CN102794178B - A kind of selective hydrogenation catalyst and preparation thereof - Google Patents
A kind of selective hydrogenation catalyst and preparation thereof Download PDFInfo
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- CN102794178B CN102794178B CN201110134888.4A CN201110134888A CN102794178B CN 102794178 B CN102794178 B CN 102794178B CN 201110134888 A CN201110134888 A CN 201110134888A CN 102794178 B CN102794178 B CN 102794178B
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Abstract
The present invention relates to a kind of selective hydrogenation catalyst, comprise Ni-B amorphous alloy and Al
2o
3-TiO
2composite oxide carrier material, the content of Ni-B amorphous alloy is 4 ~ 40wt%, and preferred Ni-B content is 4 ~ 20wt%, Ni, the mol ratio of B is 3: 1 ~ 1: 3, preferably 1: 1 ~ 1: 3.The invention still further relates to the preparation method of above-mentioned catalyst.Catalyst of the present invention can be used for the selective hydrogenation of diene, is particularly useful for C
10~ C
16selec-tive hydrogenation in long-chain normal diene hydrocarbon, has catalytic activity high, selective height, the feature that low temperature active is good.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst of petroleum hydrocarbon, particularly relate to the selec-tive hydrogenation catalyst of long-chain normal diene hydrocarbon.The invention still further relates to the preparation of above-mentioned catalyst.
Background technology
Long-chain (C
10~ C
16) positive structure monoolefine is one of important source material of higher aliphatic and synthetic detergent, in current world wide, the production of long-chain normal monoolefine mainly adopts the long-chain normal paraffin dehydrogenation Palcol technique of American UOP company.C in this technique
10~ C
16the monoolefine material produced through dehydrogenation unit of long chain alkane in alkadienes containing 1 ~ 3wt%, the existence of these alkadienes can cause a large amount of side reactions in follow-up alkylation process, reduce productive rate and the quality of alkylbenzene, affect sulfonic acid color and luster after alkylbenzene sulfonation, and cause acid catalyst inactivation.Utilize diolefin hydrogenate method by the diolefin hydrogenate in dehydrogenation product, generate monoolefine, on the basis of improving alkylbenzene productive rate, can effectively improve the quality of alkylbenzene.Up to now, palladium-based catalyst is considered to most effective as selective hydrogenation catalyst, and has been widely used in industrial production.Palladium-based catalyst shows good hydrogenation activity and selective at normal temperatures and pressures, but industrial reality often requires that reaction is carried out under higher temperature and pressure, as: for avoiding increasing huge condensing plant, industrial actual requirement long-chain normal diene selec-tive hydrogenation carries out between 100 to 180 DEG C.But at relatively high temperatures, the selective of palladium catalyst greatly reduces.Often adopt for the catalytic performance improving catalyst and with the following method palladium catalyst is improved, as added the second metal component; Change carrier composition or kind control the interaction between carrier and palladium; Add in reaction system to electron species; Control the Acidity of Aikalinity of carrier.The selective hydrogenation of alkynes in the selective hydrogenation of in alkene 1,3-butadiene and alkene but above-mentioned research focuses mostly on, and palladium catalyst is expensive, the poor performance of sulfur resistive and arsenic poisoning.Therefore a kind of non-noble metal high efficiency selected hydrogenation catalyst is invented very important.
Chinese patent CN1153617C discloses a kind of selective hydrogenation of long-chain normal diene catalyst, selects molybdenum nitride and nitrogen molybdenum oxide, this γ-Mo
2n catalyst is with MoO
3for raw material, NH
3and H
2mist be nitridizing agent, adopt temperature programmed nitridation legal system standby.The method deficiency is that reaction temperature is high, and pressure is large, and ammonia has corrosion to metallic reactors at high temperature under high pressure, and is difficult to synthesis in enormous quantities.US Patent No. 4695560, US4523048, US4761509 and Chinese patent CN1032157 disclose the process for selective hydrogenation of the diolefin in dehydrating alkanes product, and the feature of the catalyst that the method uses is with Al
2o
3for the Raney nickel of carrier, this catalyst before use must through vulcanizing treatment, and for reaching certain reactivity, selective hydrogenation will carry out being greater than under the condition of 200 DEG C, under these conditions, have part cracking side-reaction and occur, add the consumption of material.Chinese patent CN1268549A describes a kind of for removing C
10~ C
16the process for selective hydrogenation of middle straight chain diene, the feature of the catalyst that the method uses is with Al
2o
3the palladium catalyst of carrier, for the diolefin hydrogenation conversion ratio and generation monoene improving catalyst is selective, the process employs multi-stek hydrogenation technique, thus adds equipment investment.
