CN109569700A - For tar made fuel oil hydrogenation catalyst - Google Patents
For tar made fuel oil hydrogenation catalyst Download PDFInfo
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- CN109569700A CN109569700A CN201710895344.7A CN201710895344A CN109569700A CN 109569700 A CN109569700 A CN 109569700A CN 201710895344 A CN201710895344 A CN 201710895344A CN 109569700 A CN109569700 A CN 109569700A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The present invention relates to tar made fuel oil hydrogenation catalyst is used for, desulfurization degree, denitrification percent and fuel oil low yield in the prior art are mainly solved the problems, such as.For the present invention by using the catalyst of tar made fuel oil, the catalyst includes active component, auxiliary agent and carrier；The active component includes being selected from Ni, any one in Mo and W, auxiliary agent includes that the technical solution of Zn achieves preferable effect, can be used for coal tar and/or ethylene bottom oil plus in hydrogen made fuel oil.
Description
Technical field
The invention belongs to hydrogenation of tar to produce technical field of fuel oil, and in particular to add hydrogen to urge to for tar made fuel oil
Agent.
Background technique
The outstanding problem that energy supply problem has become China's economic development and faces safely.It is limited in petroleum resources
In the case of, energy fuel available sources are expanded, developing deep process technology and product has the display and strategic importance of major case.Coal tar
Oil, is the by-product of coal coking, destructive distillation and gasification, and output in domestic is more than 10,000,000 tons.Current country's coal tar adds
Work is using a part for extracting the chemicals such as naphthols.It burns up, generates big as low-quality fuel oil after another part simple process
The sewage or NO of amountx、SOxEtc. atmosphere pollutions.The heteroatomic depths such as the sulphur nitrogen oxygen using the achievable coal tar raw material of hydrogenation technique
Degree removing, insatiable hunger alkene and aromatic hydrocarbons saturation improve its stability to improve coal tar H/C ratio, obtain high-grade fuel oil, and subtract
Few environmental pollution.Ethylene bottom oil is the by-product in ethylene production, and main component is aromatic compound, and C/Hratio is high, ash
Divide content very low.Ethylene bottom oil is largely taken as inferior fuel to burn up other than being used as carbon black raw material on a small quantity, however it is not
Easy firing, calorific value is low, and is also easy to produce black smoke and coking when burning, causes environmental pollution.Therefore, using tar as raw material, by adding
Hydrogen technique production fuel oil can produce apparent economic and social benefit, and the status of China's energy shortage is effectively relieved.
The research and development of coal tar hydrogenating production petrol and diesel oil technology have expansion at home and rapidly develop, such as document " coal tar
The experimental study of oil plus hydrogen made fuel oil " (Tian little Zang industry security and environmental protection, 2007,33 (7): 56-57) and document " high temperature
Coal tar hydrogenating produces gasoline and diesel oil " (Beijing, Lv Caishan, Liu Aihua, Da Jianwen petrochemical industry, 2006,35 (1): 33-
36) experimental study of coal tar hydrogenating has been carried out respectively, but resulting octane number and diesel cetane-number are relatively low, not up to
National standard.It is less about the report of coal tar hydrogenating both at home and abroad, the report (such as patent US3253202) of only seldom amount
Related introduction is carried out.Ethylene bottom oil adds the research of hydrogen production petrol and diesel oil technical aspect less, at present only minimal amount of report
(such as patent CN200810228387.0) has carried out related introduction.
The target of hydrogenation of tar technology is the good petrol and diesel oil fuel of production and improves oil product yield as far as possible, and core exists
In catalyst.The final effect that hydrogenation of tar produces fuel oil depends on catalyst performance, and the ingredient (active group of catalyst
Point, auxiliary agent and carrier), preparation method and condition (condition of molding, maturing temperature and roasting medium etc.) determine the property of catalyst
Energy.The identical catalyst of chemical composition, if preparation method and condition difference, microscopic property (such as active material of catalyst
The dispersing uniformity etc. that grain size, catalyst pore-size distribution and active component show in catalyst) it is different, so as to cause catalysis
The performance of agent has very big difference.
When prior art catalyst adds hydrogen fuel oil for coal tar and/or ethylene bottom oil, fuel oil low yield, and fuel oil
Middle sulfur-bearing rate and Nitrogen content are higher.
Summary of the invention
The first technical problem to be solved by the present invention is that desulfurization degree in the prior art, denitrification percent and fuel oil production yield rate are low
The problem of, tar made fuel oil hydrogenation catalyst is provided, which has the excellent of desulfurization degree, denitrification percent and fuel oil high income
Point.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is the application using catalyst described in one of above-mentioned technical problem.
