hydrobon catalyst preparation method of claim 2, it is characterized in that: dipping is under the conventional no ultrasonic wave condition of 20-80KHz ultrasonic wave conditioned disjunction, to carry out.
4. like the said Hydrobon catalyst preparation method of claim 2, it is characterized in that: peptizing agent is 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.
5. like the said Hydrobon catalyst preparation method of claim 2, it is characterized in that: binding agent is one or more the mixture in sesbania powder, sodium carboxymethylcellulose, palm wax, paraffin, animal glue, starch, dextrin, molasses, the polyvinyl alcohol.
6. like the said Hydrobon catalyst preparation method of claim 2, it is characterized in that: extrusion aid is one or more the mixture in sesbania powder, tartaric acid, graphite powder, the citric acid.
7. the application process of Hydrobon catalyst as claimed in claim 1 is characterized in that:
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, before the Hydrobon catalyst bed, load the natural montmorillonite or other the acid natural crystals that account for Hydrobon catalyst quality 5-30% with shallow degree cracking function; Or the natural crystal that diluted with the heat-resisting inert material of quartz sand; Or the heat-resisting inert material of quartz sand, or do not load packed goods hydrocracking catalyst in second section fixed bed reactors; Feed coal tar is successively through first section and second section fixed bed reactors; Carry out the hydrofining reaction and the hydrocracking lighting reaction of feed coal tar respectively, before the raw material coal tar, Hydrobon catalyst and hydrocracking catalyst all need carry out presulfurization with vulcanizing agent.
8. the application process of Hydrobon catalyst as claimed in claim 7, it is characterized in that: feed coal tar comprises the high temperature without any processing, the full cut of middle gentle coalite tar; The various coal tar that filtration or electric desalting and dewatering were handled; 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, extract is: naphthalene, anthracene, phenol.
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| CN103691465B (en) * | 2013-12-18 | 2016-04-06 | 宁波金远东工业科技有限公司 | For the Catalysts and its preparation method of coal tar hydrocracking |
| CN105233867B (en) * | 2014-07-11 | 2017-07-11 | 中国石油化工股份有限公司 | Presulfurization sulfur-resistant transformation catalyst and preparation method |
| CN106795443B (en) * | 2014-07-17 | 2022-05-13 | 沙特基础全球技术有限公司 | Upgrading hydrogen-depleted streams using hydrogen donor streams in hydropyrolysis processes |
| CN105295997A (en) * | 2015-11-03 | 2016-02-03 | 何巨堂 | Arrangement method of downward-flowing type high oxygen and hydrocarbon hydrogenation reactor layered catalyst bed |
| CN106669712B (en) * | 2015-11-11 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of deep hydrodesulfurizationof of diesel oil catalyst and preparation method thereof |
| CN108212168A (en) * | 2016-12-22 | 2018-06-29 | 中国石油天然气股份有限公司 | Modified hydrodesulfurization catalyst and preparation method and application thereof |
| CN110538676B (en) * | 2018-05-29 | 2021-12-28 | 中国石油化工股份有限公司 | Catalyst for hydrogenation refining of cracked tar |
| CN110540864B (en) * | 2018-05-29 | 2021-08-03 | 中国石油化工股份有限公司 | Method for refining pyrolysis tar |
| CN110538659B (en) * | 2018-05-29 | 2021-12-28 | 中国石油化工股份有限公司 | Catalyst for refining cracked tar |
| CN110538658B (en) * | 2018-05-29 | 2021-11-30 | 中国石油化工股份有限公司 | Method for hydrofining cracked tar |
| CN110028984A (en) * | 2019-04-26 | 2019-07-19 | 河南百优福生物能源有限公司 | Biomass pyrolysis liquid hydrogenation deoxidation oil hydrocracking catalyst and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861748A (en) * | 2006-05-08 | 2006-11-15 | 珠海市三金煤制油技术有限公司 | Main hydrogenating catalyst of coal liquification hydrogen supplying solvent and preparation process thereof |
| CN1903984A (en) * | 2005-07-27 | 2007-01-31 | 上海坤维化工科技有限公司 | Hydrogenation method for coal tar processing and its equipment |
| CN101885984A (en) * | 2010-07-09 | 2010-11-17 | 中国科学院过程工程研究所 | Combined technology for producing clean fuel oil by hydrogenation of coal tar and catalyst thereof |
| CN101905163A (en) * | 2010-08-20 | 2010-12-08 | 上海胜帮煤化工技术有限公司 | Coal tar hydrorefining catalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7510645B2 (en) * | 2005-11-04 | 2009-03-31 | Uop Llc | Hydrocracking catalyst containing beta and Y zeolites, and process for its use to produce naphtha |
-
2010
- 2010-12-10 CN CN2010105985054A patent/CN102068992B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903984A (en) * | 2005-07-27 | 2007-01-31 | 上海坤维化工科技有限公司 | Hydrogenation method for coal tar processing and its equipment |
| CN1861748A (en) * | 2006-05-08 | 2006-11-15 | 珠海市三金煤制油技术有限公司 | Main hydrogenating catalyst of coal liquification hydrogen supplying solvent and preparation process thereof |
| CN101885984A (en) * | 2010-07-09 | 2010-11-17 | 中国科学院过程工程研究所 | Combined technology for producing clean fuel oil by hydrogenation of coal tar and catalyst thereof |
| CN101905163A (en) * | 2010-08-20 | 2010-12-08 | 上海胜帮煤化工技术有限公司 | Coal tar hydrorefining catalyst and preparation method thereof |
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