CN105126914A - Highly dispersed catalytic system, preparation method and application thereof - Google Patents
Highly dispersed catalytic system, preparation method and application thereof Download PDFInfo
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- CN105126914A CN105126914A CN201510484803.3A CN201510484803A CN105126914A CN 105126914 A CN105126914 A CN 105126914A CN 201510484803 A CN201510484803 A CN 201510484803A CN 105126914 A CN105126914 A CN 105126914A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 150000002940 palladium Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 53
- 238000010792 warming Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003426 co-catalyst Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- -1 dry roasting Chemical compound 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a highly dispersed catalytic system, a preparation method and application thereof. The catalytic system is prepared by dissolving an organic palladium salt and a cocatalyst in a disperse phase, and carrying out hydrogen reduction. The catalytic system has a particle size of 1nm-100nm, and the metal palladium accounts for 0.01-1% of the total mass of the catalytic system. The obtained catalytic system has no carrier, is used for an acetylene-to-ethylene preparation process, has the characteristics of small dosage, low cost, high effective coefficient and high space-time yield, avoids deep hydrogenation of acetylene, and improves the acetylene conversion rate and ethylene yield. At the same time, the defects that large solid particles are likely to promote bubble merging, block a gas distributor and cause equipment wear, etc. are overcome, thus being conducive to uniform distribution of slurry bed gas-liquid-solid three phases.
Description
Technical field
The present invention relates to a kind of high dispersive catalyst system and catalyzing and its preparation method and application, belong to petrochemicals synthesis and new catalytic material technical field.
Background technology
Ethene is most important basic material in petrochemical industry, is called as " mother of petrochemical industry ".Cracking is passed through at present primarily of oil or low-carbon alkanes.And in naphtha pyrolysis stove ethene out, containing trace acetylene, it is to the toxic effect of follow-up ethylene polymerization, therefore needs acetylene content to be down to below 10ppm.
There are some researches show at present, utilize preparing ethylene by selective hydrogenation of acetylene a kind of new raw material can be provided to originate for ethylene industry, reduce ethene to the degree of dependence of petroleum resources and production cost of ethylene, have broad application prospects.Prior art discloses the method that acetylene liquid phase selective hydrogenation in slurry bed system prepares ethene.Wherein, in gas-solid catalysis system, introduce liquid phase solvent, it has high Selective dissolution to acetylene, has low Selective dissolution to ethene; Catalyst is dispersed in liquid phase solvent, utilizes liquid phase solvent to the high Selective dissolution implementation procedure coupling of acetylene, improve the selective of ethene.But those skilled in the art know, paste state bed reactor is gas-liquid-solid phase reaction, requires gas-liquid-solid Homogeneous phase mixing, but must be carried on carrier due to fixed bde catalyst, and its particle diameter is limited, and larger beaded catalyst disperses uneven in slurries; And bulky grain solid also easily blocks gas distribution holes in slurry bed system; In addition, also there is the defects such as hydrogenation activity is low, addition large, preparation complexity, equipment attrition.Therefore, be necessary to propose that a kind of particle diameter is little, the catalyst of good dispersion.
Summary of the invention
The object of this invention is to provide a kind of high dispersive catalyst system and catalyzing being applicable to producing ethylene with acetylene hydrogenation slurry bed system.Described catalyst system and catalyzing particle diameter is little, effectively prevent the problem of fixed bed large granular catalyst blocking gas distributor and equipment attrition, uses it in slurry bed system and both decreased catalyst amount, turn improve conversion of alkyne.
To achieve these goals, the present invention adopts following technical scheme:
A kind of high dispersive catalyst system and catalyzing, it is dissolved in decentralized photo by organic palladium salt, co-catalyst, obtains through hydrogen reducing; Described catalyst system and catalyzing particle diameter is between 1nm-100nm.
In the catalyst system and catalyzing that the present invention obtains, Metal Palladium accounts for the 0.01-1% of catalyst system and catalyzing gross mass.
It is little that high dispersive catalyst system and catalyzing of the present invention has particle diameter, carrier-free, for dispersed better in slurry bed system, effectively improve catalyst utilization and ethylene yield, large granular catalyst also can be avoided simultaneously to block gas distributor and equipment, the acetylene problem such as deep hydrogenation in catalyst carrier.
In catalyst system and catalyzing of the present invention, described organic palladium salt be selected from two (acetylacetone,2,4-pentanedione) palladium, hexafluoroacetylacetone palladium, tetrakis triphenylphosphine palladium, two (acetonitrile) palladium bichloride or (2,2-bipyridyl) dichloro palladium one or more.
In catalyst system and catalyzing of the present invention, described co-catalyst be selected from oil-soluble silver salt, nickel salt, ruthenium salt or cerium salt etc. one or more.
In catalyst system and catalyzing of the present invention, described decentralized photo be selected from glycerine, benzene, toluene, chloroform, acetone, paraffin, dimethyl sulfoxide (DMSO), ethylenediamine, pyridine, METHYLPYRROLIDONE, dimethyl formamide, oxolane, cyclohexanone one or more; One or more in preferably glycerine, chloroform or METHYLPYRROLIDONE, wherein, containing in the decentralized photo of METHYLPYRROLIDONE, METHYLPYRROLIDONE quality accounts for more than 80% of decentralized photo gross mass.
