CN102794178A - Selective hydrogenation catalyst and preparation thereof - Google Patents
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- CN102794178A CN102794178A CN2011101348884A CN201110134888A CN102794178A CN 102794178 A CN102794178 A CN 102794178A CN 2011101348884 A CN2011101348884 A CN 2011101348884A CN 201110134888 A CN201110134888 A CN 201110134888A CN 102794178 A CN102794178 A CN 102794178A
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Abstract
The invention relates to a selective hydrogenation catalyst which comprises an Ni-B amorphous alloy and an Al2O3-TiO2 composite oxide supporter material, wherein the content of the Ni-B amorphous alloy is 4-40 wt%, preferably 4-20 wt%; and the Ni/B mol ratio is 3:1-1:3, preferably 1:1-1:3. The invention also relates to a preparation method of the catalyst. The catalyst provided by the invention can be used for selective hydrogenation of diolefins, and is especially suitable for selective hydrogenation of C10-C16 long-chain normal diolefins. The catalyst has the characteristics of high catalytic activity, high selectivity and favorable low-temperature activity.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst of petroleum hydrocarbon, the selection hydrogenation that particularly relates to the long-chain normal diene hydrocarbon is used catalyst.The invention still further relates to above-mentioned Preparation of catalysts.
Background technology
Long-chain (C
10～C
16) positive structure monoolefine is one of important source material of higher aliphatic and synthetic detergent, the production of long-chain normal monoolefine mainly is the long-chain normal paraffin dehydrogenation Palcol technology of employing American UOP company in the world wide at present.C in this technology
10～C
16Long chain alkane in the monoolefine material of dehydrogenation unit production, contain the alkadienes of 1～3wt%; Existing in the follow-up alkylation process of these alkadienes can cause a large amount of side reactions; The productive rate and the quality of alkylbenzene have been reduced; Influence sulfonic acid color and luster after the alkylbenzene sulfonation, and cause the acid catalyst inactivation.Utilize the diolefin hydrogenate method with the diolefin hydrogenate in the dehydrogenation product, generate monoolefine, can on the basis of improving the alkylbenzene productive rate, improve the quality of alkylbenzene effectively.Up to now, palladium-based catalyst is considered to effective as selective hydrogenation catalyst, and has been widely used in the commercial production.Palladium-based catalyst shows good hydrogenation activity and selectivity at normal temperatures and pressures; Yet reality often requires to be reflected under higher temperature and the pressure and carries out in the industry; As: for avoiding increasing huge condensing plant, industry practice requires long-chain normal diene to select hydrogenation between 100 to 180 ℃, to carry out.But under higher temperature, the selectivity of palladium catalyst greatly reduces.Adopt following method that palladium catalyst is improved for the catalytic performance that improves catalyst is normal, as add second metal component; Change carrier composition or kind and control the interaction between carrier and the palladium; In reaction system, add and give the electronics material; The Acidity of Aikalinity of control carrier.The selective hydrogenation of alkynes in the selective hydrogenation of in alkene 1,3-butadiene and the alkene but above-mentioned research focuses mostly on, and palladium catalyst cost an arm and a leg the poor performance of anti-sulphur and arsenic poisoning.Therefore it is very important to invent a kind of non-noble metal high efficiency selected hydrogenation catalyst.
Chinese patent CN1153617C discloses a kind of selective hydrogenation of long-chain normal diene catalyst, selects molybdenum nitride and nitrogen molybdenum oxide for use, this γ-Mo
2The N catalyst is with MoO
3Be raw material, NH
3And H
2Mist be nitridizing agent, adopt the preparation of temperature programmed nitridation method.This method deficiency is that reaction temperature is high, and pressure is big, and ammonia has corrosion to metallic reactors under HTHP, and is difficult in enormous quantities synthetic.U.S. Pat 4695560, US4523048, US4761509 and Chinese patent CN1032157 disclose the process for selective hydrogenation of the diolefin in the dehydrating alkanes product, being characterized as with Al of the employed catalyst of this method
2O
3Be the Raney nickel of carrier, this catalyst before use must be through vulcanizing treatment, and for reaching the certain reaction activity; Selective hydrogenation will carry out under greater than 200 ℃ condition; Under this condition, have the part cracking side-reaction and take place, increased the consumption of material.Chinese patent CN1268549A has introduced a kind of C that is used to remove
10～C
16In the process for selective hydrogenation of straight chain diene, being characterized as of the employed catalyst of this method with Al
2O
3The palladium catalyst of carrier is the diolefin hydrogenation conversion ratio and the generation monoene selectivity that improve catalyst, and this method has adopted the multistage hydrogenation technique, thereby has increased equipment investment.
