CN1344585A - Noble metal catalyst method of resisting CO poisoning - Google Patents
Noble metal catalyst method of resisting CO poisoning Download PDFInfo
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- CN1344585A CN1344585A CN 00124906 CN00124906A CN1344585A CN 1344585 A CN1344585 A CN 1344585A CN 00124906 CN00124906 CN 00124906 CN 00124906 A CN00124906 A CN 00124906A CN 1344585 A CN1344585 A CN 1344585A
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Abstract
The present invention provides one method of raising and stabilizing the activity of noble metal catalyst. It is featured by that cocatalyst containing Ni is added into hydroreaction system with Pt, Pd, Ru and/or Rh noble metal catalyst and producing toxic CO matter. The said cocatalysts are amorphous alloy catalyst with Ni as main active component, loaded Ni-containing amorphous alloy catalyst, raneys nickel catalyst or loaded Ni catalyst with Ni as main active component. The ration between addition amount of the cocatalyst and the noble metal is 0.01-50.
Description
The present invention relates to a kind ofly reduce carbon monoxide that reaction produced facing of noble metal catalyst in the H-H reaction to the poisoning of this noble metal catalyst using, thereby improve and the method for stabilizing catalyst activity; Particularly relate to producing the H-H reaction of facing of carbon monoxide accessory substance, as the hydrogenation reaction of benzoic acid or substituted benzoic acid, in the terephthalic acid (TPA) hydrofining reaction, the method for the activity of such catalysts of raising and stable platiniferous, palladium, ruthenium and/or rhodium.
As good hydrogenation catalyst, noble metal catalyst is widely used in the numerous areas of industries such as petrochemical industry, pharmacy, fine chemistry industry.From alkynes, alkene to saturated hydrocarbons, benzene, substituted benzene are to cycloalkane, the aromatic heterocycle derivative is in the reaction of Hete rocyclic derivatives etc., especially in chemical fibre industry in the SNIA technology, the purification of terephthalic acid technology in the polyester industrial, pharmaceuticals industry of preparation caprolactam in the hydrogenation reaction of cumfrey, noble metal catalyst has very big consumption.Noble metal catalyst commonly used has Pt/C, Pt/ silica gel, PtO
2, Pd/C, Pd/ diatomite, PdO
2, Ru/C, RuO
2, Rh/C, Ru-Pd/C etc.
In the catalytic reaction of the compound that contains carboxyl, since the decarboxylation side reaction tend to produce CO, be noble metal catalyst if react employed, then the CO of Chan Shenging can be adsorbed on the surface of noble metal catalyst by force, cause catalyst poisoning, reduce activity of such catalysts.
For example, the toluene method of SNIA company prepares in the process route of caprolactam (SNIA technology), and benzoic acid hydrogenation is the important step of preparation caprolactam technology.The SNIA technology of producing caprolactam comprises that mainly toluene oxidation system benzoic acid, benzoic acid hydrogenation prepare cyclohexane-carboxylic acid, cyclohexane-carboxylic acid and make processes such as caprolactam through amidatioon.What wherein the benzoic acid hydrogenation process was used is precious metals pd/C catalyst.The primary product of Pd/C catalysis benzoic acid hydrogenation reaction is cyclohexane-carboxylic acid (CCA), and side reaction is mainly hydrogenation of carboxylic acids and generates corresponding alcohol, and the CCA decarboxylation generates CO
2And CO.CO is adsorbed on the surface of Pd by force, causes the Pd/C catalyst poisoning, reduces activity of such catalysts.Active production and the benefit of giving on the low side of recycling catalyst brought two direct consequences, and the one, produce load and can not improve; The 2nd, sharply increase fresh catalyst quantity delivered and palladium and reclaim frequency, thereby strengthened the possibility of precious metals pd loss.(Z is for estimating the value of Pd/C catalyst activity at Z=1.0-1.2 for common fresh Pd/C (5% load capacity) catalyst activity, the hydrogen-absorption speed of representation unit time catalyst) between, and the active Z of Pd/C fluctuates about 0.2 in the actual production, far below fresh Pd/C activity of such catalysts, keep catalyst activity levels, must regularly add fresh catalyst to hydrogenation system.So the performance of benzoic acid hydrogenation Pd/C catalyst is the key of restriction benzoic acid hydrogenation technical development and SNIA technological development, also is the bottleneck problem in the caprolactam manufacturing process always.
