CN104689830B - A kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins - Google Patents
A kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins, belong to petrochemical industry.The catalyst is with TiO2‑Al2O3Composite oxides are carrier, load main active metal component Pd and help active metal component Ni.The preparation method of the catalyst includes that first active metal component Ni will be helped to be supported on carrier, loads main active metal component Pd again later.It is greatly, activity stabilized to hold " green oil " amount for the hydrogenation activity and high selectivity of the catalyst.Compared with loading a variety of main active components in the prior art and helping the catalyst of active component, catalyst provided by the invention reduces the type of active component, reduces production cost, simplifies preparation process.
Description
Technical field
The present invention relates to a kind of selective hydrogenation catalysts to belong to for the alkynes and diolefin hydrogenate in mixed olefins
In petrochemical industry.
Background technology
The catalyst of load Pd and Ni has long been used for various hydrogenation techniques, which includes in various mixing hydrocarbon streams
The selection of acetylene hydrocarbon compound and diolefin adds hydrogen and cracking and the selection of catalytic gasoline to add hydrogen etc..
In order to improve the selectivity of catalyst, add hydrogen general the various mixing hydrocarbon streams containing acetylene hydrocarbon compound and diolefin
Using the bimetallic or multicomponent catalyst of Pd or Pd and other metal compatibilities, such as US7,217,760B2 disclose NH4I processing
Pd-Ag catalyst, US7,009,085B2 discloses the Pd-Ag catalyst using P or Br modified supports.
M.L.Derrien Et Al.(Studies in Surface Science and Catalyst,Vol27,
Page613 (1986)), and Elsvier and K James Sasski (Petrochemical and Gas Processing,
113PTQ Autumn, 1997) think that Pt-supported catalyst adds hydrogen to have unstability, reason the selection of vinylacetylene
Complex compound can be formed with Pd in hydrogenation process for vinylacetylene, Pd complex compounds dissolve in hydrocarbon stream and lead to activearm
Divide the loss of Pd so that catalyst activity reduction.
CN1604955A disclose it is a kind of selection plus hydrogen multicomponent catalyst, including Pd or containing Pd and its one kind the 8th
Race's metal is selected from Pt, Ir, Ru, Co or Ni and at least two metals are selected from Ag, Zn or Bi, and the active component of catalyst is carried on
On aluminium oxide, the BET surface area of the carrier is 20~70m2/ g, alumina support are molding excessive oxidation aluminium, and apparent accumulation is close
Degree is 0.7~0.8g/cm2, it is the mixed crystallization form of α, γ, θ, σ, ρ, η, κ and χ.The catalyst is for hydrogenating various insatiable hungers
With the acetylene and alkadienes in hydrocarbon stream.
CN102039130A discloses a kind of selective hydrogenation catalyst, including porous inorganic carrier, is carried on porous carrier
On main active component Pd, Au and Ag and it is at least one selected from Bi, Zr, Ce, Zn, Ni, Cu, K, Mg, Ba, Ca, Sn, Pd, Mn,
La, Ti, Sr and Na's helps active component, which can make the work of catalyst due to the synergistic effect of various active component
Property and selectivity be significantly improved, and with good antioxygen poisoning and anti-carbon monoxide fluctuating nature, have selection
Add hydrogen and selection Oxidation of Carbon Monoxide difunctional, which also has the regeneration period long, the features such as service life is long, still,
The active metal type of the catalyst is more, involves great expense.
It is various mixing hydrocarbon streams in acetylene hydrocarbon compound and diolefin selection hydrogenation process in, be adsorbed on catalyst table
The components such as alkynes and diolefin on face are easy by adding hydrogen dimerization, so again combinate form at C6~C24High polymer, i.e., it is so-called
The generation of " green oil ", " green oil " the blocking catalyst duct generated, causes the activity and selectivity of catalyst constantly to decline, is
The activity and selectivity for keeping catalyst is needed using the measures such as reaction temperature are improved, and corresponding is alkynes and diene
The components polymerisation such as hydrocarbon is also aggravated, and " green oil " production quantity increases, and causes catalyst frequent regeneration, and influence catalyst uses the longevity
Life.