Amorphous alloy is one type and has the atomic arrangement shortrange order and the material of long-range disordered structure characteristics has excellent catalytic performance.Since nineteen sixty, Duwez etc. have prepared amorphous alloy first through melting quench method.After this develop more economic, simple and direct chemical reduction method, can prepare ultrafine amorphous attitude alloy in this way.Amorphous alloy has isotropism, active sites is evenly distributed, the coordination of active atomic height is unsaturated and unique characteristics such as electronic state; Thereby in a lot of catalytic reactions, demonstrated unique high activity and high selectivity, especially have excellent catalytic performance aspect the hydrogenation reaction of unsaturated compound especially.Compare with the pure state amorphous alloy, carried non-crystal alloy has that specific area is big, heat endurance is high, low cost and other advantages.Present amorphous alloy hydrogenation catalyst mainly is with SiO
2, Al
2O
3Be carrier, the amorphous alloy active component of load is NiB and NiP, the further development but these catalyst are still needed on active and mechanical strength.
The research of existing catalyst performance to amorphous alloy mainly concentrates on the reactions such as selection hydrogenation, aldehyde ketone hydrogenation, nitro compound, nitrile hydrogenation and co hydrogenation of alkynes in the selection hydrogenation, aromatic hydrocarbons partial hydrogenation, alkene of short-chain olefin hydrogenation, diene (concentrating on cyclopentadiene); Disclose the NiB alloy like patent CN1179358A and be carried on the catalyst that obtains on silica gel, aluminium oxide or the active carbon; Under room temperature or higher temperature, prepare, this catalyst can be used for selection hydrogenation, ketone hydrogenation, nitro compound and the nitrile hydrogenation reaction of aromatic hydrocarbons partial hydrogenation, alkynes.Because the reaction very exothermic of metal ion and hydroboron; And above-mentioned Preparation of catalysts is reflected under room temperature or the higher temperature carries out; Therefore possibly cause hot-spot; The alloying pellet that the result causes generating is reunited or crystallization the size of the amorphous alloy particle that obtains and particle diameter skewness.
At present, it is few to select to be hydrogenated into the amorphous catalyst document of long-chain normal monoolefine about the long-chain normal diene hydrocarbon.Current topmost problem is that the high-performance of development low reaction temperatures, high activity, high selectivity, high stability is selected hydrogenation catalyst.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned prior art, a kind of new selection hydrogenation catalyst is provided, this catalyst has the catalytic activity height, the advantage that selectivity and conversion ratio are high.The present invention also provides above-mentioned selection hydrogenization catalyst preparation method.
The invention provides a kind of selection hydrogenation catalyst, with Al
2O
3-TiO
2Composite oxides are carrier, loading NiB amorphous metal alloy.
In the above-mentioned catalyst, the content of Ni-B is 4～40wt%, preferred 4～20wt%; The mol ratio of Ni and B is 3: 1～1: 3, preferred 1: 1～1: 3; Nickel loading is 4～20wt% based on gross mass.
In the said 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, preferred 120～150m
2/ g; Pore volume is 0.3～1.0ml/g, is preferably 0.5～1.0ml/g; The most probable aperture is 60～140 dusts, preferred 110～140 dusts.The shape of this carrier can be cylindricality, sphere, bar shaped, cloverleaf pattern or gear shape, preferred cloverleaf pattern.TiO in this carrier
2Content based on Al
2O
3Be 5～20wt%.
