CN102784653B - Catalyst for producing clean fuel oil by using coal tar and preparation method of catalyst - Google Patents
Catalyst for producing clean fuel oil by using coal tar and preparation method of catalyst Download PDFInfo
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- CN102784653B CN102784653B CN201210268290.9A CN201210268290A CN102784653B CN 102784653 B CN102784653 B CN 102784653B CN 201210268290 A CN201210268290 A CN 201210268290A CN 102784653 B CN102784653 B CN 102784653B
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Abstract
The invention discloses a catalyst for producing clean fuel oil by using coal tar and a preparation method of the catalyst. The catalyst comprises a carrier and active components and is characterized in that the carrier comprises alumina, monox and magnesia; the active components are composed of WO3 and NiO or of MoO3 and NiO; the catalyst further comprises an auxiliary agent composed of K2O and Ga2O3; and the quality of the carrier accounts for 62-88% of the total quality of the catalyst, the quality of the active components accounts for 11-32% of the total quality of the catalyst, and the quality of the auxiliary agent accounts for 1-6% of the total quality of the catalyst. The catalyst has high hydrogen desulfurization, hydrodenitrification, hydrodeoxygenation, aromatics saturation and ring-opening reaction activity and proper acid sites, inhibits coking of easy-to-coke substances in coal tar as coked substances can block a reactor, improves stability of catalyst, and allow petroleum naphtha and diesel oil with low sulfur and nitrogen content to be obtained by hydrotreating coal tar.
Description
Technical field
The present invention relates to a kind of catalyst of producing clean fuel oil for coal tar and preparation method thereof.
Background technology
Along with the fast development of World Economics, needs for fuel oil are more and more, simultaneously also more and more stricter for the quality requirement of oil product, and day by day reducing as the petroleum resources of traditional liquid fuel, therefore alleviate in the urgent need to developing new alternative oil product the nervous situation of oil that the mankind will face.At present, China's Energy Situation is " oil starvation, weak breath, rich coal ", and in the situation that petroleum resources are limited, exploitation has important reality and strategic importance by the technology of coal production clear gusoline.
Coal tar, as the byproduct of producing blue charcoal, coke, coal gasification, is produced approximately 1500 tons per year at present, and wherein most coal tar is not reasonably utilized.Part of coal tar cuts the various cuts in diversity through pretreatment distillation, adopt the method for physics or chemistry to extract the materials such as benzene, phenol, naphthalene to various cuts again, the residue (accounting for coal tar 70%～80%) after extraction substantially flow into fuel market burned fall or as pipeline anti-corrosive paint, waterproof material etc.; Some coal tar even directly comes into the market as low heat value industrial fuel oil.Traditional coal tar processing utilizes technique more backward, the difficulty separating and purify is larger, is difficult for formation scale, contains unsaturated component such as a large amount of alkene, polycyclic aromatic hydrocarbon etc. in coal tar simultaneously, sulphur, nitrogen, oxide and content of impurities are high, and directly burning can produce a large amount of NO
xand SO
xdeng pollutant, produce more solid grain contamination, environment is caused to serious harm.
Coal tar is the liquid product obtaining in destructive distillation and Gas-making, has the characteristic of natural crude oil, but compared with ordinary crude oils, density is large, and viscosity is high, sulfur content is high, especially nitrogen content is high, carbon residue is high, asphalitine is high, therefore of poor quality, is difficult to processing.Result of study in recent years shows, can be removed sulphur, nitrogen, the oxygen in coal tar and be made alkene and aromatic saturation by hydrogenation technique, improves coal tar H/C ratio, improves its stability, obtains high-grade fuel oil.Taking coal tar as raw material, adopt hydrogenation means to produce clean fuel oil, not only there is significant economic benefit, and there is obvious social benefit, also can be alleviation China energy starved present situation and make contributions.