In order to obtain better dispersion effect, also ionic liquid can be added in decentralized photo; Described ionic liquid accounts for the 0.01-5% of decentralized photo mass fraction.Described ionic liquid be selected from [BMIM] [BF4], [BMIM] [BF4], [BMIM] Cl, [BMPyrr] [EtHPO3] or [BMPyrr] [OAC] one or more.
The present invention does not do further restriction to the consumption of organic palladium salt, co-catalyst, and the addition of said components is to realize it and dissolve completely in the solution and to make in system Metal Palladium mass fraction for 0.01-1%.
The present invention also provides a kind of preparation method of above-mentioned catalyst system and catalyzing, comprises the steps:
1) organic palladium salt, co-catalyst are dispersed in decentralized photo, form homogeneous solution;
2) by after solution warms to reduction temperature, pass into hydrogen and carry out reduction reaction, obtain dispersed catalysts.
In above-mentioned preparation method, step 2) in, described reducing condition is: be slowly warming up to 80-85 DEG C of constant 0.5h, then be warming up to 110-120 DEG C constant be 0.5h, continue to be warming up to 120-200 DEG C and carry out reduction 0.2-5h, hydrogen gas space velocity is 0.1s
-1-1s
-1.
Reduction reaction of the present invention can be carried out in reaction unit of the present invention realizing of grasping of those skilled in the art, and this is not particularly limited to again in the present invention.As one of preferred embodiment for the present invention, described reduction reaction can also be carried out in batch tank stirred reactor, and wherein Hydrogen Vapor Pressure is 0.2-1.2MPa.
The present invention also provides the application of above-mentioned catalyst system and catalyzing in preparing ethylene by selective hydrogenation of acetylene, preferred slurry bed process preparing ethylene by selective hydrogenation of acetylene.During concrete use, catalyst system and catalyzing is directly added in slurry bed system liquid phase solvent and disperse.Catalyst system and catalyzing of the present invention can be used for but is not limited to producing ethylene with acetylene hydrogenation slurry bed system.
Catalyst system and catalyzing carrier-free of the present invention, uniform particle sizes that can be less, is stably scattered in slurry bed system liquid phase.Prepare in ethylene process at acetylene and use this catalyst system and catalyzing, both catalyst amount can be reduced, cost-saving, be conducive to again improving conversion of alkyne, avoid large granular catalyst and promote that minute bubbles merge, blocking gas distributor and equipment attrition, acetylene is the problem such as deep hydrogenation in catalyst carrier.
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Concrete steps are as follows:
1) get chloroform 10g, glycerine 10g, METHYLPYRROLIDONE 80g, mixes and is made into decentralized photo;
N in molar ratio
(Pd): n
(Ag)=1:2.5 gets two (acetylacetone,2,4-pentanedione) palladium 0.286g, co-catalyst silver nitrate is dissolved in decentralized photo, obtains mixed liquor;
2) mixed liquor is slowly warming up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, continue to be warming up to 150 DEG C and pass into hydrogen reducing 2h, obtain catalyst system and catalyzing 1;
Wherein, hydrogen gas space velocity is 0.1s
-1, gained catalyst system and catalyzing 1 average diameter of particles is 13nm.
Embodiment 2
Concrete steps are as follows:
1) get glycerine 10g, METHYLPYRROLIDONE 90g, mixes and is made into decentralized photo, in molar ratio n
(Pd): n
(Ni)=1:2 gets two (acetonitrile) palladium bichloride 2.44g, co-catalyst nickel acetylacetonate is dissolved in decentralized photo, obtains mixed liquor;
2) mixed liquor is slowly warming up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, continue to be warming up to 200 DEG C and pass into hydrogen reducing 0.2h, obtain catalyst system and catalyzing 2;
Wherein, hydrogen gas space velocity is 1s
-1, gained catalyst system and catalyzing 2 average diameter of particles is 97nm.
Embodiment 3
Concrete steps are as follows:
1) get chloroform 10g, ionic liquid [BMIM] [BF4] 5g, METHYLPYRROLIDONE 85g, mixes and is made into decentralized photo; N in molar ratio
(Pd): n
(Ce)=1:1 gets hexafluoroacetylacetone palladium 2.61g, co-catalyst trifluoromethayl sulfonic acid cerium is dissolved in decentralized photo, obtains mixed liquor;
2) mixed liquor is slowly warming up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, continue to be warming up to 120 DEG C and pass into hydrogen reducing 5h, obtain catalyst system and catalyzing 3;
Wherein, hydrogen gas space velocity is 0.5s
-1, gained catalyst system and catalyzing average diameter of particles is 7nm.
Comparative example 1
N in molar ratio
(Pd): n
(Ag)=1:2.5 gets palladium bichloride and silver acetate is soluble in water, by infusion process at 40 order γ-Al
2o
30.03% ω t Metal Palladium in load, dry roasting, hydrogen reducing obtains solid catalyst.