In the said catalyst carrier be prepared as known technology, can adopt sol-gel process, or aluminate or aluminium salt precipitation method, coprecipitation, preparations such as aluminium salt neutralisation and aluminium alcoholates Hydrolyze method.Preparation method among the patent CN1184289 of preferred Beijing Chemical Research Institute Yanshan Mountain branch.As can prepare according to following mode: the use specific surface is 100～200m
2/ g, pore volume are 0.5～1.5ml/g, and the most probable aperture is that the aluminium oxide of 80～200 dusts immerses in the compound titanium solution, the consumption of wherein said solution at least with the total pore volume equivalent of said aluminium oxide, and stirred 10～30 minutes; With impregnated aluminium oxide under 100～150 ℃ temperature dry 4～10 hours, in 500～900 ℃ temperature lower calcination 4～8 hours, make the aluminium oxide-titanium oxide composite oxide carrier that contains 5～20wt% titanium oxide based on alumina weight then.
In an embodiment of the present invention, said catalyst is C
10～C
16The selection 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 the above-mentioned catalyst, the content of Ni-B amorphous alloy is 4～40wt%, preferred 4～20wt%; The mol ratio of Ni and B is 3: 1～1: 3, preferred 1: 1～1: 3; Nickel loading is 4～20wt% based on gross mass.The long-chain normal diene hydrocarbon selects hydrogenation to generate the long-chain normal monoolefine.
The present invention also provides a kind of technology for preparing above-mentioned catalyst, comprising:
(1) with Al
2O
3-TiO
2Composite oxide carrier adds in the nickel salt solution, and dipping stirs, and filters washing;
(2) at 0～30 ℃, under the inert atmosphere, add metal hydroboron solution, stir, produce up to no gas.
In above-mentioned preparation technology's the preferred enforcement:
(1) with TiO
2Be Al
2O
35～20% Al of weight
2O
3-TiO
2Composite oxide carrier adds in the nickel salt solution, and dipping stirred 4 hours, filters washing;
(2) under 0～10 ℃, under the blanket of nitrogen, add metal hydroboron solution, in 15～25min, add, vigorous stirring produces up to no gas simultaneously.
Among the above-mentioned preparation technology; Said nickel salt is appreciated that the nickel salt that adopts usually with catalyst into selective hydrogenation; Can include but not limited to: the sulfate of nickel, nitrate, solubility carboxylate, hypophosphites and halide are preferably nickelous sulfate, nickel nitrate, nickel chloride and nickel acetate.The not special restriction of the type of said nickel salt solution; Can be the aqueous solution, also can be the organic nickel salting liquid that ethanol, benzene etc. form as solvent, but use organic nickel salting liquid cost higher; And also have pollution problem, so the present invention preferably uses the aqueous solution of inorganic nickel.
Among the above-mentioned preparation technology, the preferred potassium borohydride of described metal hydroboron, sodium borohydride or its mixture.The not special restriction of the type of said metal hydroboron solution; Can be the aqueous solution, also can be the organic solution that ethanol etc. forms as solvent, but use the organic solution cost higher; And also have pollution problem, so the present invention preferably uses the aqueous solution of metal hydroboron.
Catalyst through above-mentioned prepared can directly use; Also can filter, wash to neutrality, absolute ethanol washing, place absolute ethyl alcohol to preserve.
Catalyst of the present invention, than preparing down with inert atmosphere under the low reaction temperatures, the reunion or the crystallization of the alloying pellet that can avoid generating obtain the catalyst that amorphous state granular size and particle diameter are evenly distributed.Through NiB is loaded on TiO with chemical reduction method
2-Al
2O
3On the complex carrier, compare, can improve the decentralization of reactive metal, help reactant and contact closely, thereby improve the activity of catalytic hydrogenation, and can change its electronic property with catalyst active center with using aluminium oxide.Because TiO
2The adding carrier on more B acid site is arranged, and the B acid on support type Ni catalyst carrier surface has the electronic induction effect to the Ni cluster, makes it to appear " electronics shortage " performance.When the metal surface presented " electronics shortage " state, the metallic atom cloud density reduced, and the hydrogenation activity of alkadienes strengthens thereupon, explained that the B acid site on the carrier can improve the hydrogenation performance of Ni catalyst.This catalyst has bigger aperture; (the v) above channel diameter of %＞100 dusts on the preferred carrier 97; For the diene selective hydrotreating reaction, hydrogen and the reactant molecule collision frequency in catalyst active center promptly can be improved in the duct that increases catalyst; Can increase the colloidal sol ability of catalyst again, improve its stability.
