CN1070215A - Hydrogenization catalyst preparation method - Google Patents
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- CN1070215A CN1070215A CN 91108646 CN91108646A CN1070215A CN 1070215 A CN1070215 A CN 1070215A CN 91108646 CN91108646 CN 91108646 CN 91108646 A CN91108646 A CN 91108646A CN 1070215 A CN1070215 A CN 1070215A
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Abstract
The present invention has introduced a kind of hydrogenation process that is applicable to aromatic hydrocarbons or unsaturated hydrocarbons, especially after hydrofining or hydrocracking, obtain with lubricating oil distillate, sulphur and nitrogen content be the deep hydrofinishing Preparation of catalysts method of raw material production food (medicine) grade white oil process less than industrial white oil or the hydrocracking tail oil that 10ppm, aromaticity content are not more than 6 (weight) % all.The present invention is owing to adopted γ-Al
2O
3The moulding of precursor elder generation again after the roasting, be the precursor of nickel and molybdenum and soak molybdenum earlier and soak nickel again after roasting with the ammonia soln that contains molybdenum and nickel compound containing, with technology such as low-temperature bake, low-temperature reductions, its catalytic activity is had increased significantly than the catalyzer with the ordinary method preparation.
Description
The invention belongs to the hydrogenation catalyst preparation method, particularly be applicable to the hydrogenation process of aromatic hydrocarbons or unsaturated hydrocarbons, especially after hydrofining or hydrocracking, obtain with lube cut, that sulphur and nitrogen content all are not more than 6(less than 10ppm, aromaticity content is heavy) industrial white oil or the hydrocracking tail oil of % be the deep hydrofinishing Preparation of catalysts method of raw material production food (medicine) grade white oil process.
Industrial production food (medicine) grade white oil, normally adopt following method:
Earlier to lube cut, under the effect of the catalyzer that contains VIII family metal and VI family metal, carry out hydrofining, obtaining sulphur and nitrogen content, all to be not more than 6(less than 10ppm, aromaticity content heavy) industrial white oil or the hydrocracking tail oil of %; And then its product carried out deep hydrofinishing, removing remaining sulphur, nitrogen and aromatic hydrocarbons, and obtain food (medicine) grade white oil.
At present, the deep hydrofinishing catalyzer of industrial use generally speaking has two types: a kind of is precious metal such as platinum, palladium catalyst, and this type of catalyst activity is higher, but owing to need with the less precious metal of raw material resources, thereby cost an arm and a leg; Another kind is nickel/alumina catalyst, though this type of catalyzer activity is lower, cheap, raw material resources are enriched, are easy to get, and extremely application prospects is arranged.Therefore, a kind of catalyzer in back has been carried out extensive studies both at home and abroad in recent years, to improve its catalytic activity.
Introduced among the USP4490480 a kind of be used for methanation or aliphatic acid hydrogenation, have 80～300 meters
2Nickel/the aluminium oxide catalyst of surface-area of/gram nickel, and catalyst system can contain the molybdenum auxiliary agent, so that it reduces the susceptibility to poisonous substance.But this catalyzer adopts high-temperature roasting in preparation process, in use adopt high temperature reduction, has not only increased energy consumption, also easily causes the nickel crystallite gathering of catalyst surface and causes that catalytic activity descends; In addition, if contain sulfate radical in the carrier (in the aluminium hydroxide product with Tai-Ace S 150-sodium metaaluminate method production, generally all contain sulfate radical), then during high temperature reduction, reduction hydrogen also easily and the sulfate radical generation chemical reaction in the aluminum oxide, the sulfide that generation is poisoned nickel catalyzator, and make catalyst activity reduction.
Introduced a kind of deep hydrofinishing nickel/aluminium oxide catalyst that is used to produce white oil among the EP290100, this catalyzer is owing to adopted the technology of high-temperature roasting carrier, reduced the interaction of active component nickel and aluminum oxide, increased the aperture of catalyzer simultaneously, thereby catalytic activity is increased.But this catalyzer adopts high-temperature roasting equally in preparation, adopts high temperature reduction before using, and therefore has the shortcoming of aforesaid method equally.