Again for example, from cumfrey with to the normal PtO that adopts the technology of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid
2, noble metal catalyst such as Pd/C, similarly, owing to the CO that side reaction produced can make catalyst poisoning that life of catalyst is shortened.Prolong the service life of expensive noble metal catalyst so take some countermeasures, important and practical meanings is arranged.
The purpose of this invention is to provide a kind of the reduction in the H-H reaction and react carbon monoxide the poisoning that is produced this noble metal catalyst in facing of use noble metal catalyst, thereby the method for raising and stabilizing catalyst activity, this method can make reaction system have the composition of intoxication to reduce to noble metal, this activity of such catalysts is improved a lot, and have good stable.
The method of raising provided by the present invention and stable noble metal catalyst activity is characterized in that: using noble metal catalyst and can produce the nickeliferous catalyst promoter of adding in the H-H reaction system that faces of carbon monoxide poisonous substance; Wherein said nickeliferous catalyst promoter wherein preferably is amorphous alloy catalyst, Raney's nickel catalyst or the methanation catalyst of main active component with nickel for being the amorphous alloy catalyst of main active component, nickeliferous carried non-crystal alloy catalyst, Raney's nickel catalyst with nickel or being nickel catalyst carried (as the methanation catalyst) etc. of main active component with nickel; The addition of said auxiliary agent is Ni/ noble metal=0.01-50, preferred 0.1-10 (weight ratio).
The said use noble metal catalyst and the example that faces H-H reaction that can produce the carbon monoxide poisonous substance have the hydrogenation reaction of benzoic acid or substituted benzoic acid in the method provided by the invention, the terephthalic acid (TPA) hydrofining reaction, the hydrogenation reaction of aliphatic unsaturated carboxylic acid or its ester etc.The hydrogenation reaction of wherein said substituted benzoic acid comprises the benzoic hydrogenation reaction that the C1-C5 alkyl replaces, for example from cumfrey with to the reaction of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid.The reaction condition of these reactions determines that according to prior art the present invention has no particular limits it according to concrete reaction and employed catalyst.
Said noble metal catalyst is a corresponding catalyst used in the said reaction in the method provided by the invention, and the present invention has no particular limits it.These catalyst comprise the catalyst of platiniferous, palladium, ruthenium and/or rhodium, and concrete example has Pt/C, Pt/ silica gel, PtO
2, Pd/C, Pd/ diatomite, PdO
2, Ru/C, RuO
2, Rh/C, Ru-Pd/C etc.
Said in the method for raising provided by the present invention and stable noble metal catalyst activity is to be 45 ± 1 ° at 2 θ in its X-ray diffractogram of amorphous alloy catalyst of main active component to locate to occur a diffuse maximum (steamed bun shape diffuse scattering peak) with nickel, and the Al of the Ni that consists of 10-95 weight % of this catalyst, 20-80 weight %, the Fe of 0-25 weight % and 0-10 weight % are selected from one or more elements in the group of being made up of P, Co, Cr, Mn, W and Mo.The CN1073726A that the applicant proposes, CN1152475A, CN1234294A and application number are in the Chinese patent application of 00105686.7 (is basis for priority with 99106166.7) these amorphous alloy catalysts to be had detailed description, incorporate these documents into the present invention as a reference at this.
