CN1272399A - Hydrorefining catalyst and its preparation method - Google Patents
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Abstract
The present invention provides an amorphous alloy hydrofining catalyst and its preparation method. Said catalyst is formed from (wt%) 60-98% of Ni, 0-20% of Fe, 0-20% of one selected from Cr, Co, Mo, Mn and W and 0.5-30% of aluminium, in which the Fe content plus content of metal selected from Cr, Co, Mo, Mn and W is not zero at the same time, and a wide diffusion peak is produced only at 45 plus or minus 1 deg. in the range of that 2 theta is 20-80 deg. in X-ray diffraction pattern of said catalyst. Said invented catalyst can be used in hydrogenation process of unsaturated compounds of aromatic hydrocarbon, acetylenic hydrocarbon, olefine, nitro-compound, oxo-compound and nitriles, specially in hydrofining process of caprolactam.
Description
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method.
At chemical field especially field of fine chemical, there are many technical process need carry out hydrogenation reaction, the hydrogenation process of unsaturated compounds such as aromatic hydrocarbons, alkynes, alkene, nitro compound, carbonyls, nitrile for example, the hydrofinishing of many crude products such as caprolactam etc.; These hydrogenation process catalyst system therefors are generally skeleton nickel (Raney nickel) catalyst; This catalyst for many years in industrial use, technical maturity, for a long time never its alternative catalysts in industrial use.Recent years, its activity of so-called amorphous alloy catalyst and the selectivity of report all surpassed Raney nickel catalyst, and the gesture that replaces Raney nickel catalyst is arranged greatly.
Amorphous alloy is a class new catalytic material, its inner atom is a shortrange order, the long-range lack of alignment, this makes that its surface-active center number is more and even, but common amorphous alloy is very little because of specific surface, activity is lower, even after various chemistry and physical method processing, its specific surface also can't be above 10 meters
2/ gram, thus limited its prospects for commercial application.For this reason, CN1073726A adopt with aluminium in advance with Ni or Fe or Co-RE-P alloying, through fast quenching and moulding, remove wherein the method for aluminium with sodium hydroxide solution again and prepare a kind of big surface amorphous alloy, its specific surface can reach 50～130 meters
2/ gram, so huge surface area makes the practical application of this big surface amorphous alloy become possibility, for example when being used for the saturated hydrogenation reaction of alkene and aromatic hydrocarbons, its activity is apparently higher than Raney nickel catalyst (referring to CN1146443A).
CN1152475A discloses a kind of high-ferromagnetic non-crystalline alloy catalyst, and it consists of the nickel of 45～91 weight %, the iron of 2～40 weight % and the phosphorus of surplus.This catalyst has the catalytic activity higher than the CN1073726A catalyst.
USP3,839,011 discloses a kind of Raney nickel catalyst and preparation method thereof, this Preparation of catalysts method is the alloy of fusion to be put in the mobile water cool off, can obtain loose frangible catalyst, but adopt this method also to be not enough to obtain to have the amorphous alloy catalyst of stable amorphous structure.
USP5,090,997 disclose a kind of preparation method of Raney nickel catalyst, this method is that alloy with the fusion mixture of first water or water and gas under the temperature that is higher than 50～500 ℃ of fusing points atomizes, alloy water that will atomize then or air carry out the routine cooling, can obtain fine grain Raney nickel catalyst.The cooling velocity of the cooling means that this method adopted is lower, is difficult to form the high catalyst of non-crystallization degree.
Caprolactam is a primary raw material of producing nylon-6.Refining behind the caprolactam is the important step of producing caprolactam.The production of caprolactam comprises that prepared from benzene and hydrogen cyclohexane, cyclohexane oxidation preparing cyclohexanone, cyclohexanone oximate preparing cyclohexanone oxime, cyclohexanone oxime transposition generate technical process such as caprolactam, in product, except that caprolactam, also can generate some undersaturated accessory substances.The physico-chemical property of these unsaturated accessory substances and caprolactam are very approaching, are difficult to remove by extraction and still-process.And the existence of these impurity will influence the caprolactam polymerization process, be directly connected to the quality of nylon-6 product, therefore must remove.Refiningly behind the caprolactam make unsaturated impurity saturated by hydrogenation process with exactlying, its physical property and caprolactam are drawn back, so that by extracting and still-process is removed these impurity.All adopt Raney Ni catalyst in existing this back process for refining.From present industrial development level, Raney Ni catalyst activity is lower, large usage quantity, and the removal of impurity is limited in one's ability, and the finished product quality of caprolactam is lower, does not satisfy the needs of industrial development.