Amorphous alloy is the material that a class has atomic arrangement shortrange order and longrange disorder design feature, has excellent catalytic performance.Since nineteen sixty, Duwez etc. have prepared amorphous alloy first by melting quench method.After this developed more economic, simple and direct chemical reduction method, ultrafine amorphous state alloy can have been prepared in this way.The characteristics such as the electronic state that amorphous alloy has isotropism, active sites is evenly distributed, the coordination of active atomic height is unsaturated and unique, thus in a lot of catalytic reaction, show unique high activity and high selectivity, especially in the hydrogenation reaction of unsaturated compound, there is excellent catalytic performance especially.Compared with pure state amorphous alloy, carried non-crystal alloy has that specific area is large, heat endurance is high, low cost and other advantages.Current amorphous alloy hydrogenation catalyst, mainly with SiO
2, Al
2o
3for carrier, the amorphous alloy active component of load is NiB and NiP, the further development but these catalyst are still needed in activity and mechanical strength.
The research of the existing catalyst performance to amorphous alloy mainly concentrates on short-chain olefin hydrogenation, the selec-tive hydrogenation of diene (concentrating on cyclopentadiene), aromatic moiety hydrogenation, the selec-tive hydrogenation of alkynes in alkene, aldehyde ketone hydrogenation, nitro compound, the reactions such as nitrile hydrogenation and co hydrogenation, as patent CN1179358A discloses NiB Alloy in silica gel, the catalyst that aluminium oxide or active carbon obtain, prepare at room temperature or at higher temperatures, this catalyst can be used for aromatic moiety hydrogenation, the selec-tive hydrogenation of alkynes, ketone hydrogenation, nitro compound and nitrile hydrogenation reaction.Due to the reaction very exothermic of metal ion and hydroboron, and the preparation feedback of above-mentioned catalyst carries out at room temperature or at higher temperatures, therefore hot-spot may be caused, result causes the alloying pellet generated to be reunited or crystallization, and size and the domain size distribution of the amorphous particles obtained are uneven.
At present, become the amorphous catalyst document of long-chain normal monoolefine few about long-chain normal diene hydrocarbon selec-tive hydrogenation.Current topmost problem is the high-performance selective hydrogenation catalyst of development low reaction temperatures, high activity, high selectivity, high stability.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art, provide a kind of new selective hydrogenation catalyst, it is high that this catalyst has catalytic activity, the advantage that selective and conversion ratio is high.Present invention also offers the preparation method of above-mentioned selective hydrogenation catalyst.
The invention provides a kind of selective hydrogenation catalyst, with Al
2o
3-TiO
2composite oxides are carrier, loading NiB amorphous metal alloy.
In above-mentioned catalyst, the content of Ni-B is 4 ~ 40wt%, preferably 4 ~ 20wt%; The mol ratio of Ni and B is 3: 1 ~ 1: 3, preferably 1: 1 ~ 1: 3; Nickel loading is 4 ~ 20wt% based on gross mass.
In described catalyst, Al
2o
3-TiO
2the content of composite oxide carrier is 60.0 ~ 96.0%, and the specific area of this carrier is 60 ~ 150m
2/ g, preferably 120 ~ 150m
2/ g; Pore volume is 0.3 ~ 1.0ml/g, is preferably 0.5 ~ 1.0ml/g; Most probable pore size is 60 ~ 140 dusts, preferably 110 ~ 140 dusts.The shape of this carrier can be cylindricality, spherical, bar shaped, cloverleaf pattern or gear shape, preferred cloverleaf pattern.TiO in this carrier
2content based on Al
2o
3be 5 ~ 20wt%.