Introduced a kind of nickel/aluminium oxide catalyst among the USP4191664 with the coprecipitation method preparation, this catalyzer adopts high-temperature roasting and high temperature reduction equally, except the shortcoming that aforesaid method is arranged, because this catalyzer adopts the coprecipitation method preparation, thereby also has a shaping of catalyst difficulty, intensity difference, shortcoming such as work-ing life is short.
Introduced a kind of preparation method of nickel/aluminium oxide catalyst among the CN89106476, this method is owing to adopted repeatedly technology such as dipping, low-temperature bake and low-temperature reduction, make catalyst activity increase, but because nickel content is higher, in preparation process, often need to adopt repeatedly dipping and repeatedly roasting, thereby make that preparation process is comparatively complicated, cost is also higher.
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of and have higher catalytic activity and advantages of excellent stability and prepare better simply method for preparing catalyst.
Technical characterictic of the present invention is:
(1) with the precursor powder of gama-alumina or the precursor powder and the silicon compound powder mixing aftershaping of gama-alumina, under 550～750 ℃ of air, roasting 1～6 hour makes carrier.
(2) carrier that above-mentioned (1) is obtained, be immersed in the ammonia soln of the molybdate compound for preparing in advance, under the condition of room temperature～80 ℃, soaked 2～4 hours, filter, at 80～150 ℃ down after dry 2～16 hours, 200～600 ℃ of roastings are 2～8 hours under air and/or the water vapor, obtain containing the carrier of molybdenum.
(3) product that again (2) is obtained is immersed in the ammonia soln of the nickel compound containing for preparing in advance, soaks 1～6 hour under the condition of room temperature～60 ℃, filter, 80～150 ℃ dry 4～16 hours down.
(4) repeat once the operation of (3) again.
(5) product that (4) are obtained, under 200～350 ℃ the condition, roasting can obtain described catalyzer in 4～8 hours under air.
The precursor of described gama-alumina is amorphous hydroted alumina, false boehmite, book diaspore, gibbsite, surge aluminium stone or promise diaspore, preferably false boehmite or book diaspore, wherein can contain auxiliary agent,, distribute and surface properties to improve alumina pore as phosphorus, silicon etc.
Described silicon compound preferably dioxide-containing silica is that 80～90(is heavy) pure aluminium silicate microballoon powder or the dioxide-containing silica of % be that 20～30(is heavy) silicon sol of %.
The ordinary method of metal load type catalyst carrier is adopted in the moulding of gama-alumina precursor, as dripping ball forming, extrusion molding etc.That carrier can adopt is spherical, sheet or strip; Wherein strip can be circle bar or special-shaped bar, as trilobal cross, four blade profiles, dumbbell shape etc.When carrier adopts extrusion molding, need to add conventional peptizing agent, as mineral acid or organic acids such as nitric acid, citric acid, oxalic acid, and extrusion aid, as field mountain valley with clumps of trees and bamboo powder, starch, Mierocrystalline cellulose etc.
The ammonia soln of described molybdate compound is to adopt ordinary method to make, that is: with molybdate compound, it is formulated in 2～25% ammoniacal liquor being dissolved in weight percent concentration.Wherein molybdate compound is molybdate or molybdic oxide, preferably ammonium molybdate.
The ammonia soln of described nickel compound containing is by nickel compound containing, ammoniacal liquor and the ammonium salt identical with the negatively charged ion of used nickel compound containing, makes (referring to the preparation method of nickel ammine in the general materialization handbook) according to ordinary method.Wherein nickel compound is nickelous carbonate or basic nickel carbonate.
During with the ammonia soln impregnated carrier of molybdate compound, normally adopt the method for excessive dipping, admittedly liquid/be 2～5: 1(is heavy).
During with the ammonia soln impregnated carrier of nickel compound containing, normally adopt the method for excessive dipping, admittedly liquid/be 2～4: 1(is heavy).
The described molybdenum carrier maturing temperature that contains, preferably 450～550 ℃.
Preferably 240～280 ℃ of the maturing temperatures of described nickel-molybdenum/aluminium oxide catalyst, roasting time preferably 3～6 hours.