The core of coal tar hydrogenating technology is catalyst, the final effect that its hydrogenation is produced fuel oil depends on catalyst performance, and catalyst performance forms (active component, auxiliary agent and carrier) and preparation method and conditional decision by catalyst, wherein catalyst has formed deciding factor.With respect to petroleum distillate, coal tar is more difficult to hydrotreatment, therefore the catalyst that is applicable to coal tar hydrogenating process needs more active component content, simultaneously owing to containing more large molecule and more easy green coke material and metal component in coal tar, require hydrogenation catalyst to there is larger pore volume and specific area, moreover in coal tar, contain a large amount of aromatic hydrocarbons, require deeply hydrodearomatized, and under the prerequisite that as far as possible reduces chain rupture, make to greatest extent aromatic saturation and open loop, therefore require catalyst to there is suitable acidity.
The Chinese invention patent that existing a kind of publication number is CN100337747C discloses a kind of catalyst for coal tar hydrogenation modification and preparation method thereof and application.Catalyst carrier is made up of aluminium oxide, silica and Modified Zeolite Y, active component is the mixture of tungsten oxide, molybdenum oxide and nickel oxide or the mixture of tungsten oxide and nickel oxide, uses this catalyst can remove sulfur impurity, nitrogen, colloid and asphalitine, the saturated aromatic component in coal tar and make the open loop of part aromatic hydrocarbons.But it is not very good that its shortcoming is effect.Therefore this technical scheme needs to improve.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of catalyst of producing clean fuel oil for coal tar, this catalyst can effectively remove sulphur, nitrogen, oxygen, colloid, the bitum impurity in coal tar, make the open loop of part aromatic hydrocarbons, can suppress the easily coking of green coke material in coal tar simultaneously.
The present invention will solve the technical scheme that above-mentioned first technical problem adopts: this produces the catalyst of clean fuel oil for coal tar, formed by carrier and active component, it is characterized in that: described carrier is made up of aluminium oxide, silica, magnesia, and described active component is by WO
3with NiO or MoO
3with NiO composition, and in catalyst, there is K
2o and Ga
2o
3the auxiliary agent of composition, and described carrier accounts for 62～88% of catalyst gross mass, described active component accounts for 11～32% of catalyst gross mass, and described auxiliary agent accounts for 1～6% of catalyst gross mass.
Al in above-mentioned carrier
2o
3can account for 67～81% of carrier gross mass, SiO
2can account for 6～12% of carrier gross mass, MgO can account for 7～27% of carrier gross mass.
Above-mentioned active component is by WO
3while composition with NiO, described WO
3can account for 8～23% of catalyst gross mass, described NiO can account for 3～9% of catalyst gross mass; When active component is by MoO
3while composition with NiO, described MoO
3can account for 6～18% of catalyst gross mass, and described NiO can account for 5～14% of catalyst gross mass.
K in above-mentioned auxiliary agent
2o can account for 0.8～4.9% of catalyst gross mass, described Ga
2o
3can account for 0.2～1.1% of catalyst gross mass.
It is reasonable, easy to prepare that second technical problem that the present invention will solve is to provide a kind of technique, and the catalyst of preparation can effectively remove sulphur, nitrogen, oxygen, colloid, the bitum impurity in coal tar, make the open loop of part aromatic hydrocarbons, can suppress the easily coking of green coke material in coal tar simultaneously.
The present invention will solve the technical scheme that above-mentioned second technical problem adopt: above-mentioned preparation method of producing the catalyst of clean fuel oil for coal tar, is characterized in that: comprise the steps:
One, carrier preparation
Press the composition of carrier, the ethyl orthosilicate of amount of calculation is dissolved in appropriate absolute ethyl alcohol, flood at normal temperatures Al
2o
3to 2-24 hour, after dipping, in the temperature of 80～150 DEG C, be dried 4-12 hour, then roasting 2～8 hours in the temperature of 300～1000 DEG C, make silica-alumina supports, then in the silica-alumina supports of making, add the magnesium-containing compound of amount of calculation, add again the peptizing agent that accounts for solid gross mass 0.4～6.7%, add the binding agent that accounts for solid gross mass 0.1～2.8%, add the extrusion aid that accounts for solid gross mass 1.8～8.9%, kneading becomes plastic aftershaping, after moulding, in the temperature of 80～150 DEG C, be dried 4～12 hours, again 300～1000 DEG C of temperature roastings 2～8 hours, make carrier,
Two, the dipping of active component
Molybdenum salt and the nickel salt of the tungsten salt of amount of calculation and ammonium nitrate or amount of calculation are mixed with to the aqueous solution, carrier made step 1 is placed in to the aqueous solution at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C, be dried 4～12 hours, roasting 2～8 hours in the temperature of 300～1000 DEG C again, makes catalyst semi-finished product;
Three, the dipping of auxiliary agent
The sylvite of amount of calculation and gallium nitrate are mixed with to the aqueous solution, catalyst semi-finished product made step 2 are placed in to the aqueous solution that sylvite and gallium nitrate be mixed with at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C, be dried 4～12 hours, roasting 2～8 hours in the temperature of 300～1000 DEG C again, makes described catalyst.