One of to solve above-mentioned technical problem, technical scheme is as follows:
For tar made fuel oil hydrogenation catalyst, the catalyst includes active component, auxiliary agent and carrier；The activity
Component includes being selected from Ni, any one in Mo and W, auxiliary agent includes Zn.The auxiliary agent increases desulfurization degree, denitrification percent and vapour bavin
Oil yield.
In above-mentioned technical proposal, the active component content is preferably 1~50g/L.
In above-mentioned technical proposal, the content of the auxiliary agent is preferably 0.5~10g/L.
In above-mentioned technical proposal, the active component preferably includes Ni, Mo and W.
In above-mentioned technical proposal, the content of Ni is preferably 4~12g/L.
In above-mentioned technical proposal, the content of Mo is preferably 8~18g/L.
In above-mentioned technical proposal, the content of W is preferably 3~10g/L.
In above-mentioned technical proposal, one of technical solution more preferably, the auxiliary agent includes Zn and Cd, and two elements are mentioning
There is synergistic effect in terms of high desulfurization rate, denitrification percent and fuel oil yield.The weight ratio of Zn and Cd is not particularly limited at this time, such as
But be not limited to 0.1~10, more specific ratio example can be 0.20,0.30,0.40,0.50,0.80,0.90,1.0,1.50,
2.00、2.50、3.00、3.50、4.00、4.50、5.00、5.50、6.00、6.50、7.00、7.50、8.00、8.50、9.00、
9.50 etc..
In above-mentioned technical proposal, the two of technical solution more preferably, the auxiliary agent includes Zn and Fe, and two elements are mentioning
There is synergistic effect in terms of high desulfurization rate, denitrification percent and fuel oil yield.The weight ratio of Zn and Fe is not particularly limited at this time, such as
But be not limited to 0.1~10, more specific ratio example can be 0.20,0.30,0.40,0.50,0.80,0.90,1.0,1.50,
2.00、2.50、3.00、3.50、4.00、4.50、5.00、5.50、6.00、6.50、7.00、7.50、8.00、8.50、9.00、
9.50 etc..
In above-mentioned technical proposal, the three of technical solution more preferably, the auxiliary agent further includes Cd and Fe, and Cd and Fe exist
There is synergistic effect in terms of improving desulfurization degree, denitrification percent and fuel oil yield.The weight ratio of Cd and Fe is not particularly limited at this time, example
Such as, but not limited to, 0.1~10, more specific ratio example can be 0.20,0.30,0.40,0.50,0.80,0.90,1.0,
1.50、2.00、2.50、3.00、3.50、4.00、4.50、5.00、5.50、6.00、6.50、7.00、7.50、8.00、8.50、
9.00,9.50 etc..
In above-mentioned technical proposal, it has been found that the auxiliary agent includes Zn, Cd and Fe simultaneously, and three is improving desulfurization degree, taking off
Trielement synergistic effect is gone back in terms of nitrogen rate and fuel oil yield.
In above-mentioned technical proposal, the carrier is not particularly limited, and those skilled in the art can reasonably select and need not
It makes the creative labor, but preferably at least one of self-alumina and modenite.
In above-mentioned technical proposal, the carrier more preferably includes aluminium oxide and modenite.
In above-mentioned technical proposal, the weight fraction ratio of aluminium oxide and modenite is preferably (75~95): (5~25).
To solve above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, comprising the following steps:
(1) carrier is mixed with active component solution；
(2) dry；
(3) it roasts；
(4) it is mixed with compounding agent solution；
(5) dry；
(6) it roasts.
In above-mentioned technical proposal, dry process conditions are not particularly limited, such as, but not limited to step (2) and step
(5) drying temperature is independently selected from 60~120 DEG C (80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C of non limiting example etc. within this range
Deng), step (2) and step (5) drying time such as, but not limited at least stand alone as 6 hours, such as 6~18 hours (herein
Non limiting example 7,8,9,10,11,12 etc. in range)；Step (3) and step (6) maturing temperature preferably independently be selected from 400~
600 DEG C, more preferable 350~550 DEG C, step (3) and step (6) calcining time preferably independently are selected from 3~8 hours；The atmosphere of roasting
It is preferred that air.
In above-mentioned technical proposal, the shape of hydrogenation catalyst is not particularly limited, such as can be spherical shape, bar shaped, annular,
Wheel shape, cylinder, clover, bunge bedstraw herb or sheet.
In above-mentioned technical proposal, for the drying equipment of catalyst preparation, common vacuum oven can be, air blast is done
Dry case, rotary dryer, spray dryer, Caterpillar-type dryer or film drier etc..
In above-mentioned technical proposal, for the roasting apparatus of catalyst preparation, it can be common vertical continuous roasting furnace, turn
Cylinder roaster or kiln formula roaster etc..