In described catalyst carrier be prepared as known technology, can sol-gel process be adopted, or aluminate or aluminium salt precipitation method, coprecipitation, the preparations such as aluminium salt neutralisation and aluminium alcoholates Hydrolyze method.Preparation method in the patent CN1184289 of Yanshan Mountain branch of preferred Beijing Chemical Research Institute.As prepared in the following manner: be 100 ~ 200m with specific surface
2/ g, pore volume is 0.5 ~ 1.5ml/g, and most probable pore size is that the aluminium oxide of 80 ~ 200 dusts immerses in compound titanium solution, and the consumption of wherein said solution is at least total pore volume equivalent with described aluminium oxide, and stirs 10 ~ 30 minutes; By impregnated aluminium oxide at the temperature of 100 ~ 150 DEG C dry 4 ~ 10 hours, then in the temperature lower calcination 4 ~ 8 hours of 500 ~ 900 DEG C, the obtained alumina-silica titanium composite oxide carrier containing 5 ~ 20wt% titanium oxide based on alumina weight.
In an embodiment of the present invention, described catalyst is C
10~ C
16the selective hydrogenation catalyst of long-chain normal diene hydrocarbon, this catalyst is with Al
2o
3-TiO
2composite oxides are carrier, loading NiB amorphous metal alloy.In above-mentioned catalyst, the content of Ni-B amorphous alloy is 4 ~ 40wt%, preferably 4 ~ 20wt%; The mol ratio of Ni and B is 3: 1 ~ 1: 3, preferably 1: 1 ~ 1: 3; Nickel loading is 4 ~ 20wt% based on gross mass.Long-chain normal diene hydrocarbon selec-tive hydrogenation generates long-chain normal monoolefine.
Present invention also offers a kind of technique preparing above-mentioned catalyst, comprising:
(1) by Al
2o
3-TiO
2composite oxide carrier, adds in nickel salt solution, and dipping stirs, and filters, washing;
(2) at 0 ~ 30 DEG C, under inert atmosphere, add metal hydroboron solution, stir, until produce without gas.
In the preferred enforcement of above-mentioned preparation technology:
(1) by TiO
2for Al
2o
3weight 5 ~ 20% Al
2o
3-TiO
2composite oxide carrier, adds in nickel salt solution, and dipping stirring 4 hours, filters, washing;
(2) at 0 ~ 10 DEG C, under blanket of nitrogen, add metal hydroboron solution, add in 15 ~ 25min, simultaneously vigorous stirring, until produce without gas.
In above-mentioned preparation technology, described nickel salt can be understood as the nickel salt that selective hydrogenation catalyst adopts usually, can include but not limited to: the sulfate of nickel, nitrate, soluble carboxylate, hypophosphites and halide, be preferably nickelous sulfate, nickel nitrate, nickel chloride and nickel acetate.The type of described nickel salt solution is not particularly limited, can be the aqueous solution, also can be the organic nickel salting liquid that ethanol, benzene etc. are formed as solvent, but use organic nickel salting liquid cost higher, and also have pollution problem, therefore the present invention preferably uses the aqueous solution of inorganic nickel.
In above-mentioned preparation technology, the described preferred potassium borohydride of metal hydroboron, sodium borohydride or its mixture.The type of described metal hydroboron solution is not particularly limited, can be the aqueous solution, also can be the organic solution that ethanol etc. is formed as solvent, but use organic solution cost higher, and also have pollution problem, therefore the present invention preferably uses the aqueous solution of metal hydroboron.
The catalyst prepared by above-mentioned technique can directly be used; Also, after can filtering, being washed to neutrality, absolute ethanol washing, be placed in absolute ethyl alcohol and preserve.
Catalyst of the present invention, prepares at a lower reaction temperature with under inert atmosphere, can avoid reunion or the crystallization of the alloying pellet generated, obtain the catalyst of amorphous particle size and even particle size distribution.By by NiB with chemical reduction method load at TiO
2-Al
2o
3on complex carrier, with use alumina phase ratio, the decentralization of active metal can be improved, be conducive to reactant and catalyst active center's close contact, thus improve the activity of catalytic hydrogenation, and its electronic property can be changed.Due to TiO
2add on carrier and have more B acid site, and the B of supported Ni catalyst carrier surface acid has electronic induction effect to Ni cluster, makes it to present " electronics shortage " performance.When metal surface presents " electronics shortage " state, metallic atom cloud density reduces, and the hydrogenation activity of alkadienes strengthens thereupon, illustrates that the Hydrogenation of Ni catalyst can be improved in the B acid site on carrier.This catalyst has larger aperture, 97 (v) more than % channel diameter > 100 dust on preferred carrier, diene selective hydrotreating is reacted, increase the duct of catalyst, namely hydrogen and the reactant molecule collision frequency in catalyst active center can be improved, the colloidal sol ability of catalyst can be increased again, improve its stability.