As improvement, described magnesium-containing compound can be preferably one or more in magnesium hydroxide, magnesia, magnesium carbonate, magnesium nitrate, magnesium acetate, magnesium oxalate.
As improvement, described peptizing agent can be preferably one or more in nitric acid, hydrochloric acid, acetic acid.
As improvement, described binding agent can be preferably one or more in the blue or green powder in field, paraffin, starch, carboxymethyl cellulose, dextrin, polyvinyl alcohol.
As improvement, described extrusion aid can be preferably one or more in the blue or green powder in field, tartaric acid, citric acid.
As improvement, described tungsten salt can be preferably one or more in ammonium paratungstate, ammonium metatungstate, sodium tungstate, potassium tungstate.
As improvement, described molybdenum salt can be preferably one or more in ammonium molybdate, potassium molybdate, sodium molybdate.
As improvement, described nickel salt may be selected to be one or more in nickel nitrate, nickel acetate, citric acid nickel, nickel chloride.
Improve, described sylvite may be selected to be one or more in potassium nitrate, potash, saleratus, potassium sulfate, potassium chloride again.
Compared with prior art, the invention has the advantages that this catalyst is in to coal tar hydrogenating desulfurization, hydrodenitrogeneration, hydrogenation deoxidation, can improve active, make aromatic saturation and open loop, and owing to having added auxiliary agent potassium in catalyst, suppress the coking and blocking reactor of easy green coke material in coal tar, improved the stability of catalyst; After coal tar fraction adopts catalyst hydrogenation of the present invention to process, can make naphtha and the diesel oil of low-sulfur, low nitrogen.Not only enhance productivity, and the quality ideal of products of separated, be a kind of very practical product and preparation method with thering is economic worth, be worthy of popularization.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The catalyst for coal tar production clean fuel oil of the present embodiment, is made up of carrier and active component, and described carrier is made up of aluminium oxide, silica, magnesia, and described active component is by WO
3with NiO or MoO
3with NiO composition, and have with K in catalyst
2o and Ga
2o
3the auxiliary agent of composition, and described carrier accounts for 62～88% of catalyst gross mass, described active component accounts for 11～32% of catalyst gross mass, and described auxiliary agent accounts for 1～6% of catalyst gross mass.Al in above-mentioned carrier
2o
3account for 67～81% of carrier gross mass, SiO
2account for 6～12% of carrier gross mass, MgO accounts for 7～27% of carrier gross mass.Above-mentioned active component is by WO
3while composition with NiO, described WO
3account for 8～23% of catalyst gross mass, described NiO accounts for 3～9% of catalyst gross mass; When active component is by MoO
3while composition with NiO, above-mentioned MoO
3account for 6～18% of catalyst gross mass, and described NiO accounts for 5～14% of catalyst gross mass.K in above-mentioned auxiliary agent
2o accounts for 0.8～4.9% of catalyst gross mass, above-mentioned Ga
2o
3account for 0.2～1.1% of catalyst gross mass.