Catalyst of the present invention loads on the aluminium oxide-titanium oxide composite oxide carrier with NiB, can increase the mechanical strength of catalyst, and compression strength reaches 180N/cm, far surpasses the anti-pressure ability of carried non-crystal NiB catalyst of the same type.The high strength carrier is difficult for broken in catalyst filling and use, can repeated multiple times regenerate, and therefore helps improving the stability of catalyst, prolongs the time of catalyst even running, and improves hydrogenation activity, has good low temperature active simultaneously.
Catalyst of the present invention is with commonly used with Al in the industry
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 be taken into account Al
2O
3Excellent catalytic activity and TiO
2Anti-carbon, anti-poisoning capability can further improve the catalytic performance and the stability of Ni-B catalyst.Catalyst of the present invention is used for C
10～C
16The selective hydrogenation of long-chain normal diene hydrocarbon; Can obviously improve diene conversion ratio and diolefin hydrogenation and generate the monoene selectivity; Can reach the purpose that removes long-chain normal diene, increases long-chain normal monoene output through one section or two-stage hydrogenation technology, can simplify technical process and reduce equipment investment.
Through the catalyst of the present invention's preparation, the selective hydrogenation that can be used for a small amount of diene in the monoolefine generates monoolefine, is particularly useful for C
10～C
16Long-chain normal diene hydrocarbon-selective hydrogenation generates the long-chain normal monoolefine.
The specific embodiment
Below by instance preferential embodiment of the present invention has been carried out further elaboration, should be appreciated that preferred embodiment described herein only is used for explanation and explains the present invention, and be not used in qualification the present invention.
Embodiment 1:
Al among the patent CN1184289C of the carrier employing Yanshan Mountain, Beijing Chemical Research Institute branch
2O
3-TiO
2Composite oxide carrier takes by weighing 5g Al
2O
3-TiO
2, titanium oxide is 5% of an aluminium oxide quality, under agitation slowly joins in the 20ml nickel sulfate solution; Concentration of nickel sulfate is 5% in the theoretical negative carrying capacity of Ni, and dipping stirred 4 hours, filters; Filter cake adds 12ml distilled water, under 0 ℃, nitrogen protection, adds a certain amount of 1mol/L KBH
4Solution makes Ni: the mol ratio of B is 1: 1, in 15min, drips off.Vigorous stirring produces up to no gas.Make catalyst 1, data are seen table 1.
Embodiment 2:
Al among the patent CN1184289C of the carrier employing Yanshan Mountain, Beijing Chemical Research Institute branch
2O
3-TiO
2Composite oxide carrier takes by weighing 5g Al
2O
3-TiO
2, titanium oxide is 5% of an aluminium oxide quality, under agitation slowly joins in the 20ml nickel nitrate aqueous solution; Nickel nitrate concentration is 10% in the theoretical negative carrying capacity of Ni, and dipping stirred 4 hours, filters; Filter cake adds 12ml distilled water, under 0 ℃, nitrogen protection, adds a certain amount of 1mol/L KBH
4Solution makes Ni: the mol ratio of B is 1: 2, in 15min, drips off.Vigorous stirring produces up to no gas.Make catalyst 2, data are seen table 1.
Embodiment 3:
Al among the patent CN1184289C of the carrier employing Yanshan Mountain, Beijing Chemical Research Institute branch
2O
3-TiO
2Composite oxide carrier takes by weighing 5g Al
2O
3-TiO
2, titanium oxide is 10% of an aluminium oxide quality, under agitation slowly joins in the 20ml nickel chloride aqueous solution; Nickel chloride concentration is 15% in the theoretical negative carrying capacity of Ni, and dipping stirred 4 hours, filters; Filter cake adds 12ml distilled water, under 0 ℃, nitrogen protection, adds a certain amount of 1mol/L KBH
4Solution makes Ni: the mol ratio of B is 1: 2.5, in 15min, drips off.Vigorous stirring produces up to no gas.Make catalyst 3, data are seen table 1.