The catalyst content that makes according to the method described above (is benchmark with the catalyst weight) is: Ni9.0～22.0(is heavy) %, Mo2.0～12.0(is heavy) and %, SiO
20～18(weight) aluminum oxide of % and surplus.
The catalyzer that makes according to the method described above is applicable to sulphur and nitrogen content all less than 10ppm aromatic hydrocarbons or hydrogenation reaction of unsaturated hydrocarbon process, particularly after hydrofining or hydrocracking, obtain with lube cut, that sulphur and nitrogen content all are not more than 6(less than 10ppm, aromaticity content is heavy) industrial white oil or the hydrocracking tail oil of % be the unifining process of raw material production food (medicine) grade white oil.
When the catalyzer that makes according to the method described above was used to produce the unifining process of food (medicine) grade white oil, catalyzer needed before use under hydrogen, and through 150～350 ℃, preferably 240～280 ℃ were reduced 4～48 hours.
The present invention is owing to adopted the technology of preparing of the ammonia soln impregnated carrier that contains molybdenum and nickel compound containing, it is compared with the prior art for preparing nickel or nickel-molybdenum/alumina body series catalysts with coprecipitation method, have catalyzer and be easy to that moulding, intensity height, life-span are long, active constituent is evenly distributed and the catalytic activity advantages of higher; The present invention is owing to adopted and soak molybdenum earlier soak nickel again after roasting, with soak low-temperature bake behind the nickel, use before the technology of low-temperature reduction, make it not only reduce the interaction of impurity in active constituent nickel and carrier interactions and reducing atmosphere and the carrier, also avoided simultaneously the accumulation of metal phenomenon of the catalyst surface that causes owing to high-temperature roasting, thereby with adopt high-temperature roasting to prepare nickel or nickel-molybdenum/alumina body series catalysts, adopt the prior art of high temperature reduction to compare in using, have the advantage such as more high catalytic activity, stability etc. of catalyzer; The present invention compares with single nickel catalyzator owing to introduced the molybdenum auxiliary agent, has higher catalytic activity.
In a word, the present invention is owing to adopted γ-Al
2O
3Precursor elder generation's moulding roasting again, be the precursor of nickel and molybdenum and soak molybdenum earlier and after roasting, soak nickel again with the ammonia soln that contains molybdenum and nickel compound containing, and low-temperature bake, the low-temperature reduction technology, its catalytic activity is had increased significantly, therefore, when certain hydrogenation degree of depth requires, use catalyzer provided by the invention, than the catalyzer that uses prior art, not only can reduce the nickel amount of metal of catalyzer widely, thereby reduced the catalyzer cost, simultaneously can also reduce temperature of reaction and pressure, thereby reduce energy consumption, reduced requirement to equipment, the insecurity of having avoided high top pressure operation to bring; In addition, also can improve air speed, to enhance productivity.
Further describe technical characterstic of the present invention below by embodiment and Comparative Examples.
Example 1
Example 1 has been introduced the preparation process of carrier.
Aluminium hydroxide and an amount of nitric acid, citric acid, field mountain valley with clumps of trees and bamboo powder and water are mediated evenly, extrusion molding, 120 ℃ of dryings 4 hours, roasting can obtain strip carrier a～d(in 2～6 hours and see Table 1 under 550～750 ℃ of air).
Each raw material sources in the table:
SB is from the Germany import; A is 3822 dry glue powders that Fushun No.3 Petroleum Factory produces, and contains the phosphorus of 1.7 heavy % and the SiO of 5 heavy %
2; B is the dry glue powder that the refinery, Chang Ling produces, and contains the SO of 0.7 heavy %
4 -2; 1. silicide is that the refinery, Chang Ling produces silicon aluminium microsphere, contains the silicon-dioxide of 87 heavy %; 2. silicide is the sial solution that Changhong chemical plant, 90 middle school, Beijing produces, and contains the silicon-dioxide of 25 heavy %; Concentration of nitric acid is 65 heavy %, chemical pure; Citric acid is a food grade; Field mountain valley with clumps of trees and bamboo powder is that Shanghai local products company produces.
Example 2
Example 2 has been introduced the preparation process that contains the molybdenum carrier.