Above-mentioned preparation method of producing the catalyst of clean fuel oil for coal tar, comprises the steps:
One, carrier preparation
Press the composition of carrier, the ethyl orthosilicate of amount of calculation is dissolved in appropriate absolute ethyl alcohol, flood at normal temperatures Al
2o
3to 2-24 hour, after dipping, in the temperature of 80～150 DEG C, be dried 4-12 hour, then roasting 2～8 hours in the temperature of 300～1000 DEG C, make silica-alumina supports, then in the silica-alumina supports of making, add the magnesium hydroxide of amount of calculation, add again the hydrochloric acid that accounts for solid gross mass 0.4～6.7%, add the paraffin that accounts for solid gross mass 0.1～2.8%, add the blue or green powder in field that accounts for solid gross mass 1.8～8.9%, kneading becomes plastic aftershaping, after moulding, in the temperature of 80～150 DEG C, be dried 4～12 hours, again 300～1000 DEG C of temperature roastings 2～8 hours, make carrier,
Two, the dipping of active component
Ammonium molybdate and the nickel nitrate of the ammonium tungstate of amount of calculation and ammonium nitrate or amount of calculation are mixed with to the aqueous solution, carrier made step 1 is placed in to the aqueous solution at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C, be dried 4～12 hours, roasting 2～8 hours in the temperature of 300～1000 DEG C again, makes catalyst semi-finished product;
Three, the dipping of auxiliary agent
The potassium nitrate of amount of calculation and gallium nitrate are mixed with to the aqueous solution, catalyst semi-finished product made step 2 are placed in to the aqueous solution that potassium nitrate and gallium nitrate be mixed with at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C, be dried 4～12 hours, roasting 2～8 hours in the temperature of 300～1000 DEG C again, makes described catalyst.
Describe the present invention in detail below by instantiation, but do not limit the scope of the invention.
Embodiment mono-:
Adopt equi-volume impregnating, 50.21g ethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol, add 132.80gAl
2o
3, under normal temperature, flood 4h, after dipping, in 120 DEG C of dry 8h, after hydrolysis, in 800 DEG C of roasting 4h, make required silica-alumina supports.In the silica-alumina supports making, add 68.7g magnesium nitrate hexahydrate, add the peptizing agent that accounts for solid gross mass 2.3%, account for the binding agent of solid gross mass 1.8%, account for the extrusion aid of solid gross mass 3.9%, kneading becomes after plastic, adopt cylindric crowded hole grinding tool extruded moulding, extrusion diameter 3.5mm, length 5.0mm.Dry 8h in 120 DEG C of baking ovens, 800 DEG C of roasting 4h, make final shaping carrier.
27.56g ammonium tungstate and 60.72g Nickelous nitrate hexahydrate are mixed with to the aqueous solution, will under above prepared shaping carrier normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h.5.15g potassium nitrate and 4.37g gallium nitrate are mixed with to the aqueous solution, will under above prepared catalyst normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h, obtain final catalyst for hydro-upgrading.
Embodiment bis-:
Adopt equi-volume impregnating, 15.95g ethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol, add 129.20gAl
2o
3, under normal temperature, flood 4h, after dipping, in 120 DEG C of dry 8h, after hydrolysis, in 800 DEG C of roasting 4h, make required silica-alumina supports.In the silica-alumina supports making, add 34.26g tri-hydrocarbonate of magnesias, add the peptizing agent that accounts for solid gross mass 1.6%, account for the binding agent of solid gross mass 1.2%, account for the extrusion aid of solid gross mass 2.7%, kneading becomes after plastic, adopts clover to squeeze hole abrasive tool moulding, clover diameter 3.5mm.Dry 8h in 120 DEG C of baking ovens, 800 DEG C of roasting 4h, make final shaping carrier.
57.86g sodium tungstate and 33.48g Nickelous nitrate hexahydrate are mixed with to the aqueous solution, will under above prepared shaping carrier normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h.13.31g potassium nitrate and 1.64g gallium nitrate are mixed with to the aqueous solution, will under above prepared catalyst normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h, obtain final catalyst for hydro-upgrading.
Embodiment tri-:
Adopt equi-volume impregnating, 57.55g ethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol, add 116.20gAl
2o
3, under normal temperature, flood 4h, after dipping, in 120 DEG C of dry 8h, after hydrolysis, in 800 DEG C of roasting 4h, make required silica-alumina supports.In the silica-alumina supports making, add 104.29g Magnesium acetate (Mg(OAc)2) tetrahydrate, add the peptizing agent that accounts for solid gross mass 4.7%, account for the binding agent of solid gross mass 2.1%, account for the extrusion aid of solid gross mass 3.3%, kneading becomes after plastic, adopt cylindric crowded hole grinding tool extruded moulding, extrusion diameter 3.5mm, length 5.0mm.Dry 8h in 120 DEG C of baking ovens, 800 DEG C of roasting 4h, make final shaping carrier.