Embodiment 4
Al among the patent CN1184289C of the carrier employing Yanshan Mountain, Beijing Chemical Research Institute branch
2O
3-TiO
2Composite oxide carrier takes by weighing 5g Al
2O
3-TiO
2, titanium oxide is 10% of an aluminium oxide quality, under agitation slowly joins in the 20ml nickel acetate aqueous solution; Nickel acetate concentration is 20% in the theoretical negative carrying capacity of Ni, and dipping stirred 4 hours, filters; Filter cake adds 12ml distilled water, under 0 ℃, nitrogen protection, adds a certain amount of 1mol/L KBH
4Solution makes Ni: the mol ratio of B is 1: 3, in 15min, drips off.Vigorous stirring is not till extremely reaction has gas to generate.Make catalyst 4, data are seen table 1.
Embodiment 5:
Al among the patent CN1184289C of the carrier employing Yanshan Mountain, Beijing Chemical Research Institute branch
2O
3-TiO
2Composite oxide carrier takes by weighing the Al of 5g
2O
3-TiO
2, titanium oxide is 10% of an aluminium oxide quality, under agitation slowly joins the 50ml nickel acetate aqueous solution, nickel acetate concentration is 20% in the theoretical negative carrying capacity of Ni.Dipping stirred 4 hours, filtered, and filter cake adds in the distilled water of 12ml.Under 0 ℃, nitrogen protection, add a certain amount of 1mol/L NaBH
4Solution makes Ni: the mol ratio of B is 1: 3, adds in the 20min.Vigorous stirring is not till extremely reaction has gas to generate.Make catalyst 5, data are seen table 1.
Table 1
Comparative Examples 1:
The catalyst of embodiment 1 among the patent CN1268549A is to intend thin water Al
2O
3Powder is a raw material, and with the method moulding of spin, through 120 ℃ of dryings 5 hours, γ-Al was processed in 550 ℃ of roastings 5 hours
2O
3Bead is used PdCl
2Aqueous solution dipping, through 120 ℃ of dryings 4 hours, H was used in 500 ℃ of roastings 4 hours then
2Reduced 3 hours down at 100 ℃, make the catalyst C-1 that finished product contains Pd 0.2wt%.
Comparative Examples 2:
The catalyst of embodiment 4 among the patent CN1974005A is got 2g nonionic three block high polymers (polyethylene oxygen-polypropylene oxygen-polyethylene oxygen) EO
20PO
70EO
20(P123) be dissolved in the 15ml water, add the HCI of 60ml concentration 2mol/L, stir 1h and be placed in 40 ℃ of water-baths; Behind the stir about 0.5h, slowly drip 4.25g ethyl orthosilicate (TEOS) solution, continue to stir 24h; Pack in the stainless steel cauldron, place 100 ℃ of baking oven constant temperature 24h.Gained white opacity liquid is filtered, washing, 100 ℃ of dryings, 550 ℃ of roasting 6h promptly get SBA-15.Get the 2.64ml butyl titanate and add in the 110ml absolute ethyl alcohol, shake up the 20gSBA-15 carrier that adding makes, rotary evaporation is extremely done, 120 ℃ of dried overnight, and 550 ℃ of roasting 4h get carrier 3.0%TiO
2-SBA-15.
Get the PdCl of 10ml distilled water and 20ml
2The aqueous solution (concentration 3.0105gPd/L) places 80 ℃ of water-bath 30min, under agitation adds the above-mentioned 3.0%TiO of 20g
2-SBA-15,80 ℃ of water bath methods, 120 ℃ of oven dry are spent the night.The activation dechlorination condition of catalyst is following: with the flow bubbling air activation 1h of 50ml/min, again at uniform temp, feed 80 ℃ saturated steam dechlorination 1h under the same traffic under 500 ℃.Get C-2 catalyst 0.3%Pd/3.0%TiO
2-SBA-15.
Embodiment 6
The catalytic performance of evaluate catalysts 1～5.