The purpose of this invention is to provide a kind of amorphous alloy Hydrobon Catalyst And Its Preparation Method, this amorphous alloy Hydrobon catalyst non-crystallization degree is higher and stable, and activity is higher, and removal of impurity ability is stronger, is specially adapted to the hydrofinishing of caprolactam.
Amorphous alloy Hydrobon catalyst provided by the present invention is basically by the Ni of 60～98 weight %, the Fe of 0～20 weight %, 0～20 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo, Mn and W, and the aluminium of 0.5～30 weight % forms, and wherein the amount of Fe and the amount that is selected from the metal in the group of being made up of Cr, Co, Mo, Mn and W are not 0 simultaneously; 2 θ only locate to occur a wide diffuse maximum at 45 ± 1 ° in 20～80 ° the scope in the X-ray diffractogram of this catalyst.
Catalyst provided by the present invention preferably consists of: the Ni of 70～95 weight %, and the Fe of 0.1～15 weight %, 0～15 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo, Mn and W and the aluminium of 1～15 weight %.
Catalyst provided by the present invention is preferred to consist of: the Ni of 75～90 weight %, and the Fe of 0.3～10 weight %, 0.5～8 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo, Mn and W and the aluminium of 2～10 weight %.
Catalyst provided by the present invention is preferably by will be by the nickel of 40 to 70 weight %, 30 to the aluminium less than 50 weight %, the iron of 0 to 15 weight %, with the fused mass of the alloy that Cr, Co, Mo, Mn or W formed of 0 to 15 weight % with greater than 1000 ℃/second, the cooling velocity that is preferably greater than 10000 ℃/second is solidified fast; Should quick-setting alloy at 300～900 ℃, preferred 450～750 ℃ of heat treatments 0.5～5 hour; Then the alloy after this heat treatment is handled to extract wherein most aluminium out with aqueous slkali and obtained.
Active component nickel in the catalyst provided by the present invention exists with the form of amorphous nickel basically.
Catalyst provided by the present invention prepares by following steps:
(1). the foundry alloy preparation
Will be by the nickel of 40 to 70 weight %, 30 to the aluminium less than 50 weight %, the fused mass of the alloy that Cr, Co, Mo or W formed of the iron of 0 to 15 weight % and 0 to 15 weight % is with greater than 1000 ℃/second, and the cooling velocity that is preferably greater than 10000 ℃/second is solidified fast;
(2). foundry alloy heat treatment
(1) resulting foundry alloy is heat-treated in the inert gas environment that is selected from hydrogen, argon gas or nitrogen, and heat treated condition is that temperature is 300-900 ℃, preferred 450-750 ℃; Heat treatment time is 0.5-5 hour, and the preferred time is 1-3 hour;
(3). activation (alkali treatment)
(2) resulting heat treated alloy is taken out aluminium with aqueous slkali handle, make the extraction and make the gained catalyst meet described composition of the presently claimed invention of most of aluminium in the alloy with the aqueous slkali reaction; Said aqueous slkali can be the solution of inorganic base or organic base, preferably the aqueous solution of alkali metal hydroxide, more preferably sodium hydrate aqueous solution; The temperature of alkali treatment is room temperature～120 ℃, is preferably 50～100 ℃; The alkali treatment time is 0.5～5 hour, is preferably 1～3 hour; The concentration and the consumption of aqueous slkali have no particular limits, can according to desired catalyst form and prior art in during the preparation Raney nickel catalyst employed alkali treatment condition determine; For example when using sodium hydrate aqueous solution, the concentration of sodium hydrate aqueous solution can be 10～40 weight %, and its consumption can be foundry alloy: NaOH=1: (0.5～4) (weight ratio);
(4). washing
With (3) resulting sample temperature is room temperature～100 ℃, preferred 60～100 ℃ water washing, and the pH of washing back solution is preferably 7～13; Washing back sample can be kept in the water, also can be kept in the ethanol, is preferably under the condition of controlled atmosphere to preserve.