To solve above-mentioned technical problem three, technical scheme is as follows: the technical side of one of above-mentioned technical problem
Catalyst described in any one of case adds the application in hydrogen made fuel oil in coal tar and/or ethylene bottom oil.
Key problem in technology of the invention is the selection of catalyst, and to the specific method of application, those skilled in the art can be closed
Reason is selected and need not be made the creative labor.Such as:
The method that hydrogenation of tar produces fuel oil, using through dehydration medium temperature coal tar and hydrogen as raw material, in fixation
Hydrogenation catalyst is loaded in bed reactor, catalyst described in any one of reaction raw materials and above-mentioned technical proposal is made to contact progress
Hydrogenation of tar produces fuel oil.
In above-mentioned technical proposal, preferably 250~400 DEG C of the temperature of reaction, more preferable 300~400 DEG C.
In above-mentioned technical proposal, 0.1~3.0h of tar liquid volume space velocity-1, more preferable 0.3~2.0h-1。
In above-mentioned technical proposal, reaction pressure 5~15MPa, more preferable 8~13MPa.
In above-mentioned technical proposal, the volume ratio 500~1800:1, more preferable 800~1500:1 of hydrogen and tar.
In above-mentioned technical proposal, the day for accounting for hydrogenation catalyst 4-25% mass can be loaded on hydrogenation catalyst bed
Right montmorillonite or other acid natural crystals with either shallow cracking function, or diluted with the heat-resisting inert material such as quartz sand
Natural crystal, can not also load.
In above-mentioned technical proposal, tar charging before, hydrogenation catalyst can with vulcanizing agent (such as: carbon disulfide or diformazan
Base disulfide etc.) presulfurization is carried out, concrete technology condition those skilled in the art of presulfurization can be reasonably selected and not
It must make the creative labor.For example, presulfurization condition can be with are as follows: 250~300 DEG C of curing temperature, sulfurized oil liquid volume air speed
0.5~2.0h-1, vulcanization reaction 3~10MPa of pressure, the volume ratio (500~2000) of hydrogen and sulfurized oil: 1, vulcanization time is
12~48 hours.
The source of tar and property is not particularly limited in catalyst of the present invention, such as can be coal tar, can be second
Alkene tar.When using coal tar, common coal tar can be handled using catalyst hydrogenation of the invention, such as but unlimited
It is as follows in the property of coal tar:
N content 5000~15000ppm, S 1000~10000ppm of content, 180 DEG C -500 DEG C of boiling range.In order to year-on-year, this hair
Coal tar N content 8200ppm, S the content 4000ppm that bright specific embodiment part uses, 180 DEG C -500 of coal tar boiling range
℃。
Sulfur content is measured by GB/T6324.4-86 " measuring method of organic liquid product Determination of Trace Sulfur ", and nitrogen content presses ZD/B
15-56-1999 " analysis method of nitrogen in oil product " measurement.
Desulfurization degree %=(sulfur content in (sulfur content in sulfur content-liquid product in coal tar)/coal tar) × 100%
Denitrification percent %=(nitrogen content in (nitrogen content in nitrogen content-liquid product in coal tar)/coal tar) × 100%
Petrol and diesel oil yield %=(petrol and diesel oil weight/coal tar weight) × 100%
In above-mentioned calculation formula, it will be appreciated by those skilled in the art that liquid product, before referring to separation petrol and diesel oil plus hydrogen is produced
Object, and be easy that the H generated after hydrogen will be added in the prior art by straightforward procedure2S or NH3Removing, such as alkali cleaning can remove
H2S, pickling can remove NH3Etc., therefore sulfur content disregards H in liquid product2S, nitrogen content disregards NH in liquid product3。
Type of reactor applied by catalyst of the present invention is not particularly limited, such as, but not limited to fixed bed reactors,
It is also possible to other kinds of reactor, such as fluidized bed, moving bed etc..
Using the present invention, desulfurization degree is up to 97.4%, and denitrification percent is up to 98.2%, and petrol and diesel oil yield is up to 90.2%, takes
Beneficial technical effect was obtained, can be used for coal tar and/or ethylene bottom oil adds in the production of hydrogen fuel oil.