Catalyst disclosed in existing patent and technology, however it remains activity and selectivity is not high, and stability is bad, i.e.,
It is higher therefore, it is necessary to research and develop a kind of activity and selectivity, it is possible to reduce " green oil " not solve the problems, such as that catalyst long period is used
It generates or holds " green oil " and measure big catalyst.
Invention content
In order to overcome the above-mentioned problems in the prior art, the present invention provide it is a kind of for mix in hydrocarbon stream alkynes and
The selective hydrogenation catalyst of alkadienes.The catalyst has the characteristics that low temperature active height, high selectivity, stability are good.The present invention
Another object is to provide the preparation method of the catalyst.
The present invention provides a kind of catalyst for the alkynes and diolefin hydrogenate in mixed olefins, the catalysis
Agent is loaded catalyst, specifically with TiO2-Al2O3Composite oxides are carrier, supported active metals component Pd and Ni.Its
Middle Pd is main active metal, and Ni is to help active metal.
Based on the total weight of the catalyst, the content of Pd is calculated as 0.005~0.8wt% with atom, preferably 0.01~
0.3wt%;The content of Ni is calculated as 1~12wt%, preferably 2~10wt% with atom.Pd and Ni can be in the form of atom or compound
In the presence of.Pd the and Ni compounds can be common Pd and Ni compounds in selective hydrogenation palladium base and nickel-base catalyst,
Preferably Pd oxides and Ni oxides, such as Pd2O and NiO.
In the catalyst, TiO2-Al2O3The content of composite oxide carrier is 87.2~99.9wt%.In the carrier
TiO2Content is 3~30wt%, preferably 5~20wt%.The most probable pore size of the carrier isPreferably0.50~0.64ml/g of Kong Rongwei, preferably 0.52~0.60ml/g;Specific surface area is 70~120m2/ g, it is excellent
It is selected as 80~110m2/g.The present invention is not particularly limited the shape of carrier, can be cylindricality, bar shaped, spherical shape or clover
Shape.Specific surface area, Kong Rong and the most probable pore size of the carrier are measured by nitrogen physisorption (BET) method.
Carrier is prepared as known technology in the catalyst, and sol-gel method, the aluminium salt precipitation method, coprecipitated may be used
The preparations such as shallow lake method, aluminium salt neutralisation or aluminium alcoholates Hydrolyze method.It is preferred that in the patent CN1184289 of Beijing Chemical Research Institute Yanshan Mountain branch
Preparation method:It is 60~160m with specific surface20.50~1.5ml/g of/g, Kong Rongwei, most probable pore size are's
Aluminium oxide immerses in compound titanium solution, the dosage of the compound titanium solution at least with the aluminium oxide total pore volume equivalent.It is quiet
It sets 10~30 minutes, impregnated aluminium oxide is 4~8 hours dry at a temperature of 100~150 DEG C, then in 400~600
DEG C roasting temperature 3~6 hours is made and is based on TiO2-Al2O3Composite oxides weight contains the TiO of 5~20wt%2TiO2-
Al2O3Composite oxide carrier.
Invention further provides the preparation methods of above-mentioned selective hydrogenation catalyst.
The method for preparing catalyst of the present invention, including first active metal component Ni will be helped to be supported on carrier, it bears again later
Carry main active metal component Pd;Or first main active metal component Pd is supported on carrier, it loads again help active metal group later
Divide Ni.Preferably, first active metal component Ni will be helped to be supported on carrier, and will load main active metal component Pd again later.
In the preparation process in accordance with the present invention, the load of the methods of conventional dipping, spraying can be used for active metal component.
It helps the load of active metal component Ni and main active metal component Pd that substep can be taken to carry out, can also take the synchronous side carried out
Formula.
Preferably, the catalyst can be prepared by the following method:
1)By TiO2-Al2O3Composite oxide carrier, which is added in nickel salt solution, to be impregnated, then dry and roasting;
2)By step 1)Obtained carrier, which is added in palladium solution, to be impregnated, and is then restored, is filtered washing and be dried to obtain described
Catalyst.