Said nickeliferous carried non-crystal alloy catalyst is that nickel and boron, nickel and phosphorus, nickel-other metal component-boron, nickel-other metal component-phosphorus even load are at SiO in the method for raising provided by the present invention and stable noble metal catalyst activity
2, active carbon, Al
2O
3Deng the carried non-crystal alloy catalyst that obtains on the porous carrier.Among CN1179358A, CN1196975A and the CN1200955A these carried non-crystal alloy catalysts there is detailed description, incorporates these documents into the present invention as a reference at this.
Said Raney's nickel catalyst is the Raney's nickel catalyst that the at present industrial employing tradition melting technique that generally uses is produced in the method for raising provided by the present invention and stable noble metal catalyst activity, and the present invention has no particular limits it.
In the method for raising provided by the present invention and stable noble metal catalyst activity said nickel catalyst carried be the at present industrial Ni-based methanation catalyst that generally uses, the present invention has no particular limits it.
The operating process of the method for raising provided by the present invention and stable noble metal catalyst activity can be that the nickeliferous auxiliary agent that will add joins in the reactor after at first mixing with noble metal catalyst again, also can directly join in the reactor separately.
Method provided by the invention is compared with the existing method that does not add nickeliferous auxiliary agent and since the CO that reaction produces absorbed by nickeliferous auxiliary agent or transform (as CO in the presence of nickeliferous auxiliary agent with H
2Reaction changes into methane), reduced the poisoning of noble metal catalyst, catalyst activity obviously improves, thereby has higher reaction processing capacity and production efficiency, operational stability also improves greatly, and owing to reduced the additional speed of fresh noble metal catalyst, thereby reduced the recovery frequency of noble metal, reduced the possibility of precious metal losses; Because the CO of system amount reduces, also reduced the load of the transformation absorption that needs for processing CO simultaneously.In a word, adopt method provided by the invention that operability is greatly improved, cost obviously reduces.
The following examples will be described further method provided by the invention.
Embodiment 1
The preparation of a kind of amorphous alloy nickel auxiliary agent that present embodiment explanation the present invention is used.
48 gram nickel, 48 gram aluminium, 1.5 gram iron, 2.5 gram chromium 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 100 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 500 grams, 20% sodium hydrate aqueous solution, controls its temperature and is 100 ℃ 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 ZA-1, is kept in the water it standby.
Embodiment 2
The preparation of a kind of amorphous alloy nickel auxiliary agent that present embodiment explanation the present invention is used.
48 gram nickel, 52 gram aluminium 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 100 microns through being ground to particle diameter, obtains foundry alloy.Foundry alloy is heat-treated in hydrogen environment, and heat treated temperature is 700 ℃, and constant temperature time is 2 hours.Foundry alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% sodium hydrate aqueous solution, controls its temperature and is 100 ℃ and constant temperature and stirred 1.5 hours.After stopping heating and stirring, decantation liquid, with 100 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered ZA-2, is kept in the water it standby.
Embodiment 3
The preparation of a kind of carried non-crystal nickel alloy auxiliary agent that present embodiment explanation the present invention is used.
Take by weighing the 10g wood activated charcoal, in 120 ℃ of oven dry.Take by weighing 2.0g four water acetic acid nickel and 12mL deionized water and be made into nickeliferous solution, the Immesion active carbon carrier, 120 ℃ of dryings obtain nickeliferous carrier.Take by weighing 2.06gKBH again
4, add the 25mL deionized water and be made into the aqueous solution, at room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, spends solid product that deionised water obtains to there not being acid group, uses absolute ethanol washing again, and the catalyst that makes is numbered ZA-3.Nickel content 4.4 (weight) %, boron content 0.27 (weight) %.
Embodiment 4
The used a kind of co-catalyst of present embodiment explanation the present invention, this co-catalyst are the conventional Raney's nickel catalyst that uses in the prior art, and nickeliferous 88wt%, aluminium 12wt% are designated as ZA-4.
Embodiment 5-8
These embodiment illustrate nickel auxiliary agent that embodiment of the invention 1-4 the provides activation situation to the Pd/C catalyst.The activation situation characterizes (representing with Z) by estimating the hydrogenation effect that adds auxiliary agent front and back Pd/C catalyst.Used Pd/C catalyst is the recycling catalyst sample of taking from the Shijiazhuang chemical fibre Co., Ltd caprolactam production apparatus benzoic acid hydrogenation production line (down together).