With 160 gram (NH
4)
6, Mo
7O
24.4H
2O(Shenyang chemical reagent one factory) heavy with 480 milliliters of 8%() ammoniacal liquor (the new photochemical factory in Beijing) mix, stirring and dissolving is diluted to 600 milliliters with deionized water, mixes to make the solution that contains molybdenum; In this solution, add a certain amount of carrier, room temperature～80 ℃ are dipping 2～4 hours down, the steeping fluid that elimination is unnecessary, 80～150 ℃ of dryings 2～6 hours, roasting 2～16 hours under 200～600 ℃, 100% air and/or water vapor again obtains containing molybdenum carrier 1～6(and sees Table 2).
Example 3
Example 3 has been introduced the Preparation of catalysts process.
Nickeliferous ammonia soln prepares with following method.
The ammoniacal liquor (the new photochemical factory in Beijing) of 1600 gram basic nickel carbonates (Fushun No.3 Petroleum Factory), 1360 gram volatile salts (Red Star chemical plant, Beijing) and 2370 milliliters 23% is placed in the container, 45 ℃ stirred in water bath 3 hours, just can obtain being used for the nickeliferous ammonia soln of impregnated catalyst.
Catalyzer prepares with following method.
Get and a certain amount ofly contain the molybdenum carrier by what above-mentioned example made, immerse in a certain amount of nickeliferous ammonia soln, the dipping in room temperature～60 ℃ 1～6 hour filters, 80～150 ℃ dry 4～16 hours down; After repeating once above-mentioned dip operation again, with resulting product, roasting is 4～8 hours under 200～350 ℃ of air, can obtain that described catalyst A～L(sees Table 3, table 4).
Comparative Examples 1
This example is the method preparation by CN89106476.
3822 aluminium hydroxides that the SB aluminium hydroxide that the Germany is produced and Fushun No.3 Petroleum Factory produce are by 4: 1(is heavy) mixed evenly after extrusion moulding, roasting obtains alumina supporter under 600 ℃ of air; Get 1200 these carriers of gram and place container, add 2000 milliliters of nickel ammine immersion liquid that contain nickel oxide 0.223 grams per milliliter solution, soaked 3 hours down, filter, 120 ℃ of dryings 6 hours at 45 ℃; Carry out the 2nd dipping, filtration, drying then, and after 6 hours, carry out dipping again 3,4 times, filter, dry and, just can obtain reference catalyst D1 in 275 ℃ of following roastings 6 hours through 275 ℃ of roastings.Relevant datas such as its composition, structure and catalytic activity see Table 4.
Comparative Examples 2
This example is the method preparation according to USP4490480.
With 200 gram γ-Al
2O
3Carrier places container, contains the nickel ammonia steeping fluid that nickel oxide is 0.233 grams per milliliter solution with 300 milliliters, and 50 ℃ were soaked 1.5 hours down, filters, in 120 ℃ of dryings 16 hours; Soak according to carry out the second time with quadrat method again; Roasting 45 minutes under 400 ℃ of air then; Products therefrom is heavy with containing molybdenum 13(again) the molybdenum ammonia solution of % 30 ℃ of dippings 2 hours down again, filter, 120 ℃ of dryings 16 hours, 450 ℃ of roastings one hour obtain comparative catalyst D2.Catalyzer needs to reduce half an hour under 500 ℃ of hydrogen before use.Relevant datas such as its composition, structure and catalytic activity see Table 4.
Comparative Examples 3
This example is the method preparation with reference to EP290100.
With the aluminium hydrate powder extrusion moulding that the refinery, Chang Ling produces, roasting is 3 hours under 1000 ℃ of air, can obtain alumina supporter; Get this carrier 40 grams and place container, adds 60 milliliters and contain the steeping fluid that nickel oxide is 0.233 grams per milliliter nickel ammonia solution, 50 ℃ were soaked 1.5 hours down, filtration, 120 ℃ of dryings 10 hours; Carry out second time dipping again, after the drying, 300 ℃ of roastings 5 hours; Flood for the third time again, after the drying,, can obtain comparative catalyst D3 through 320 ℃ of roastings 5 hours.Catalyzer needs to reduce half an hour under 500 ℃ of hydrogen before use.Relevant datas such as its composition, structure and catalytic activity see Table 4.