In one particular embodiment of the present invention, the catalyst is prepared by the following method:
i)By TiO2-Al2O3Composite oxide carrier is small with the nickel salt solution dipping 1~2 equal with catalyst ni content
When, dry 4~8 hours at a temperature of 100~150 DEG C, then in 400~600 DEG C of roasting temperatures 3~6 hours, it is made and urges
Agent precursor;
ii)By i)In the catalyst precarsor obtained palladium salt solution impregnation equal with catalyst amount containing Pd 1~2 hour,
Then 1~3 times that volume is the catalyst precarsor is added, the hydrazine hydrate solution of a concentration of 5~10wt% restores 1~2 hour,
Filtering, is washed with deionized, 4~8 hours dry at a temperature of 100~150 DEG C, and catalyst of the present invention is made.
In above-mentioned preparation method, the nickel salt can be understood as the nickel of selective hydrogenation nickel catalyst generally use
Salt can include but is not limited to:Sulfate, nitrate, soluble carboxylate, hypophosphites and the halide of nickel, preferably sulphur
Sour nickel, nickel nitrate, nickel chloride or nickel acetate.The type of the nickel salt solution is not particularly limited, and can be aqueous solution, can also
It is organic nickel salt solution that ethyl alcohol, benzene etc. are formed as solvent.But it is higher using organic nickel salt solution cost, and there is environment to ask
Topic, therefore present invention preferably uses the aqueous solutions of inorganic nickel.
In above-mentioned preparation method, the palladium salt can be understood as the palladium of selective hydrogenation palladium series catalyst generally use
Salt can include but is not limited to:Nitrate, soluble carboxylate and the halide of palladium, preferably palladium nitrate, palladium bichloride, oxalic acid
Palladium or acid chloride.The type of the palladium salt solution is not particularly limited, and can be aqueous solution, can also be the conducts such as ethyl alcohol, benzene
The organic palladium salting liquid that solvent is formed.But it is higher using organic palladium salting liquid cost, and have environmental problem, therefore the present invention is excellent
Choosing uses the aqueous solution of inorganic palladium salt.
The selection that catalyst of the present invention is mainly used in alkynes and alkadienes in mixed olefins adds hydrogen, and it is mixed to be particularly suitable for C4
The selection for closing alkynes and butadiene in alkene adds hydrogen, to substantially reduce the content of alkynes and butadiene in C4 mixed olefins, reaches
To the purpose of refined C4 mixed olefins.
Selective hydrogenation catalyst provided by the invention has the following advantages and effect:
(1)The hydrogenation activity and high selectivity of catalyst.It is selected for 84%, 1- butylene with butadiene conversion in the prior art
Selecting property is compared for 45%, and the selection using catalyst of the present invention in C4 mixed olefins logistics adds hydrogen, butadiene conversion reachable
96% is selectively can reach to 94%, 1- butylene.
(2)It is greatly, activity stabilized that catalyst holds " green oil " amount.Alkynes conversion ratio, the butadiene of selection plus hydrogen 100h and 1000h
Conversion ratio and the selectively variation of 1- butylene are little.
(3)Compared with loading a variety of main active components in the prior art and helping the catalyst of active component, the present invention provides
Catalyst reduce the type of active component, reduce production cost, simplify preparation process.
Specific implementation mode
Below by embodiment, the present invention is further illustrated, but these embodiments are not to the scope of the present invention structure
At any restrictions.
Embodiment 1
1.TiO2-Al2O3It is prepared by composite oxide carrier
It is 90m to take BET specific surface area2/ g, Kong Rongwei 0.55ml/g, most probable pore size areAl2O3100g is used
55mlTiO2The titanium sulfate solution that content is 19.05g impregnates, and stands 10~30 minutes, dry 6 hours at 110 DEG C, then in
It is roasted 4 hours at 480 DEG C, TiO is made2Content is the TiO of 16wt%2-Al2O3Composite oxide carrier A-1;
2. prepared by catalyst precarsor
A-1 composite oxide carrier 100g are taken, the nickel nitrate solution for being 11.1g with 50ml NiO contents impregnates 20~30 points
Clock, it is 6 hours dry at 110 DEG C, it is then roasted 4 hours at 450 DEG C, the catalyst precarsor B- that NiO contents are 10wt% is made
1;
3. catalyst preparation
B-1 catalyst precarsor 100g are taken, the palladium chloride aqueous solution for being 0.3g with 85ml Pd contents impregnates, after standing 1 hour
It takes out, drains away the water, restored 1 hour, be washed with deionized to no chlorine with the hydrazine hydrate aqueous solution of a concentration of 10wt% of 120ml
Ion, 6 hours dry at 110 DEG C, it is 10wt% and TiO that obtained Pd contents, which are 0.3wt%, NiO content,2Content is 16wt%'s
Pd-Ni/TiO2-Al2O3Catalyst C-1.