The Z value is that the Pd/C activity of such catalysts characterizes the hydrogen-absorption speed of representation unit time catalyst.Usually the depletion rate according to beginning hydrogen calculates.The method of measuring the Z value is: get Pd/C catalyst 2g, add (or not adding) contain that the Ni auxiliary agent mixes and the autoclave of packing in, add the 200g benzoic acid again, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 20 atm, replace 3-4 time with High Purity Hydrogen during to 150 ℃, fill hydrogen to 110atm, start stirring and pick up counting simultaneously, when the still internal pressure is reduced to 90atm, immediate record reaction time and reaction temperature, and rapidly pressure is brought up to 110atm, according to identical method, repeat multi-pass operation as requested, and continue record each reaction time (reducing to 90atm) from 110atm, catalyst sample is finished circular response usually 7 times, utilizes γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, is abscissa with time, γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z=γ
0/ 4.
The assay method of Z value can be with reference to " caprolactam device analysis method compilation " (chemical fibre Co., Ltd in Shijiazhuang writes).
Table 1 has been listed the Pd/C catalyst activity that adds behind the catalyst promoter that embodiment of the invention 1-4 provides.
Comparative Examples 1
The explanation of this Comparative Examples does not add the Pd/C activity of such catalysts situation when containing the Ni auxiliary agent.
Method according to embodiment 5-8 is estimated the Pd/C activity of such catalysts, and different is not add the amorphous alloy auxiliary agent that contains Ni, and the results are shown in Table 1 for gained.
Table 1.
Nickel promoter addition numbering auxiliary agent auxiliary agent is formed
The active Z of Pd/C
(accounting for Pd weight) embodiment 5 ZA-1 Ni
88Al
9Fe
1Cr
20.5 0.50 embodiment, 6 ZA-2 Ni
88Al
120.5 0.47 embodiment, 7 ZA-3 Ni
75B
25/ C 0.5 0.31 embodiment 8 ZA-4 Ni
88Al
120.5 0.41 Comparative Examples 10 0.16
Embodiment 9-15
These embodiment illustrate influence and the implementation result of promoter addition to the Pd/C activity.When not adding the amorphous alloy auxiliary agent, reaction system Pd/C catalyst concn is 1%, the activity of recycling catalyst is Z=0.16, and after progressively adding the amorphous alloy auxiliary agent that contains Ni according to method of the present invention, the Pd/C activity of such catalysts steadily improves (its result is as shown in table 2).When the Pd/C of system amount is 0.5%, add 1.2 times of nickel auxiliary agents, can make the Pd/C activity reach 1% level; And when adding 2 times of nickel auxiliary agents, the Pd/C activity can improve greatly.
Comparative Examples 2
The explanation of this Comparative Examples does not add the Pd/C activity of such catalysts situation when containing the Ni auxiliary agent.
Method according to embodiment 9-15 is estimated the Pd/C activity of such catalysts, and different is not add the amorphous alloy auxiliary agent that contains Ni, and the results are shown in Table 2 for gained.
Table 2.
Pd/C catalyst concn nickel promoter addition numbering auxiliary agent
The active Z of Pd/C
% (accounting for Pd weight) embodiment 9 ZA-1 1.0 0.15 0.32 embodiment 10 ZA-1 1.0 0.20 0.37 embodiment 11 ZA-1 1.0 0.40 0.41 embodiment 12 ZA-1 1.0 0.50 0.50 embodiment 13 ZA-1 1.0 0.60 0.60 embodiment 14 ZA-1 0.5 24 0.20 embodiment 15 ZA-1 0.5 40 0.30 Comparative Examples 2 0.5 0.08
Embodiment 16-19
These embodiment illustrate the implementation result of the present invention in once secret commerical test.