Catalyst provided by the invention can be used for the hydrogenation process of unsaturated compounds such as aromatic hydrocarbons, alkynes, alkene, nitro compound, carbonyls, nitrile, is particularly suitable for the unifining process of caprolactam.
Fig. 1 and Fig. 2, Fig. 3, Fig. 4 are catalyst of the present invention and comparative catalyst's X-ray diffractogram (seeing embodiment 11).
Catalyst provided by the invention is compared active obviously improve (the seeing embodiment 9) of its hydrofinishing with traditional Raney nickel catalyst, and not through heat treated amorphous alloy catalyst specific activity and stability all be significantly improved (seeing embodiment 10 and 11) mutually.
The following examples will the present invention is described further, but can not be interpreted as limitation of the invention.
Present embodiment explanation Ni-Fe-Mo-Al Preparation of catalysts.
49 gram nickel, 49 gram aluminium, 1 gram iron, 1 gram molybdenum are joined in the quartz ampoule, it is heated to fusion more than 1300 ℃ in coreless induction furnace, make its alloying, with indifferent gas this alloy liquid being sprayed onto a rotating speed from the nozzle under the quartz ampoule then is on 800 rev/mins the copper roller, logical cooling water in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is below 70 microns through being ground to particle diameter, obtains foundry alloy.Foundry alloy is heat-treated in hydrogen environment, and heat treated temperature is 600 ℃, and constant temperature time is 3 hours.Foundry alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20 weight % sodium hydrate aqueous solutions, controls its temperature and is 90 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, with 80 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered catalyst-1, is kept in the water it standby.
Embodiment 2-8
Step according to embodiment 1 prepares catalyst of the present invention, just proportioning, preparation condition such as the heat treatment temperature of catalyst and time, the temperature and time of alkali treatment (taking out aluminium), the temperature of washings etc. are different, and the preparation condition of each embodiment is listed in the table 1.The prepared catalyst of each embodiment is numbered catalyst-2 respectively to catalyst-8.
Each Preparation of catalysts condition of table 1.
| Foundry alloy is formed | Heat treatment | Take out the aluminium activation | Washing | |||||
| Temperature (℃) | Time (hour) | Foundry alloy/alkali (weight ratio) | Activation temperature (℃) | Time (hour) | Temperature of washing water (℃) | Washing back | ||
| Embodiment | ||||||||
| 2 | ?Ni 48Fe 1.5Cr 2.5Al 48 | ?600 | ????3 | ????1∶1 | ????100 | ????1 | ????80 | ????7 |
| | ?Ni 50Fe 5.5Cr 2.5Al 42 | ?600 | ????3 | ????1∶1 | ????100 | ????1 | ????80 | ????7 |
| Embodiment 4 | ?Ni 48Fe 1.5Mo 2.5Al 48 | ?600 | ????3 | ????1∶2 | ????50 | ????1 | ????80 | ????7 |
| Embodiment 5 | ?Ni 60Fe 2Cr 1Al 37 | ?700 | ????2 | ????1∶2 | ????100 | ????1.5 | ????100 | ????7 |
| Embodiment 6 | ?Ni 48Fe 2.5Mo 1.5Al 48 | ?700 | ????2 | ????1∶2 | ????100 | ????1.5 | ????100 | ????7 |
| Embodiment 7 | ?Ni 52Fe 2Al 46 | ?600 | ????3 | ????1∶2 | ????90 | ????1 | ????100 | ????7 |
| Embodiment 8 | ?Ni 52Cr 2Al 46 | ?600 | ????3 | ????1∶2 | ????90 | ????1 | ????100 | ????7 |
Comparative Examples 1-4
Comparative Examples 1 provides a kind of Raney nickel catalyst (contrast medium-1), and this catalyst is sold by the catalyst plant production of Yangzhou, Jiangsu Province, is kept at the pH value and is in 13 the buck.