Example 4
This case introduction the structure of catalyzer and the sign and the evaluation method of catalytic activity.
The specific surface of catalyzer, pore volume are tested with the method for cryogenic nitrogen absorption.
804 types that U.S. CDS company produces little continuously anti--chromatogram arrangement on, with the catalytic activity of benzene hydrogenation evaluate catalysts.Reaction conditions is: 75 ℃ of temperature of reaction, and normal pressure, catalyzer 40～60 orders, loading amount 0.12 gram, with the quartz sand dilution of 6.0 one-sizes, the mixture of benzene with 10% and 90% normal hexane is per hour charging 13.1 grams of raw material; The reaction procatalyst reduced 4 hours with High Purity Hydrogen under 300 ℃.Reaction result sees Table 4.
From the result of table 4 as can be seen, with the catalyzer of method preparation provided by the invention, its catalytic activity all is better than the catalyzer with prior art for preparing.
Example 5
This case introduction the evaluation result of catalyzer under the different reduction temperatures.
Under different reductive conditions and the reaction conditions identical, carried out catalytically active assessment with catalyst A, the results are shown in Table 5 with example 4.
This shows that under reductive condition of the present invention, catalyzer has excellent catalytic activity.
Example 6
This case introduction the oil of catalyst A and catalyzer D1 comment the result.
On 300 milliliters of downflow system continuous fixed bed reactors, be raw material with the hydrocracking tail oil, under the katalysis of catalyst A and catalyzer D1, produce food-level white oil.Reaction conditions: 220～260 ℃ of temperature, pressure 13.5MPa, air speed (volume) 0.4～1.5 o'clock
-1, hydrogen/oil (volume) 300: 1; Catalyzer before reaction under 260 ℃ of hydrogen reductase 12 4 hours, evaluation result sees Table 6.
Used stock oil character: density is 859.0 kilograms/meter
3, 38.48 millimeters of kinematic viscosity (40 ℃)
2/ second, total aromatic hydrocarbons 5.36(is heavy) %, sulphur, nitrogen content are all less than 3ppm, and easily carbon compound and ultraviolet absorptivity are all defective.
The analysis of every The data or test method in the table: viscosity, GB256; Density GB2540-81; Easy carbon compound, SY2867; Ultraviolet absorptivity adopts Germany standards of pharmacopoeia DAB-8 method.
From the result of table 6 as can be seen: be raw material with the hydrocracking tail oil, producing in the process of food-level white oil that catalyzer of the present invention is compared with the comparative catalyst, has better catalytic performance.When reaching identical quality product, catalyzer comparison of the present invention can be high than the air speed of catalyzer more than 1 times and temperature of reaction can reduce by 20 ℃.
*-atmosphere is 1: the water vapor 1(volume) and air mixture.
Table 3
Table 4
Claims (6)
1, a kind of sulphur and nitrogen content of being applicable to is all less than aromatic hydrocarbons or the hydrogenation reaction of unsaturated hydrocarbon process of 10ppm, particularly after hydrofining or hydrocracking, obtain with lube cut, sulphur and nitrogen content all be not more than the industrial white oil of 6 (weight) % or unifining process that hydrocracking tail oil is raw material production food (medicine) grade white oil less than 10ppm, aromaticity content, by Ni 9.0～22.0 (weight) %, Mo 2.0～12.0 (weight) %, SiO
2The Preparation of catalysts method that the aluminum oxide (is benchmark with the catalyst weight) of 0～18 heavy % and surplus is formed is characterized in that:
(1) preparation of carrier: with the precursor powder of gama-alumina or the precursor powder and the silicon-containing compound mixing aftershaping of gama-alumina, under 550～750 ℃ of air, roasting 1～6 hour makes carrier;
(2) Preparation of catalysts:
1. the carrier that above-mentioned (1) is obtained, be immersed in the ammonia soln of the molybdate compound for preparing in advance, under the condition of room temperature～80 ℃, soaked 2～4 hours, filter, at 80～150 ℃ down after dry 2～16 hours, 200～600 ℃ of roastings are 2～8 hours under air and/or the water vapor, obtain containing the carrier of molybdenum;
2. the product that will 1. obtain again is immersed in the ammonia soln of the nickel compound containing for preparing in advance, soaks 1～6 hour under the condition of room temperature～60 ℃, filter, 80～150 ℃ dry 4～16 hours down;
3. repeat once operation 2. again;
4. the product that will 3. obtain, under 200～350 ℃ the condition, roasting can obtain described catalyzer in 4～8 hours under air.