Catalyst of the present invention, by NiB load at alumina-silica titanium composite oxide carrier, can increase the mechanical strength of catalyst, compression strength reaches 180N/cm, far exceedes the anti-pressure ability of carried non-crystal NiB catalyst of the same type.High strength carrier is not easily broken in Catalyst packing and use procedure, can repeated multiple timesly regenerate, and is therefore conducive to the stability improving catalyst, the time of extending catalyst even running, and improves hydrogenation activity, have good low temperature active simultaneously.
Catalyst of the present invention, with industrial conventional with Al
2o
3for the palladium catalyst of carrier is compared, adopt TiO
2-Al
2o
3composite oxide carrier material load Ni-B amorphous alloy, TiO
2-Al
2o
3composite oxide carrier can take into account Al
2o
3excellent catalytic activity and TiO
2anti-carbon, anti-poisoning capability, can improve catalytic performance and the stability of Ni-B catalyst further.Catalyst of the present invention is used for C
10~ C
16the selective hydrogenation of long-chain normal diene hydrocarbon, can significantly improving diene conversion ratio and diolefin hydrogenation, to generate monoene selective, the object removing long-chain normal diene, increase long-chain normal monoene output can be reached by one section or two-stage hydrogenation technique, can process simplification and reduction equipment investment.
By catalyst prepared by the present invention, the selective hydrogenation that can be used for a small amount of diene in monoolefine generates monoolefine, is particularly useful for C
10~ C
16long-chain normal diene hydrocarbon-selective hydrogenation generates long-chain normal monoolefine.
Detailed description of the invention
Below by example, further elaboration is carried out to preferred embodiments of the present invention, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1:
Carrier adopts the Al in the patent CN1184289C of the Yanshan Mountain, Beijing Chemical Research Institute branch
2o
3-TiO
2composite oxide carrier, takes 5g Al
2o
3-TiO
2, titanium oxide is 5% of quality of alumina, under agitation slowly joins in 20ml nickel sulfate solution; concentration of nickel sulfate is in the theoretical negative carrying capacity of Ni for 5%, and dipping stirring 4 hours, filters; filter cake adds 12ml distilled water, 0 DEG C, under nitrogen protection, add a certain amount of 1mol/L KBH
4solution makes the mol ratio of Ni: B be 1: 1, drips off in 15min.Vigorous stirring, until produce without gas.Obtained catalyst 1, data are in table 1.
Embodiment 2:
Carrier adopts the Al in the patent CN1184289C of the Yanshan Mountain, Beijing Chemical Research Institute branch
2o
3-TiO
2composite oxide carrier, takes 5g Al
2o
3-TiO
2, titanium oxide is 5% of quality of alumina, under agitation slowly joins in 20ml nickel nitrate aqueous solution; nickel nitrate concentration is in the theoretical negative carrying capacity of Ni for 10%, and dipping stirring 4 hours, filters; filter cake adds 12ml distilled water, 0 DEG C, under nitrogen protection, add a certain amount of 1mol/L KBH
4solution makes the mol ratio of Ni: B be 1: 2, drips off in 15min.Vigorous stirring, until produce without gas.Obtained catalyst 2, data are in table 1.
Embodiment 3:
Carrier adopts the Al in the patent CN1184289C of the Yanshan Mountain, Beijing Chemical Research Institute branch
2o
3-TiO
2composite oxide carrier, takes 5g Al
2o
3-TiO
2, titanium oxide is 10% of quality of alumina, under agitation slowly joins in 20ml nickel chloride aqueous solution; nickel chloride concentration is in the theoretical negative carrying capacity of Ni for 15%, and dipping stirring 4 hours, filters; filter cake adds 12ml distilled water, 0 DEG C, under nitrogen protection, add a certain amount of 1mol/L KBH
4solution makes the mol ratio of Ni: B be 1: 2.5, drips off in 15min.Vigorous stirring, until produce without gas.Obtained catalyst 3, data are in table 1.