Comparative Examples 2 provides a kind of Raney nickel catalyst (contrast medium-2), and this catalyst is by U.S. ActivatedMetals ﹠amp; Chemicals company produces, and is kept at the pH value and is in 12 the buck.
Comparative Examples 3 provides a kind of heat treated catalyst (contrast medium-3) that do not pass through, the preparation method of the catalyst-2 among this Preparation of catalysts method and the embodiment 2 is identical, and different is after preparing foundry alloy without the heat treatment of hydrogen atmosphere and directly carry out the alkali treatment of back.
Comparative Examples 4 provides a kind of heat treated catalyst (contrast medium-4) that do not pass through, the preparation method of the catalyst-4 among this Preparation of catalysts method and the embodiment 2 is identical, and different is after preparing foundry alloy without the heat treatment of hydrogen atmosphere and directly carry out the alkali treatment of back.
Embodiment 9
Present embodiment illustrates catalyst provided by the invention and comparative catalyst's hexanolactam hydrofining activity.
At capacity is to add 1500 lactam aqueous solutions of restraining oneself in 2000 milliliters the there-necked flask (to contain caprolactam 30 weight %, the PM value is 120 seconds, together following) and 1 gram catalyst provided by the invention, under normal pressure, feed hydrogen (hydrogen flowing quantity is 50 liters/hour), by heating jacket heating and insulation at 90 ℃, after stirring 30 minutes (rotating speed is 540 rev/mins), take out reacted supernatant liquid and measure its PM value.
The PM value is usually used in characterizing the content of unsaturated materials in the product, generally is used to contain the more but sign of the product that content is less of unsaturated materials kind.The method of measuring the PM value of caprolactam is: the 6.0 lactams samples of restraining oneself are water-soluble, be transferred in 200 milliliters of volumetric flasks, and add water to scale, mixing gets caprolactam solution; Get 100 milliliters of colorimetric cylinders that 10 these solution of gram inject a drying, add deionized water to scale; This colorimetric cylinder and standard colorimetric tube are put on the colorimetric shelf in the water bath with thermostatic control, close the lid, when treating that solution temperature reaches 20 ℃, in solution to be measured, add 1.00 milliliters of liquor potassic permanganates (concentration is 0.002M), start stopwatch immediately, note the time of being experienced when solution colour is identical with reference colour in the colorimetric cylinder (second), this value is exactly the PM value.
The compound method of standard color solution is: with 3000 milligrams of pure Co (NO of top grade
3)
26H
2O and 12 milligrams of pure K of top grade
2Cr
2O
7Water-soluble, be diluted to 1 liter, mixing.
The assay method of PM value can be with reference to " caprolactam production and application " (" caprolactam production and application " writes group, Beijing: hydrocarbon processing publishing house, publication in 1988).
Table 2 has been listed the comparative catalyst's that catalyst that embodiment of the invention 1-8 provides and Comparative Examples 1-2 provide composition and hexanolactam hydrofining activity thereof.Catalyst of the present invention as can be seen has the hydrofinishing activity more much higher than Raney nickel catalyst.
Table 2 catalyst of the present invention is used for the effect of hexanolactam hydrofining process
| The catalyst numbering | Catalyst is formed | PM value behind the hydrogenation |
| Catalyst-1 | ????Ni 79Fe 2Mo 1.8Al 17.2 | ????800 |
| Catalyst-2 | ????Ni 87Fe 2Cr 3Al 8 | ????1590 |
| Catalyst-3 | ????Ni 80.5Fe 8Cr 3.5Al 8 | ????802 |
| Catalyst-4 | ????Ni 82Fe 5Mo 3.5Al 9.5 | ????800 |
| Catalyst-5 | ????Ni 88Fe 3.5Cr 1.5Al 7 | ????1060 |
| Catalyst-6 | ????Ni 85Fe 3.5Mo 1.5Al 10 | ????1246 |
| Catalyst-7 | ????Ni 88Fe 3Al 9 | ????786 |
| Catalyst-8 | ????Ni 88Cr 3Al 9 | ????872 |
| Contrast medium-1 | Raney nickel | ????310 |
| Contrast medium-2 | Raney nickel | ????618 |
Embodiment 10
Present embodiment explanation heat treatment is to the influence of catalyst hydrogenation activity of the present invention.