The method of mentioning among Pd/C catalyst activity evaluation method and the embodiment 5-8 is consistent.The benzoic acid hydrogenation condition is on the commercial plant: 170 ℃ of reaction temperatures, Hydrogen Vapor Pressure 1.35Mpa (gauge pressure).When not adding the amorphous alloy auxiliary agent, the active Z=0.16 of recycling catalyst generates gas CO, CO
2, CH
4Total amount is 300ppm, and the magnitude of recruitment of fresh Pd/C catalyst is double centner/sky (kg/d), and the device load is 5-6 ton/hour (t/h); After progressively adding the amorphous alloy auxiliary agent that contains Ni according to method of the present invention, the Pd/C activity of such catalysts steadily improves (its result is as shown in table 3), under the situation that adds 1.2% nickel auxiliary agent, the magnitude of recruitment of fresh Pd/C catalyst is reduced to 75kg/d, the device load increases to 9t/h, CO, CO in the tail gas of reaction back
2, CH
4Amount reduces greatly, and CCA purity improves, H
2Utilization rate improves.
Active Z CO, the CO of table 3. numbering auxiliary agent nickel promoter addition Pd/C
2, device load
(accounting for Pd/ weight) CH
4Amount t/h embodiment 16 ZA-1 0.04 0.23 250 6.5 embodiment 17 ZA-1 0.1 0.25 220 7-8 embodiment 18 ZA-1 0.16 0.28 190 8-8.5 embodiment 19 ZA-1 0.24 0.30 170 8.5-9
Embodiment 20-24
These embodiment illustrate that nickel auxiliary agent that embodiment of the invention 1-4 provides is to PtO
2The activation situation of catalyst.The activation situation adds auxiliary agent front and back PtO by estimating in the isopropyl acid hydrogenation reaction
2The hydrogenation effect of catalyst characterizes (with Z
1Expression).
The Z1 value is PtO
2Activity of such catalysts characterizes, the hydrogen-absorption speed of representation unit time catalyst.Measure Z
1The method of value is: get PtO
2Catalyst is (according to " catalyst handbook (volume such as rugged collection of tail, Chemical Industry Press, nineteen eighty-two publishes, the 702nd page) preparation) 0.5g, add (or not adding) contain that the Ni auxiliary agent mixes and the autoclave of packing in, add the 200g isopropyl acid again, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 20 atm, with High Purity Hydrogen displacement 3-4 time, fill hydrogen during to 150 ℃ to 110atm, start to stir and pick up counting simultaneously, when the still internal pressure is reduced to 90atm, immediate record reaction time and reaction temperature, and rapidly pressure is brought up to 110atm, according to identical method, repeat multi-pass operation as requested, and continue record each reaction time (reducing to 90atm from 110atm), catalyst sample is finished circular response usually 7 times, utilize γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, with time is abscissa, and γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z=γ
0/ 4.
Table 4 has been listed the PtO that adds behind the catalyst promoter that embodiment of the invention 1-4 provides
2Catalyst activity.
Comparative Examples 3
The explanation of this Comparative Examples does not add the PtO when containing the Ni auxiliary agent
2The activity of such catalysts situation.
According to the method for embodiment 20-24 to PtO
2Activity of such catalysts is estimated, and different is not add the amorphous alloy auxiliary agent that contains Ni, and the results are shown in Table 4 for gained.
Table 4.
PtO
2Catalyst concn nickel promoter addition numbering auxiliary agent
PtO
2Active Z
1
% (accounts for PtO
2Weight) embodiment 20 ZA-1 0.25 0.2 0.35 embodiment 21 ZA-2 0.25 0.2 0.31 embodiment 22 ZA-3 0.25 0.2 0.28 embodiment 23 ZA-4 0.25 0.2 0.30 embodiment 24 ZA-1 0.25 0.5 0.40 Comparative Examples 30 0.20
Embodiment 25-28
These embodiment illustrate nickel auxiliary agent that embodiment of the invention 1-4 the provides activation situation to the Ru/C catalyst.The activation situation characterizes (with Z by estimating the hydrogenation effect that adds auxiliary agent front and back Ru/C catalyst in to the ethyl benzoate hydrogenation reaction
2Expression), Ru content is 5 (weight) % in the Ru/C catalyst.