Embodiment 4
Carrier adopts the Al in the patent CN1184289C of the Yanshan Mountain, Beijing Chemical Research Institute branch
2o
3-TiO
2composite oxide carrier, takes 5g Al
2o
3-TiO
2, titanium oxide is 10% of quality of alumina, under agitation slowly joins in 20ml nickel acetate aqueous solution; nickel acetate concentration is in the theoretical negative carrying capacity of Ni for 20%, and dipping stirring 4 hours, filters; filter cake adds 12ml distilled water, 0 DEG C, under nitrogen protection, add a certain amount of 1mol/L KBH
4solution makes the mol ratio of Ni: B be 1: 3, drips off in 15min.Vigorous stirring, to reaction does not have gas to generate.Obtained catalyst 4, data are in table 1.
Embodiment 5:
Carrier adopts the Al in the patent CN1184289C of the Yanshan Mountain, Beijing Chemical Research Institute branch
2o
3-TiO
2composite oxide carrier, takes the Al of 5g
2o
3-TiO
2, titanium oxide is 10% of quality of alumina, under agitation slowly joins 50ml nickel acetate aqueous solution, nickel acetate concentration in the theoretical negative carrying capacity of Ni for 20%.Dipping stirring 4 hours, filter, filter cake adds in the distilled water of 12ml.0 DEG C, under nitrogen protection, add a certain amount of 1mol/L NaBH
4solution makes the mol ratio of Ni: B be add in 1: 3,20min.Vigorous stirring, to reaction does not have gas to generate.Obtained catalyst 5, data are in table 1.
Table 1
Comparative example 1:
The catalyst of the embodiment 1 in patent CN1268549A, to intend thin water Al
2o
3powder is raw material, shaping by the method for spin, and through 120 DEG C of dryings 5 hours, 550 DEG C of roastings 5 hours, made γ-Al
2o
3bead, uses PdCl
2aqueous impregnation, through 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, then used H
2reduce 3 hours at 100 DEG C, obtained finished product is containing the catalyst C-1 of Pd 0.2wt%.
Comparative example 2:
The catalyst of the embodiment 4 in patent CN1974005A, gets 2g nonionic triblock high polymer (polyethylene oxygen-polypropylene oxygen-polyethylene oxygen) EO
20pO
70eO
20(P123) be dissolved in 15ml water, add the HCI of 60ml concentration 2mol/L, stirring 1h is placed in 40 DEG C of water-baths, after stir about 0.5h, slow dropping 4.25g ethyl orthosilicate (TEOS) solution, continue to stir 24h, load in stainless steel cauldron, be placed in 100 DEG C of baking oven constant temperature 24h.Filtered by gained white opacity liquid, washing, 100 DEG C of dryings, 550 DEG C of roasting 6h, obtain SBA-15.Get 2.64ml butyl titanate to add in 110ml absolute ethyl alcohol, shake up and add obtained 20gSBA-15 carrier, rotary evaporated to dryness, 120 DEG C of dried overnight, 550 DEG C of roasting 4h, obtain carrier 3.0%TiO
2-SBA-15.
Get the PdCl of 10ml distilled water and 20ml
2the aqueous solution (concentration 3.0105gPd/L), is placed in 80 DEG C of water-bath 30min, under agitation adds the above-mentioned 3.0%TiO of 20g
2-SBA-15,80 DEG C of water bath methods, 120 DEG C of oven dry are spent the night.The activation dechlorination condition of catalyst is as follows: pass into air-activated 1h with the flow of 50ml/min at 500 DEG C, then in identical temperature, passes into the saturated steam dechlorination 1h of 80 DEG C under same traffic.Obtain C-2 catalyst 0.3%Pd/3.0%TiO
2-SBA-15.
Embodiment 6
The catalytic performance of evaluate catalysts 1 ~ 5.
Long-chain (C is carried out with complete molten hydrogen hydrogenation technique in fixed bed reactors
10~ C
16) normal diene selective hydrogenation.Feedstock oil containing 85.2wt% long chain alkane, 10.0wt% long chain olefine, 1.17wt% long-chain diolefin and 3.61wt% aromatic hydrocarbons is added in the autoclave of 2.0L, under 100 DEG C and 0.9MPa, dissolves H
2pass through respectively with the beds that C-1 and C-2 in catalyst 1 ~ 5 in embodiment and comparative example fills after saturated, catalyst packing volume is 10ml, reaction pressure all adopts 1.5MPa, the mol ratio joining diene in hydrogen in feedstock oil and feedstock oil is 1: 1, reaction temperature is 100 DEG C, and the liquid air speed of material is 5.0h
-1.Utilize material after gas chromatographic analysis hydrogenation.The activity and selectivity evaluation result of each catalyst is in table 2.