Comparative Examples 3 and 4 gained contrast medium-3 and contrast medium-4 catalyst are carried out hexanolactam hydrofining by the method for embodiment 9, the results are shown in Table 3 for gained, and the foundry alloy of forming for difference all can make after by heat treatment activity of such catalysts obtain in various degree raising as can be seen.
Table 3 heat treatment is to the influence of catalyst hydrogenation activity
| The catalyst numbering | Foundry alloy is formed | Processing mode | Catalyst is formed | The PM value |
| Catalyst-2 | ?Ni 48Fe 1.5Cr 2.5Al 48 | Heat treatment | ?Ni 87Fe 2Cr 3Al 8 | ??1590 |
| Contrast medium-3 | Not heat treatment | ??830 | ||
| Catalyst-4 | ?Ni 48Fe 1.5Mo 2.5Al 48 | Heat treatment | ?Ni 82Fe 5Mo 3.5Al 9.5 | ??800 |
| Contrast medium-4 | Not heat treatment | ??728 |
Embodiment 11
Present embodiment explanation catalyst of the present invention and comparative catalyst's X-ray diffraction performance (the crystalline state degree of catalyst), and heat treatment is to the influence of catalyst stability of the present invention.
Fig. 1 has described the X-ray diffractogram of catalyst-2, contrast medium-1 and contrast medium-2, and wherein 1 is that catalyst-2,2 is that contrast medium-1,3 is a contrast medium-2.
Fig. 2 has described in catalyst-2 preparation process different X-ray diffractograms that the aluminium time sampling records of taking out.
Fig. 3 has described in contrast medium-3 preparation process different X-ray diffractograms that the aluminium time sampling records of taking out.
Fig. 4 has described the X-ray diffractogram that catalyst-2 and contrast medium-3 record after placing two months after the preparation, wherein 1 is that catalyst-2,2 is a contrast medium-3.
Only about 45 °, locate to occur a mild wide diffraction maximum in its X-ray diffractogram of catalyst of the present invention as can be seen from Figure 1, show the basic amorphous structure that is; And Raney nickel catalyst (contrast medium-2) locates to occur sharp-pointed diffraction maximum at about 45 °, 52 °, 76 ° respectively, is indicated as crystalline structure.
As can be seen from Figures 2 and 3, catalyst of the present invention is because through Overheating Treatment, the non-crystallization degree of catalyst is higher.
As can be seen from Figure 4, catalyst of the present invention is owing to through Overheating Treatment, still be amorphous structure (wide diffuse scattering peak) after placing two months, and catalyst structure is more stable; And through heat treated contrast medium-3 sharp-pointed diffraction maximum does not appear after placing two months, show obviously crystalline stateization.
Claims (12)
1, a kind of amorphous alloy Hydrobon catalyst, this catalyst is by the Ni of 60～98 weight %, the Fe of 0～20 weight %, 0～20 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo, Mn and W, and the aluminium of 0.5～30 weight % forms, and wherein the amount of Fe and the amount that is selected from the metal in the group of being made up of Cr, Co, Mo, Mn and W are not 0 simultaneously; 2 θ only locate to occur a wide diffuse maximum at 45 ± 1 ° in 20～80 ° the scope in the X-ray diffractogram of this catalyst.
2, according to the catalyst of claim 1, this catalyst is by will be by the nickel of 40 to 70 weight %, 30 to the aluminium less than 50 weight %, the iron of 0 to 15 weight %, solidify fast with cooling velocity with the fused mass of the alloy that Cr, Co, Mo, Mn or W formed of 0 to 15 weight % greater than 1000 ℃/second, should quick-setting alloy 300～900 ℃ of heat treatments 0.5～5 hour, the alloy after this heat treatment is handled to extract wherein most aluminium out obtaining then with aqueous slkali.