Embodiment 2~7
Method for preparing catalyst is with embodiment 1, the difference is that changing NiO, Pd and TiO2Catalyst C- is made in content respectively
2, C-3, C-4, C-5, C-6 and C-7, active metal component and TiO in catalyst2Content be shown in Table 1.
Table 1
Catalyst is numbered | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
Pd(wt%) | 0.3 | 0.3 | 0.3 | 0.2 | 0.1 | 0.3 | 0.3 |
NiO(wt%) | 10 | 5.0 | 12.0 | 10.0 | 10.0 | 10.0 | 10.0 |
TiO2(wt%) | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 | 5.0 | 20.0 |
Embodiment 8
Catalyst C-1~C-7 is evaluated in mixing C4Catalytic performance in selection plus hydrogen.
Each 50g of C-1~C-7 catalyst is taken, is 0.2~3.0MPa in Hydrogen Vapor Pressure, temperature is 350~450 DEG C and hydrogen
Flow is to be restored 6~15 hours under conditions of 20~100ml/ minutes, and catalyst is enable to activate, and then cools to reaction temperature
Degree, charging reaction.
It is 1.0MPa in reaction pressure, reaction temperature is 38 DEG C, hydrogen/(Diene+alkynes)=1.2, mix C4Feed space velocities are
3.0h-1, recycle ratio 15:Under conditions of 1, it is passed through that iso-butane content is 1.23wt%, normal butane content is 1.84wt%, trans- 2-
Butylene 2.30wt%, 1- butene content is 5.71wt%, isobutene content 21.27wt%, cis-2-butene content be 24.18wt%,
The mixing C4 raw materials that butadiene content is 24.25wt%, alkynes content is 15.48wt% and other contents are 3.74wt%, reaction
1h utilizes material after gas chromatographic analysis plus hydrogen.Each catalyst adds hydrogen result such as table 2, wherein each numerical value is quality percentage
Number.
Table 2
Catalyst | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
Alkynes conversion ratio(%) | 77.26 | 70.80 | 78.23 | 75.58 | 65.96 | 76.42 | 77.58 |
Butadiene conversion(%) | 94.60 | 93.65 | 94.72 | 93.98 | 90.26 | 94.47 | 94.72 |
1- butylene selectivity(%) | 56.1 | 54.6 | 55.0 | 52.3 | 42.81 | 54.0 | 51.6 |
1- butylene in product(%) | 25.49 | 24.81 | 24.99 | 23.77 | 19.45 | 24.53 | 23.45 |
Butadiene in product(%) | 1.31 | 1.54 | 1.28 | 1.46 | 2.36 | 1.34 | 1.28 |
Alkynes in product(%) | 3.52 | 4.05 | 3.37 | 3.78 | 5.27 | 3.65 | 3.47 |
The calculation formula of butadiene conversion and 1- butylene selectivity:
Table 2 illustrates that compared with reaction raw materials, carrying out selectivity to mixing C4 raw materials using catalyst provided by the invention adds
Hydrogen, the content of 1- butylene improves 20% in product, and the content of butadiene has dropped 22~23%, and the content of alkynes is decrease beyond
10%。
Embodiment 9
The LD365 palladium-based catalysts of catalyst C-1 prepared by embodiment 1 and French Petroleum Institute production, Yi Jihe
The HTC-300S nickel-base catalysts of blue Akzo Nobel N.V.'s production carry out under the same conditions plus hydrogen comparison.