2, in accordance with the method for claim 1, the precursor that it is characterized in that described gamma-alumina is amorphous hydroted alumina, false boehmite, book diaspore, gibbsite, surge aluminium stone or promise diaspore, preferably false boehmite or book diaspore.
3, in accordance with the method for claim 1, it is characterized in that described silicon-containing compound preferably dioxide-containing silica be that 80～90(is heavy) pure aluminium silicate microballoon powder or the dioxide-containing silica of % be the silicon sol of 20～30 heavy %.
4, in accordance with the method for claim 1, it is characterized in that the ammonia soln of described molybdate compound and the ammonia soln of nickel compound containing, is to adopt ordinary method to make, and wherein molybdate compound is molybdate or molybdic oxide, preferably ammonium molybdate; Nickel compound is nickelous carbonate or basic nickel carbonate.
5, in accordance with the method for claim 1, it is characterized in that the described molybdenum carrier maturing temperature that contains, preferably 450～550 ℃.
6, in accordance with the method for claim 1, it is characterized in that 1(2) preferably 240～280 ℃ of 4. described maturing temperatures, roasting time preferably 3～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108646 CN1030328C (en) | 1991-09-05 | 1991-09-05 | Method for preparing hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108646 CN1030328C (en) | 1991-09-05 | 1991-09-05 | Method for preparing hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070215A true CN1070215A (en) | 1993-03-24 |
| CN1030328C CN1030328C (en) | 1995-11-22 |
Family
ID=4909397
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108646 Expired - Fee Related CN1030328C (en) | 1991-09-05 | 1991-09-05 | Method for preparing hydrogenation catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047102C (en) * | 1994-06-04 | 1999-12-08 | 中国石油化工总公司 | Preparing method for hydrofinished catalyst |
| CN100444956C (en) * | 2002-12-06 | 2008-12-24 | 阿尔伯麦尔荷兰有限公司 | Heavy feed HPC process using a mixture of catalysts |
| CN104549290A (en) * | 2005-07-30 | 2015-04-29 | 赢创德固赛有限公司 | Process for the hydrogenation of oxo-aldehydes with a high ester content |
| CN105195231A (en) * | 2015-09-21 | 2015-12-30 | 中国海洋石油总公司 | Preparation method for after-treatment hydrocracking catalyst |
| CN106925277A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | The preparation method of refinery hydrogen preparing steam reforming catalysts |
| CN109266388A (en) * | 2018-10-30 | 2019-01-25 | 东营奥星石油化工有限公司 | A kind of white oil Hydrogenation production method based on composite catalyst |
-
1991
- 1991-09-05 CN CN 91108646 patent/CN1030328C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047102C (en) * | 1994-06-04 | 1999-12-08 | 中国石油化工总公司 | Preparing method for hydrofinished catalyst |
| CN100444956C (en) * | 2002-12-06 | 2008-12-24 | 阿尔伯麦尔荷兰有限公司 | Heavy feed HPC process using a mixture of catalysts |
| CN104549290A (en) * | 2005-07-30 | 2015-04-29 | 赢创德固赛有限公司 | Process for the hydrogenation of oxo-aldehydes with a high ester content |
| CN105195231A (en) * | 2015-09-21 | 2015-12-30 | 中国海洋石油总公司 | Preparation method for after-treatment hydrocracking catalyst |
| CN106925277A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | The preparation method of refinery hydrogen preparing steam reforming catalysts |
| CN109266388A (en) * | 2018-10-30 | 2019-01-25 | 东营奥星石油化工有限公司 | A kind of white oil Hydrogenation production method based on composite catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030328C (en) | 1995-11-22 |
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