Table 2
| Catalyst | Diene conversion ratio (mol%) | Generate selective (mol%) of monoene |
| 1 | 53.60 | 27.69 |
| 2 | 73.50 | 36.8 |
| 3 | 86.94 | 41.34 |
| 4 | 83.69 | 42.64 |
| 5 | 85.69 | 49.34 |
| C-1 | 59.40 | 5.34 |
| C-2 | 76.01 | 40.20 |
Straight chain normal diene conversion ratio and diolefin hydrogenation generate monoene optionally computing formula:
It should be noted that by referring to preferred embodiment to present disclosure has been description, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present disclosure wherein described relates to specific catalyst, preparation method and embodiment, but and do not mean that present disclosure is limited to particular case disclosed in it, on the contrary, present disclosure easily extensible is to other all catalyst, preparation method and application with same composition.
Claims (7)
1. a C
l0~ C
16long-chain normal diene hydrocarbon selective hydrogenation catalyst, comprises Ni-B amorphous alloy and Al
2o
3-TiO
2composite oxide carrier material, the content of described Ni-B amorphous alloy is 4 ~ 20wt%, described Al
2o
3-TiO
2the content of composite oxide carrier material is 80 ~ 96wt%, TiO in described carrier material
2content based on Al
2o
3for 5-20wt%, in described Ni-B amorphous alloy, the mol ratio of Ni, B is 3:1 ~ 1:3.
2. catalyst according to claim 1, is characterized in that, in described Ni-B amorphous alloy, the mol ratio of Ni, B is 1:1 ~ 1:3.
3. prepare a technique for the catalyst described in claim 1 or 2, comprising:
A. by Al
2o
3-TiO
2composite oxide carrier adds in nickel salt solution, and dipping stirs, and filters, washing;
B. at the temperature of 0 ~ 30 DEG C, under inert atmosphere, add metal hydroboron solution, stir, until produce without gas.
4. technique according to claim 3, is characterized in that, in b, described temperature is 0 ~ 10 DEG C.
5. the technique according to claim 3 or 4, is characterized in that, described nickel salt is selected from nickel halogenide, nickelous sulfate, nickel nitrate, nickelous hypophosphite and soluble carboxylic acid's nickel.
6. the technique according to claim 3 or 4, is characterized in that, described nickel salt is selected from nickel nitrate, nickelous sulfate, nickel chloride and nickel acetate.
7. the technique according to claim 3 or 4, is characterized in that, described metal hydroboron is potassium borohydride, sodium borohydride or its mixture.
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| CN104248964B (en) * | 2013-06-28 | 2016-09-07 | 中国石油天然气股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN103952719B (en) * | 2014-03-28 | 2017-05-03 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
| CN105080594B (en) * | 2014-05-08 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of nickel catalyst and preparation method thereof |
| CN106492808B (en) * | 2016-09-06 | 2019-11-05 | 中国科学院广州能源研究所 | A kind of catalyst and preparation method of the reaction of catalysis lilac phenol hydrogenation deoxidation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301591A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Non-crystalline alloy catalyst for olefine selective hydrogenation |
| CN101028599A (en) * | 2007-01-26 | 2007-09-05 | 南开大学 | Production of NiB amorphous alloy catalyst by chitose medium dispersing method |
| CN101856613A (en) * | 2009-04-08 | 2010-10-13 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of petroleum hydrocarbon and preparation method and application thereof |
-
2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301591A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Non-crystalline alloy catalyst for olefine selective hydrogenation |
| CN101028599A (en) * | 2007-01-26 | 2007-09-05 | 南开大学 | Production of NiB amorphous alloy catalyst by chitose medium dispersing method |
| CN101856613A (en) * | 2009-04-08 | 2010-10-13 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of petroleum hydrocarbon and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 复合载体及其制备方法对非晶态Ni-B合金催化剂性能的影响;石秋杰等;《分子催化》;20071031;第21卷(第05期);433-437 * |
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