Comparative example 2
N in molar ratio
(Pd): n
(Ce)=1:2 gets palladium nitrate and nickel acetylacetonate is soluble in water, and by infusion process load 0.03% ω t Metal Palladium on 40 order silica, dry roasting, hydrogen reducing obtains solid catalyst.
Effect experimental
The solid catalyst of the catalyst system and catalyzing of embodiment 1-3 gained and comparative example 1,2 gained is placed in slurry bed system, in slurries, palladium metal content is 200ppm, at hydrogen alkynes volume ratio 6:1, operation air speed is 45000ml/ (gcat.h), temperature is react under 150 DEG C of conditions, by reaction end gas through chromatography, result is as follows:
As seen from the above table, catalyst system and catalyzing of the present invention is prepared in ethene slurry bubble bed at acetylene, operate air speed be 45000ml/ (gcat.h) situation under use time, catalyst system and catalyzing of the present invention in conversion of alkyne, yield of ethene all apparently higher than comparative example; Illustrate that embodiment of the present invention gained catalyst system and catalyzing effectively prevent the problem of diffusion, the further hydrogenation of ethene in large granular catalyst; And in course of reaction, decrease problem such as blocking gas distributor and equipment attrition etc.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a high dispersive catalyst system and catalyzing, is characterized in that, is to be dissolved in decentralized photo by organic palladium salt, co-catalyst, obtains through hydrogen reducing; Described catalyst system and catalyzing particle diameter is between 1nm-100nm; Metal Palladium accounts for the 0.01-1% of catalyst system and catalyzing gross mass.
2. high dispersive catalyst system and catalyzing according to claim 1, it is characterized in that, described organic palladium salt be selected from two (acetylacetone,2,4-pentanedione) palladium, hexafluoroacetylacetone palladium, tetrakis triphenylphosphine palladium, two (acetonitrile) palladium bichloride and (2,2-bipyridyl) dichloro palladium etc. one or more.
3. high dispersive catalyst system and catalyzing according to claim 1, is characterized in that, described co-catalyst be selected from oil-soluble silver salt, nickel salt, ruthenium salt or cerium salt one or more.
4. high dispersive catalyst system and catalyzing according to claim 1, it is characterized in that, described decentralized photo be selected from glycerine, benzene, toluene, chloroform, acetone, paraffin, dimethyl sulfoxide (DMSO), ethylenediamine, pyridine, METHYLPYRROLIDONE, dimethyl formamide, oxolane, cyclohexanone one or more.
5. high dispersive catalyst system and catalyzing according to claim 4, is characterized in that, described decentralized photo be selected from glycerine, chloroform or METHYLPYRROLIDONE one or more;
Wherein, containing in the decentralized photo of METHYLPYRROLIDONE, METHYLPYRROLIDONE quality accounts for more than 80% of decentralized photo gross mass.
6. high dispersive catalyst system and catalyzing according to claim 1, is characterized in that, also can add ionic liquid in decentralized photo; Described ionic liquid accounts for the 0.01-5% of decentralized photo mass fraction.
7. a preparation method for the arbitrary described high dispersive catalyst system and catalyzing of claim 1-6, is characterized in that, comprise the steps:
1) organic palladium salt, co-catalyst are dispersed in decentralized photo, form homogeneous solution;
2) by after solution warms to reduction temperature, pass into hydrogen and carry out reduction reaction, obtain dispersed catalysts.
8. preparation method according to claim 7, is characterized in that, step 2) in, described reduction step is: be slowly warming up to 80-85 DEG C of constant 0.5h, be warming up to again 110-120 DEG C constant in 0.5h, continue to be warming up to 120-200 DEG C and carry out reduction 0.2-5h, hydrogen gas space velocity is 0.1s
-1-1s
-1.
9. the arbitrary described application of high dispersive catalyst system and catalyzing in preparing ethylene by selective hydrogenation of acetylene of claim 1-6, the application preferably in slurry bed process preparing ethylene by selective hydrogenation of acetylene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107362798A (en) * | 2017-07-21 | 2017-11-21 | 北京华福工程有限公司 | Preparation method and the method for preparing ethene for the Pd M based metal catalysts of high purity acetylene Hydrogenation ethene |
| CN109174184A (en) * | 2018-08-17 | 2019-01-11 | 浙江工业大学 | A kind of support type Cabbeen-palladium catalyst of Ionic Liquid Modified and its application in acetylene hydrogenation reaction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57130940A (en) * | 1981-02-04 | 1982-08-13 | Mitsui Petrochem Ind Ltd | Preparation of ethylene glycol |
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| CN107362798B (en) * | 2017-07-21 | 2020-06-16 | 北京华福工程有限公司 | Preparation method of Pd-M-based metal catalyst for preparing ethylene by hydrogenation of high-purity acetylene and method for preparing ethylene |
| CN109174184A (en) * | 2018-08-17 | 2019-01-11 | 浙江工业大学 | A kind of support type Cabbeen-palladium catalyst of Ionic Liquid Modified and its application in acetylene hydrogenation reaction |
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