29.68g ammonium molybdate and 23.52g nickelous carbonate are mixed with to the aqueous solution, will under above prepared shaping carrier normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h.
16.31g potassium nitrate and 2.73g gallium nitrate are mixed with to the aqueous solution, will under above prepared catalyst normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h, obtain final catalyst for hydro-upgrading.
Embodiment tetra-:
Adopt equi-volume impregnating, 47.84g ethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol, add 127.80gAl
2o
3, under normal temperature, flood 4h, after dipping, in 120 DEG C of dry 8h, after hydrolysis, in 800 DEG C of roasting 4h, make required silica-alumina supports.In the silica-alumina supports making, add 12.8g magnesia, add the peptizing agent that accounts for solid gross mass 0.7%, account for the binding agent of solid gross mass 0.9%, account for the extrusion aid of solid gross mass 2.1%, kneading becomes after plastic, adopts clover to squeeze hole abrasive tool moulding, clover diameter 3.5mm.Dry 8h in 120 DEG C of baking ovens, 800 DEG C of roasting 4h, make final shaping carrier.28.57g sodium molybdate and 90.30g Nickelous nitrate hexahydrate are mixed with to the aqueous solution, will under above prepared shaping carrier normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h.9.87g potassium nitrate and 2.18g gallium nitrate are mixed with to the aqueous solution, will under above prepared catalyst normal temperature, flood 4h, dry 8h in 120 DEG C of baking ovens, 500 DEG C of roasting 4h, obtain final catalyst for hydro-upgrading.
The chemical composition of the prepared catalyst of above embodiment and main physico-chemical property are as shown in table 1.
The main physico-chemical property of catalyst for hydro-upgrading in table 1 embodiment
Embodiment five:
The performance evaluation of catalyst for hydro-upgrading of the present invention, evaluates front 280 DEG C of presulfurization 10h, then taking coal tar as raw material, carries out the catalytic hydrogenation reaction of coal tar, 380 DEG C of reaction temperatures, reaction pressure 15MPa, air speed 1.6h
-1, hydrogen: the volume ratio of coal tar is 1700: 1.Feedstock oil used and the character of hydrogenated oil are in table 2.
As can be seen from Table 2, in four kinds of catalyst, the activity of catalyst C2 is the highest, and sulphur, nitrogen removal efficiency are the highest, the amplification maximum of diesel cetane-number.
Table 2 high temperature coal-tar raw material and generation oil nature
Claims (10)
1. a catalyst of producing clean fuel oil for coal tar, is made up of carrier and active component, it is characterized in that: described carrier is made up of aluminium oxide, silica, magnesia, and described active component is by WO
3with NiO or MoO
3with NiO composition, and have with K in catalyst
2o and Ga
2o
3the auxiliary agent of composition, and described carrier accounts for 62～88% of catalyst gross mass, described active component accounts for 11～32% of catalyst gross mass, and described auxiliary agent accounts for 1～6% of catalyst gross mass.
2. catalyst according to claim 1, is characterized in that: Al in described carrier
2o
3account for 67～81% of carrier gross mass, SiO
2account for 6～12% of carrier gross mass, MgO accounts for 7～27% of carrier gross mass.
3. catalyst according to claim 1, is characterized in that: described active component is by WO
3while composition with NiO, described WO
3account for 8～23% of catalyst gross mass, described NiO accounts for 3～9% of catalyst gross mass; When active component is by MoO
3while composition with NiO, described MoO
3account for 6～18% of catalyst gross mass, and described NiO accounts for 5～14% of catalyst gross mass.
4. catalyst according to claim 1, is characterized in that: K in described auxiliary agent
2o accounts for 0.8～4.9% of catalyst gross mass, described Ga
2o
3account for 0.2～1.1% of catalyst gross mass.