Z
2Value is that the Ru/C activity of such catalysts characterizes the hydrogen-absorption speed of representation unit time catalyst.Measure Z
2The method of value is: get the Ru/C catalyst (according to " catalyst handbook (volume such as rugged collection of tail, Chemical Industry Press, nineteen eighty-two publishes, the 689th page) preparation) 2.0g, add (or not adding) contain that the Ni auxiliary agent mixes and the autoclave of packing in, add 200g again to ethyl benzoate, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 20 atm, with High Purity Hydrogen displacement 3-4 time, fill hydrogen during to 170 ℃ to 110atm, start to stir and pick up counting simultaneously, when the still internal pressure is reduced to 90atm, immediate record reaction time and reaction temperature, and rapidly pressure is brought up to 110atm, according to identical method, repeat multi-pass operation as requested, and continue record each reaction time (reducing to 90atm from 110atm), catalyst sample is finished circular response usually 7 times, utilize γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, with time is abscissa, and γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z
2=γ
0/ 4.
Table 5 has been listed the Ru/C catalyst activity that adds behind the catalyst promoter that embodiment of the invention 1-4 provides.
Comparative Examples 4
The explanation of this Comparative Examples does not add the Ru/C activity of such catalysts situation when containing the Ni auxiliary agent.
Method according to embodiment 25-28 is estimated the Ru/C activity of such catalysts, and different is not add the amorphous alloy auxiliary agent that contains Ni, and the results are shown in Table 5 for gained.
Table 5.
Ru/C catalyst concn nickel promoter addition numbering auxiliary agent
The active Z of Ru/C
2
% (accounting for Ru weight) embodiment 25 ZA-1 1 0.4 0.50 embodiment 26 ZA-2 1 0.4 0.47 embodiment 27 ZA-3 1 0.4 0.4 embodiment 28 ZA-4 1 0.4 0.42 Comparative Examples 40 0.30
Claims (10)
1, a kind of raising and the method for stable noble metal catalyst activity is characterized in that: at the noble metal catalyst that uses platiniferous, palladium, ruthenium and/or rhodium and can produce the nickeliferous catalyst promoter of adding in the H-H reaction system that faces of carbon monoxide poisonous substance; Wherein said nickeliferous catalyst promoter is for being the amorphous alloy catalyst of main active component, nickeliferous carried non-crystal alloy catalyst, Raney's nickel catalyst with nickel or being the nickel catalyst carried of main active component with nickel; The addition of said auxiliary agent is Ni/ noble metal=0.01-50 (weight ratio).
2, according to the method for claim 1, wherein said use noble metal catalyst and can produce the carbon monoxide poisonous substance face the hydrogenation reaction of H-H reaction as benzoic acid or substituted benzoic acid, terephthalic acid (TPA) hydrofining reaction, the perhaps hydrogenation reaction of aliphatic unsaturated carboxylic acid or its ester.
3, according to the method for claim 2, wherein the hydrogenation reaction of said substituted benzoic acid prepares the reaction of the naphthenic acid of C1-C5 alkyl replacement for the benzoic acid hydrogenation of C1-C5 alkyl replacement.
4, according to the method for claim 3, wherein the hydrogenation reaction of said substituted benzoic acid is a cumfrey or to the reaction of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid.
5, according to the process of claim 1 wherein said H-H reaction prepares naphthenic acid as benzoic acid hydrogenation the reaction of facing of using noble metal catalyst and can producing the carbon monoxide poisonous substance.
6, according to the process of claim 1 wherein that said noble metal catalyst is a corresponding catalyst used in the said reaction, these catalyst comprise Pt/C, Pt/ silica gel, PtO
2, Pd/C, Pd/ diatomite, PdO
2, Ru/C, RuO
2, Rh/C or Ru-Pd/C.