Specific embodiment
[embodiment 1]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 2]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dry 10h, 490 DEG C of air gas with 900ml iron nitrate aqueous solution (containing 4 grams of Fe)
5h is roasted in atmosphere obtains catalyst.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Fe, 4g/L.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 3]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dry 10h, 490 DEG C of air gas with 900ml zinc nitrate aqueous solution (containing 4 grams of Zn)
5h is roasted in atmosphere obtains catalyst.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Zn, 4g/L.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 4]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dry 10h, 490 DEG C of air gas with 900ml cadmium nitrate aqueous solution (containing 4 grams of Cd)
5h is roasted in atmosphere obtains catalyst.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Cd, 4g/L.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 5]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dryings with 900ml zinc nitrate-cadmium nitrate aqueous solution (containing 2 grams of Zn and 2 gram of Cd)
10h, roasting 5h obtains catalyst in 490 DEG C of air atmospheres.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Zn, 2g/L；Cd, 2g/L.3, it is catalyzed
Agent evaluation
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 6]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dryings with 900ml zinc nitrate-iron nitrate aqueous solution (containing 2 grams of Zn and 2 gram of Fe)
10h, roasting 5h obtains catalyst in 490 DEG C of air atmospheres.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Zn, 2g/L；Fe, 2g/L；.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 7]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor is mixed, 110 DEG C of dryings with 900ml cadmium nitrate-iron nitrate aqueous solution (containing 2 grams of Cd and 2 gram of Fe)
10h, roasting 5h obtains catalyst in 490 DEG C of air atmospheres.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Cd, 2g/L；Fe, 2g/L.
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
[embodiment 8]
1, prepared by carrier
By commercially available 100 parts by weight of active aluminium hydroxide dry glue powder, 10 parts by weight of mordenite molecular sieve original powder, 1:1 nitric acid 8
Parts by weight, 2.1 parts by weight of citric acid, 45 parts by weight of 5 parts by weight of sesbania powder and distilled water are uniformly mixed, and are squeezed out, 110 DEG C of dryings
10h roasts 5h in 470 DEG C of air atmospheres, obtains the cylindrical vector that diameter is a length of 3mm of 1.3mm.
2, catalyst preparation
1L cylindrical vector and 900ml nickel nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (are wherein contained into 7 grams of Ni, 11
Gram Mo and 5 gram of W) mixing, 110 DEG C of dry 8h roast 5h in 450 DEG C of air atmospheres and obtain catalyst precarsor.
Catalyst precarsor and 900ml zinc nitrate-cadmium nitrate-iron nitrate aqueous solution (are contained into 1.5 grams of Zn, 1 gram Cd and 1.5 gram
Fe it) mixes, 110 DEG C of dry 10h, roasting 5h obtains catalyst in 490 DEG C of air atmospheres.
Through icp analysis, catalyst composition are as follows: Ni, 7g/L；Mo, 11g/L；W, 5g/L；Zn, 1.5g/L；Cd, 1g/L；Fe,
1.5g/L。
3, evaluating catalyst
50ml catalyst is loaded in fixed bed reactors, using the aviation for containing 3% (mass concentration) dimethyl disulfide
Kerosene carries out presulfurization to catalyst as sulfurized oil.Conditions of vulcanization are as follows: 280 DEG C of curing temperature, sulfurized oil liquid volume air speed
1.5h-1, Hydrogen Vapor Pressure 5MPa, the volume ratio 1000:1 of hydrogen and sulfurized oil, vulcanization time is 24 hours.
Catalyst after vulcanization carries out coal tar hydrogenating reaction.Reaction condition are as follows: 380 DEG C of reaction temperature, coal tar liquid
Volume space velocity 0.6h-1, reaction pressure 10MPa, the volume ratio 1100:1 of hydrogen and coal tar.
For ease of illustration and compare, the composition of catalyst and evaluating catalyst result are listed in table 1.
The composition and evaluating catalyst result of 1 catalyst of table
Claims (10)
1. being used for tar made fuel oil hydrogenation catalyst, the catalyst includes active component, auxiliary agent and carrier；The active group
It is selected from Ni, any one in Mo and W, auxiliary agent includes Zn.
2. catalyst according to claim 1, it is characterized in that active component content is 1~50g/L.
3. catalyst according to claim 1, it is characterized in that the carrier in aluminium oxide and modenite at least
It is a kind of.
4. catalyst according to claim 3, it is characterized in that the carrier includes aluminium oxide and modenite.
5. catalyst according to claim 4, it is characterized in that the weight ratio of aluminium oxide and modenite is (75~95): (5
~25).
6. the preparation method of catalyst described in any one of Claims 1 to 5, comprising:
(1) carrier is mixed with active component solution；
(2) dry；
(3) it roasts；
(4) it is mixed with compounding agent solution；
(5) dry；
(6) it roasts.
7. according to the method described in claim 6, it is characterized in that step (2) and step (5) drying temperature are independently selected from 60~120
℃。
8. according to the method described in claim 6, it is characterized in that step (3) and step (6) maturing temperature be independently selected from 400~
600℃。
9. according to the method described in claim 6, it is characterized in that step (3) and step (6) calcining time to be independently selected from 3~8 small
When.
10. catalyst described in any one of Claims 1 to 5 adds answering in hydrogen made fuel oil in coal tar and/or ethylene bottom oil
With.
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| CN114425356A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Hydrogenation catalyst combination and application thereof |
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