HTC-300S catalyst 50g are taken, in the case where Hydrogen Vapor Pressure is 0.5MPa with the hydrogen flow rate of 250ml/min/g catalyst
It is passed through hydrogen, entire catalyst bed is heated to 230 DEG C, is kept for 1 hour, catalyst is enable to activate, is then cooled to anti-
Answer temperature, charging reaction.
C-1 and LD365 catalyst 50g are respectively taken, the catalyst activation process of embodiment 9 is repeated.Using same as Example 9
Raw material and reaction condition carry out hydrogenation reaction, tri- kinds of catalyst of C-1, LD365 and HTC-300S plus hydrogen result such as table 3.
Table 3
Catalyst | C-1 | LD365 | HTC-300S |
Alkynes conversion ratio(%) | 77.26 | 72.35 | 66.47 |
Butadiene conversion(%) | 94.60 | 84.86 | 72.17 |
1- butylene selectivity(%) | 56.1 | 45.42 | 40.32 |
1- butylene in product(%) | 25.49 | 20.64 | 18.32 |
Butadiene in product(%) | 1.31 | 3.67 | 6.75 |
Alkynes in product(%) | 3.52 | 4.28 | 5.19 |
Note:The palladium content of LD365 catalyst is 0.33wt%
Table 3 illustrates, compared with existing LD365 and HTC-300S catalyst, using catalyst provided by the invention to mixed
It closing C4 raw materials and carries out selective hydrogenation, the content of 1- butylene improves 5~7% in product, and the content of butadiene has dropped 3~6%,
The content of alkynes has dropped 1~2%.
Embodiment 10
It is 90m to take BET specific surface area2/ g, Kong Rongwei 0.55ml/g, most probable pore size areAl2O3Carrier 100g.
Lanthanum nitrate is weighed, incipient impregnation carrier is used after being dissolved in water, it is then 6 hours dry in 120 DEG C, so that final catalyst is contained
Lanthanum amount is 0.5wt%.Palladium nitrate solution is taken, palladium nitrate solution is sprayed on above-mentioned carrier using incipient impregnation method, is made most
Whole catalyst amount containing palladium is 0.03wt%, 6 hours dry in 120 DEG C, and 480 DEG C roast 4 hours, meanwhile, using identical isometric
Dipping method load silver and bismuth, make the silver content of final catalyst and bismuth-containing amount be respectively 0.09wt% and 0.03wt%, and dry,
Roasting.It is calculated according to equivalent impregnation method, takes suitable HAuCl3, the Na of 0.02M is added2CO3Solution, adjust pH value be 5.5~
6.0 obtained gold solutions, spray on above-mentioned carrier, after standing 12 hours, impregnate above-mentioned carrier 8 hours with the ammonium hydroxide of 2wt%, spend
Ionized water washs repeatedly removes chlorion, 6 hours dry in 120 DEG C, is roasted 4 hours in 400 DEG C, is made and contains
0.03Pd0.01Au0.09Ag0.09Bi0.5La/Al2O3Catalyst BH1.
TiO is taken respectively2And SiO2Carrier 100g is made and contains according to the identical method of BH1 catalyst is prepared
0.03Pd0.01Au0.09Ag0.09Bi0.5La/TiO2Catalyst BH2 and 0.03Pd0.01Au0.09Ag0.09Bi0.5La/
SiO2Catalyst BH3.
C-1, BH1, BH2 and BH3 catalyst 50g are respectively taken, the catalyst activation process of embodiment 9 is repeated.Using with implementation
9 identical raw material of example and reaction condition carry out hydrogenation reaction, the results are shown in Table 4.
Table 4
As seen from Table 4, using polymetallic catalyst BH1, BH2 and BH3 for mixing C4Selection plus hydrogen are urged with the present invention
Agent compares, and the alkynes conversion ratio and butadiene conversion for starting 100 hours four kinds of catalyst are not much different, still, with
The increase difference of experimental period increases, and in 300 hours experimental periods, the alkynes conversion ratio of BH1, BH2 and BH3 decline respectively
5.8%, 8.76% and 8.77%, butadiene conversion has dropped 5.84%, 6.1% and 7.31% respectively, and catalyst alkynes of the present invention
Hydrocarbon conversion rate and butadiene conversion are basically unchanged, and illustrate multimetal reforming catalyst BH1, BH2 and BH3 for mixing C4Hydrogenation activity
It is unstable.