5. an arbitrary described preparation method who produces the catalyst of clean fuel oil for coal tar in claim 1 to 4, is characterized in that: comprise the steps:
One, carrier preparation
Press the composition of carrier, the ethyl orthosilicate of amount of calculation is dissolved in appropriate absolute ethyl alcohol, flood at normal temperatures Al
2o
3to 2-24 hour, after dipping, in the temperature of 80～150 DEG C, be dried 4-12 hour, then roasting 2～8 hours in the temperature of 300～1000 DEG C, make silica-alumina supports, then in the silica-alumina supports of making, add the magnesium-containing compound of amount of calculation, add again the peptizing agent that accounts for solid gross mass 0.4～6.7%, add the binding agent that accounts for solid gross mass 0.1～2.8%, add the extrusion aid that accounts for solid gross mass 1.8～8.9%, kneading becomes plastic aftershaping, after moulding, in the temperature of 80～150 DEG C, be dried 4～12 hours, again 300～1000 DEG C of temperature roastings 2～8 hours, make carrier,
Two, the dipping of active component
Molybdenum salt and the nickel salt of amount of calculation are mixed with to the aqueous solution, carrier made step 1 is placed in to the aqueous solution at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C dry 4～12 hours, then roasting 2～8 hours in the temperature of 300～1000 DEG C, catalyst semi-finished product made;
Three, the dipping of auxiliary agent
The sylvite of amount of calculation and gallium nitrate are mixed with to the aqueous solution, catalyst semi-finished product made step 2 are placed in to the aqueous solution that sylvite and gallium nitrate be mixed with at normal temperatures to be flooded 2～24 hours, then in the temperature of 80～150 DEG C, be dried 4～12 hours, roasting 2～8 hours in the temperature of 300～1000 DEG C again, makes described catalyst.
6. preparation method according to claim 5, is characterized in that: described magnesium-containing compound is one or more in magnesium hydroxide, magnesia, magnesium carbonate, magnesium nitrate, magnesium acetate, magnesium oxalate.
7. preparation method according to claim 5, is characterized in that: described peptizing agent is one or more in nitric acid, hydrochloric acid, acetic acid.
8. the each method of system according to claim 5, is characterized in that: described binding agent is one or more in the blue or green powder in field, paraffin, starch, carboxymethyl cellulose, dextrin, polyvinyl alcohol.
9. the each method of system according to claim 5, is characterized in that: described extrusion aid is one or more in the blue or green powder in field, tartaric acid, citric acid.
10. preparation method according to claim 5, is characterized in that: described sylvite is one or more in potassium nitrate, potash, saleratus, potassium sulfate, potassium chloride.
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| CN103695030B (en) * | 2013-12-18 | 2015-10-21 | 宁波金远东工业科技有限公司 | The method of the producing diesel by hydrogenating anthrancene oil in coal tar |
| 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 |
| CN104785274B (en) * | 2015-04-13 | 2017-03-29 | 河北工业大学 | A kind of preparation method of this build of large aperture Ni Mo hydrogenation deoxidation catalysts |
| CN109701537A (en) * | 2018-12-21 | 2019-05-03 | 胡平 | A kind of catalyst for pre-hydrogenation and its preparation method and application |
| CN111054447A (en) * | 2019-11-29 | 2020-04-24 | 山西永东化工股份有限公司 | Catalyst capable of purifying and condensing catalytic cracking of coal tar and application thereof |
| CN113083351B (en) * | 2021-04-08 | 2022-01-14 | 中国矿业大学 | Application of high-activity ruthenium molecular sieve catalyst Ru/Ga-SH5 in aspect of catalytic hydrodeoxygenation |
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| CN1772846A (en) * | 2005-11-17 | 2006-05-17 | 中国石油化工集团公司 | Coal tar hydrogenating modification catalyst and its prepn and application |
| CN101574659A (en) * | 2009-06-15 | 2009-11-11 | 中国科学院山西煤炭化学研究所 | Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1772846A (en) * | 2005-11-17 | 2006-05-17 | 中国石油化工集团公司 | Coal tar hydrogenating modification catalyst and its prepn and application |
| CN101574659A (en) * | 2009-06-15 | 2009-11-11 | 中国科学院山西煤炭化学研究所 | Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications |
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