7, according to the process of claim 1 wherein that said nickeliferous catalyst promoter is for being amorphous alloy catalyst, Raney's nickel catalyst or the methanation catalyst of main active component with nickel.
8, according to the method for claim 1, wherein said is to be 45 ± 1 ° at 2 θ in its X-ray diffractogram of amorphous alloy catalyst of main active component to locate to occur a diffuse maximum with nickel, and the Al of the Ni that consists of 10-95 weight % of this catalyst, 20-80 weight %, the Fe of 0-25 weight % and 0-10 weight % are selected from one or more elements in the group of being made up of P, Co, Cr, Mn, W and Mo.
9, according to the process of claim 1 wherein that said nickeliferous carried non-crystal alloy catalyst is that the amorphous state component that is selected from nickel and boron, nickel and phosphorus, nickel-other metal component-boron, nickel-other metal component-phosphorus loads on and is selected from SiO
2, active carbon, Al
2O
3Porous carrier on the carried non-crystal alloy catalyst that obtains.
10, according to the process of claim 1 wherein that the addition of said auxiliary agent is Ni/ noble metal=0.1-10 (weight ratio).
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|---|---|---|---|
| CNB001249061A CN1136975C (en) | 2000-09-25 | 2000-09-25 | Noble metal catalyst method of resisting Co poisoning |
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|---|---|---|---|
| CNB001249061A CN1136975C (en) | 2000-09-25 | 2000-09-25 | Noble metal catalyst method of resisting Co poisoning |
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| CN1136975C CN1136975C (en) | 2004-02-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055935A (en) * | 2012-12-16 | 2013-04-24 | 青岛博益特生物材料有限公司 | Hydro-catalyst |
| CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
| CN108440311A (en) * | 2018-03-29 | 2018-08-24 | 万华化学集团股份有限公司 | A kind of Hydrogenation for diaminodiphenyl-methane method |
| CN112473719A (en) * | 2021-01-25 | 2021-03-12 | 潍坊科技学院 | Preparation method of porous carbon-nitrogen material loaded nano bimetallic catalyst and use method of catalyst in benzoic acid hydrogenation reaction |
| CN112552138A (en) * | 2020-12-29 | 2021-03-26 | 阚晓震 | Low-cost synthesis process for producing cyclohexane by benzene hydrogenation |
-
2000
- 2000-09-25 CN CNB001249061A patent/CN1136975C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055935A (en) * | 2012-12-16 | 2013-04-24 | 青岛博益特生物材料有限公司 | Hydro-catalyst |
| CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
| CN106492856B (en) * | 2016-10-18 | 2019-02-26 | 中国科学院深圳先进技术研究院 | NiP-Pd catalyst and its preparation method and application |
| CN108440311A (en) * | 2018-03-29 | 2018-08-24 | 万华化学集团股份有限公司 | A kind of Hydrogenation for diaminodiphenyl-methane method |
| CN108440311B (en) * | 2018-03-29 | 2020-11-20 | 万华化学集团股份有限公司 | Method for preparing diaminodicyclohexyl methane by hydrogenation |
| CN112552138A (en) * | 2020-12-29 | 2021-03-26 | 阚晓震 | Low-cost synthesis process for producing cyclohexane by benzene hydrogenation |
| CN112473719A (en) * | 2021-01-25 | 2021-03-12 | 潍坊科技学院 | Preparation method of porous carbon-nitrogen material loaded nano bimetallic catalyst and use method of catalyst in benzoic acid hydrogenation reaction |
| CN112473719B (en) * | 2021-01-25 | 2021-06-29 | 潍坊科技学院 | Preparation method of porous carbon-nitrogen material loaded nano bimetallic catalyst and use method of catalyst in benzoic acid hydrogenation reaction |
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| Publication number | Publication date |
|---|---|
| CN1136975C (en) | 2004-02-04 |
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