Embodiment 11
Evaluation catalyst of the present invention is to mixing C4The stability of selection plus hydrogen.
Example 1 prepare C-1 catalyst 80g, repeat embodiment 9 catalyst activation process, using with embodiment 9
Identical mixing C4 raw materials and reaction condition carry out hydrogenation reaction, change the reaction time, add hydrogen result such as table 5.
Table 5
As can be seen from Table 4, C-1 catalyst was reacted after 1000 hours, and activity and selectivity does not decline, and showed this
Inventing C-1 catalyst has higher appearance " green oil " ability and good stability.
In conclusion the active metal type that selective hydrogenation catalyst provided by the invention uses is few, can significantly improve
The butadiene and alkynes content in C4 raw materials are mixed, there is selectivity well.And after the longer usage time of experience, still have
Preferable stability.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (8)
1. a kind of catalyst preparing 1- butylene for alkynes in mixed olefins and diolefin hydrogenate, the catalyst with
TiO2-Al2O3Composite oxides are carrier, load main active metal component Pd and help active metal component Ni, are based on the catalysis
The content of the total weight of agent, Pd is calculated as 0.2~0.3wt% with atom, and the content of Ni is calculated as 7.87~10wt% with atom.
2. catalyst according to claim 1, which is characterized in that the TiO2-Al2O3TiO in composite oxide carrier2Contain
Amount is 3~30wt%.
3. catalyst according to claim 2, which is characterized in that the TiO2-Al2O3TiO in composite oxide carrier2Contain
Amount is 5~20wt%.
4. catalyst according to claim 1, which is characterized in that the TiO2-Al2O3Composite oxide carrier most may be used
Several apertures are0.50~0.64ml/g of Kong Rongwei;Specific surface area is 70~120m2/g。
5. catalyst according to claim 4, which is characterized in that the TiO2-Al2O3Composite oxide carrier most may be used
Several apertures are0.52~0.60ml/g of Kong Rongwei;Specific surface area is 80~110m2/g。
6. a kind of preparation method according to any one of Claims 1 to 5 catalyst, including:
1) by TiO2-Al2O3Composite oxide carrier, which is added in nickel salt solution, to be impregnated, then dry and roasting;
2) carrier that step 1) obtains is added in palladium solution and is impregnated, then restored, filter and wash and be dried to obtain the catalysis
Agent.
7. according to the method described in claim 6, it is characterized in that, reduction described in step 2) is to pass through hydrazine hydrate reduction.
8. the method according to the description of claim 7 is characterized in that including:
I) by TiO2-Al2O3Composite oxide carrier is impregnated 1~2 hour with the nickel salt solution equal with catalyst ni content,
Dry 4~8 hours at a temperature of 100~150 DEG C, then in 400~600 DEG C of roasting temperatures 3~6 hours, catalysis is made
Agent precursor;
Ii) by the palladium salt solution impregnation equal with catalyst amount containing Pd 1~2 hour of catalyst precarsor obtained in i), then
1~3 times that volume is the catalyst precarsor is added, the hydrazine hydrate solution of a concentration of 5~10wt% restores 1~2 hour, mistake
Filter, is washed with deionized, 4~8 hours dry at a temperature of 100~150 DEG C, and the catalyst is made.
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CN114950465B (en) * | 2022-06-30 | 2023-08-08 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in alkene and alkyne saturated hydrogenation |
CN114950471B (en) * | 2022-06-30 | 2023-07-25 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene |
CN115007155B (en) * | 2022-07-07 | 2024-03-26 | 中国科学院青岛生物能源与过程研究所 | Supported nickel-containing catalyst, preparation method thereof and method for preparing olefin by catalyzing alkyne hydrogenation by using supported nickel-containing catalyst |
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CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
CN101432247A (en) * | 2004-10-20 | 2009-05-13 | 催化蒸馏技术公司 | Selective hydrogenation process and catalyst |
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