In fixed bed reactors, carry out long-chain (C with the full hydrogen hydrogenation technique that dissolves
10～C
16) the normal diene selective hydrogenation.The feedstock oil that will contain 85.2wt% long chain alkane, 10.0wt% long-chain monoolefine, 1.17wt% long-chain diolefin and 3.61wt% aromatic hydrocarbons is added in the autoclave of 2.0L, 100 ℃ and the following dissolving of 0.9MPa H
2The beds to saturated back through filling with C-1 in catalyst among the embodiment 1～5 and the Comparative Examples and C-2 respectively; The catalyst packing volume is 10ml; Reaction pressure all adopts 1.5MPa; The mol ratio that joins diene in hydrogen and the feedstock oil in the feedstock oil is 1: 1, and reaction temperature is 100 ℃, and the liquid air speed of material is 5.0h
-1Utilize material behind the gas chromatographic analysis hydrogenation.Each activity of such catalysts and selective evaluation result see table 2.
Table 2
| Catalyst | Diene conversion ratio (mol%) | Generate the selectivity (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 optionally computing formula of monoene:
Should be noted in the discussion above that through present disclosure being described, but be to be understood that to wherein used word is descriptive and explanatory vocabulary with reference to preferred embodiment, rather than limited vocabulary.Can be by in the scope that is defined in claim of the present invention the present invention being modified, and in not deviating from scope of the present invention and spirit, the present invention is revised.Although the present disclosure of wherein describing relates to specific catalyst, preparation method and embodiment; But and do not mean that present disclosure is limited to wherein disclosed particular case; On the contrary, present disclosure can extend to other all have catalyst, preparation method and the application of same composition.
Claims (10)
1. select hydrogenation catalyst for one kind, comprise Ni-B amorphous alloy and Al
2O
3-TiO
2The composite oxide carrier material.
2. catalyst according to claim 1 is characterized in that, the content of said Ni-B amorphous alloy is 4～40wt%; Preferred 4～20wt%.
3. catalyst according to claim 1 and 2 is characterized in that, the mol ratio of Ni, B is 3: 1～1: 3 in the said Ni-B amorphous alloy, preferred 1: 1～1: 3.
4. according to any described catalyst in the claim 1～3, it is characterized in that nickel loading is 4～20wt% based on gross mass in the said Ni-B amorphous alloy.
5. according to any described catalyst in the claim 1～4, it is characterized in that said catalyst is C
10～C
16The long-chain normal diene hydrocarbon is selected hydrogenation catalyst, comprises Ni-B amorphous alloy and Al
2O
3-TiO
2Composite oxide carrier material, the content of Ni-B amorphous alloy are 4～20wt%; The mol ratio of Ni, B is 1: 1～1: 3 in the said Ni-B amorphous alloy; Nickel loading is 4～20.0wt% based on gross weight in the said Ni-B amorphous alloy.
6. according to any described catalyst in the claim 1～5, it is characterized in that said selection hydrogenation catalyst is used for the selection hydrogenation of diolefin, is preferred for C
10～C
16The selection hydrogenation of long-chain normal diene hydrocarbon.
7. technology for preparing any described catalyst in the claim 1～5 comprises:
A. with Al
2O
3-TiO
2Composite oxide carrier adds in the nickel salt solution, and dipping stirs, and filters washing;
B. under 0～30 ℃, under the inert atmosphere, add metal hydroboron solution, stir, produce up to no gas.
8. technology according to claim 7 is characterized in that, in b, said temperature is 0～10 ℃.
9. according to claim 7 or 8 described technologies, it is characterized in that said nickel salt is selected from nickel halogenide, nickelous sulfate, nickel nitrate, nickelous hypophosphite and solubility nickel carboxylate, preferred nickel nitrate, nickelous sulfate, nickel chloride and/or nickel acetate.
10. according to any described preparation technology in the claim 7～9, it is characterized in that the metal hydroboron is potassium borohydride, sodium borohydride or its mixture.
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| CN105080594A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Nickel-based catalyst and preparation method therefor |
| 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 |
| CN106492808A (en) * | 2016-09-06 | 2017-03-15 | 中国科学院广州能源研究所 | A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method |
| 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 |
| CN118874549A (en) * | 2024-09-27 | 2024-11-01 | 山东新和成药业有限公司 | A composite catalyst and its preparation method and application |
| CN118874549B (en) * | 2024-09-27 | 2024-12-24 | 山东新和成药业有限公司 | Composite catalyst and preparation method and application thereof |
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