3, according to the catalyst of claim 2, cooling velocity wherein is greater than 10000 ℃/second.
4, according to the catalyst of claim 2, heat treatment temperature wherein is 450～750 ℃, and the time is 0.5～5 hour.
5, according to the catalyst of claim 1, the consisting of of this catalyst: the Ni of 70～95 weight %, the Fe of 0.1～15 weight %, 0～15 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo and W and the aluminium of 1～15 weight %.
6, according to the catalyst of claim 5, the consisting of of this catalyst: the Ni of 75～90 weight %, the Fe of 0.3～10 weight %, 0.5～8 weight % is selected from a kind of metal in the group of being made up of Cr, Co, Mo, Mn and W and the aluminium of 2～10 weight %.
7, according to the catalyst of claim 1, active component nickel wherein exists with the form of amorphous nickel basically.
8, the described Preparation of catalysts method of claim 1, this method is made up of following step basically:
(1). will be by the nickel of 40 to 70 weight %, 30 to the aluminium less than 50 weight %, and the fused mass of the alloy that Cr, Co, Mo, Mn or W formed of the iron of 0 to 15 weight % and 0 to 15 weight % solidifies fast with the cooling velocity greater than 1000 ℃/second;
(2). (1) resulting quick-setting alloy is heat-treated in a kind of inert gas environment, and heat treated condition is that temperature is 300～900 ℃, and the time is 0.5～5 hour;
(3). (2) resulting heat treated alloy is taken out aluminium with aqueous slkali handle, make the extraction and make the gained catalyst meet the described composition of claim 1 of most of aluminium in the alloy with the aqueous slkali reaction;
(4). with the alloy temperature after (3) resulting alkali treatment is 20～100 ℃ water washing, and the pH of washing back solution is 7～13.
9, according to the preparation method of claim 8, wherein the said heat treated condition of step (2) is that temperature is 450～750 ℃, and the time is 1～3 hour.
10, according to the preparation method of claim 8, wherein the said aqueous slkali of step (3) is the aqueous solution of NaOH, and wherein its alkali purification temp is room temperature～120 ℃, and the alkali treatment time is 0.5～5 hour.
11, according to the preparation method of claim 10, wherein its alkali purification temp is 50～100 ℃.
12, according to the preparation method of claim 8, wherein the temperature of the said washings of step (4) is 60～100 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7230145B2 (en) | 2001-03-22 | 2007-06-12 | Showa Denko K.K. | Catalyst for producing both end-hydroxyl group-terminated diols, process for producing the catalyst, process for producing the diols by using the catalyst, and both end-hydroxyl group-terminated diols obtained by the process |
| CN101274895B (en) * | 2007-03-30 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrogenation reduction method for aromatic nitro compound |
| CN102050742B (en) * | 2009-10-27 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethylamino propylamine through hydrogenating dimethylamino propionitrile in presence of nickel |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4001484A1 (en) * | 1990-01-19 | 1991-08-01 | Bayer Ag | METHOD FOR PRODUCING POWDER-FORMAL ALUMINUM ALLOYS |
| CN1047375C (en) * | 1995-09-26 | 1999-12-15 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenation method for olefines or aromatic hydrocarbon |
| CN1052668C (en) * | 1995-12-20 | 2000-05-24 | 中国石油化工总公司石油化工科学研究院 | High-ferromagnetic non-crystalline alloy catalyst |
-
2000
- 2000-04-18 CN CN00105686A patent/CN1093003C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7230145B2 (en) | 2001-03-22 | 2007-06-12 | Showa Denko K.K. | Catalyst for producing both end-hydroxyl group-terminated diols, process for producing the catalyst, process for producing the diols by using the catalyst, and both end-hydroxyl group-terminated diols obtained by the process |
| CN101274895B (en) * | 2007-03-30 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrogenation reduction method for aromatic nitro compound |
| CN102050742B (en) * | 2009-10-27 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethylamino propylamine through hydrogenating dimethylamino propionitrile in presence of nickel |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
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| CN1093003C (en) | 2002-10-23 |
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| CX01 | Expiry of patent term |
Granted publication date: 20021023 |