CN105126914B - A kind of high dispersive catalyst system and catalyzing and its preparation method and application - Google Patents
A kind of high dispersive catalyst system and catalyzing and its preparation method and application Download PDFInfo
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- CN105126914B CN105126914B CN201510484803.3A CN201510484803A CN105126914B CN 105126914 B CN105126914 B CN 105126914B CN 201510484803 A CN201510484803 A CN 201510484803A CN 105126914 B CN105126914 B CN 105126914B
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- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000003426 co-catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 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
- 150000002940 palladium Chemical class 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 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
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000009467 reduction 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 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
- 150000000703 Cerium Chemical class 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 239000003921 oil Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- 235000010358 acesulfame potassium Nutrition 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 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 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 7
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229910052593 corundum Inorganic materials 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 hydrogen alkynes Chemical class 0.000 description 1
- 239000004615 ingredient Substances 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
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 238000000197 pyrolysis Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 150000003462 sulfoxides Chemical class 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
- 229910001845 yogo sapphire Inorganic materials 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
Abstract
The present invention relates to a kind of high dispersive catalyst system and catalyzings and its preparation method and application.The catalyst system and catalyzing is dissolved in dispersed phase by organic palladium salt, co-catalyst, made from hydrogen reducing；The catalyst system and catalyzing grain size is between 1nm 100nm；Metal Palladium accounts for the 0.01 1% of catalyst system and catalyzing gross mass.Gained catalyst system and catalyzing carrier-free avoids acetylene deep hydrogenation in acetylene ethylene process, dosage to be few, at low cost, coefficient of efficiency is high, space-time yield is big, improves conversion of alkyne and yield of ethene；The defects of big solid particle easily promotes bubble to merge, blocks gas distributor and equipment attrition is overcome simultaneously, is conducive to slurry bed system gas-liquid-solid three-phase and is evenly distributed.
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
Ethylene is most important basic material in petrochemical industry, is referred to as " mother of petrochemical industry ".At present mainly by oil
Or low-carbon alkanes pass through cracking.And in the ethylene that naphtha pyrolysis stove comes out, containing trace acetylene, to follow-up ethylene
The toxic effect of polymerisation, it is therefore desirable to which acetylene content is down to 10ppm or less.
Have at present studies have shown that a kind of new raw material can be provided for ethylene industry using preparing ethylene by selective hydrogenation of acetylene
Source reduces ethylene to the degree of dependence and production cost of ethylene of petroleum resources, has broad application prospects.The prior art is public
The method that acetylene liquid phase selective hydrogenation in slurry bed system prepares ethylene is opened.Wherein, it is molten that liquid phase is introduced in gas-solid catalysis system
Agent, has high selection dissolubility to acetylene, has low Selective dissolution to ethylene；Catalyst is dispersed in liquid phase solvent
In, PROCESS COUPLING is realized to the high selection dissolubility of acetylene using liquid phase solvent, improves the selectivity of ethylene.However, this field
Technical staff knows that paste state bed reactor is gas-liquid-solid phase reaction, it is desirable that gas-liquid-solid uniformly mixes, but due to fixed-bed catalytic
Agent must be carried on carrier, and grain size is limited, and larger beaded catalyst disperse in slurries it is uneven；And bulky grain is solid
Body also easily blocks gas distribution holes in slurry bed system；In addition, that there is also hydrogenation activities is low, addition is big, it is complicated to prepare, equipment mill
The defects of damage.Therefore, it is necessary to propose that a kind of grain size is small, catalyst of good dispersion.
Invention content
The object of the present invention is to provide a kind of high dispersive catalyst system and catalyzings suitable for producing ethylene with acetylene hydrogenation slurry bed system.It is described
Catalyst system and catalyzing grain size is small, effectively prevents the problem of fixed bed large granular catalyst blocks gas distributor and equipment attrition, will
It is used to not only reduce in slurry bed system catalyst amount, but also improves conversion of alkyne.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of high dispersive catalyst system and catalyzing is dissolved in dispersed phase by organic palladium salt, co-catalyst, is made through hydrogen reducing
's；The catalyst system and catalyzing grain size is between 1nm-100nm.
In the obtained catalyst system and catalyzing of the present invention, Metal Palladium accounts for the 0.01-1% of catalyst system and catalyzing gross mass.
High dispersive catalyst system and catalyzing of the present invention has grain size small, carrier-free, more preferable for dispersibility in slurry bed system, has
Effect improves catalyst utilization and ethylene yield, while also can avoid large granular catalyst and blocking gas distributor and equipment, second
Alkynes is in catalyst carrier the problems such as deep hydrogenation.
In catalyst system and catalyzing of the present invention, organic palladium salt is selected from two（Acetylacetone,2,4-pentanedione）Palladium, hexafluoroacetylacetone palladium,
Four（Triphenylphosphine）It is palladium, double（Acetonitrile）Palladium bichloride or（2,2- bipyridyls）It is one or more in dichloro palladium.
In catalyst system and catalyzing of the present invention, the co-catalyst is in oil-soluble silver salt, nickel salt, ruthenium salt or cerium salt etc.
It is one or more.
In catalyst system and catalyzing of the present invention, the dispersed phase is selected from glycerine, benzene, toluene, chloroform, acetone, paraffin, diformazan
One kind or more in base sulfoxide, ethylenediamine, pyridine, n-methyl-2-pyrrolidone, dimethylformamide, tetrahydrofuran, cyclohexanone
Kind；One or more of preferably glycerine, chloroform or n-methyl-2-pyrrolidone, wherein containing N- methyl -2- pyrroles
In the dispersed phase of pyrrolidone, n-methyl-2-pyrrolidone quality accounts for 80% or more of dispersed phase gross mass.
In order to obtain better dispersion effect, ionic liquid can also be added in dispersed phase；The ionic liquid accounts for dispersion
The 0.01-5% of phase mass fraction.The ionic liquid is selected from [BMIM] [BF4], [BMIM] [BF4], [BMIM] Cl, [BMPyrr]
It is one or more in [EtHPO3] or [BMPyrr] [OAC].
The present invention does not further limit organic palladium salt, the dosage of co-catalyst, and the additive amount of said components is to realize
It is completely dissolved and Metal Palladium mass fraction in system is made to be 0.01-1% in the solution.
The present invention also provides a kind of preparation methods of above-mentioned catalyst system and catalyzing, include the following steps：
1）Organic palladium salt, co-catalyst are dispersed in dispersed phase, homogeneous solution is formed；
2）After solution is warming up to reduction temperature, it is passed through hydrogen and carries out reduction reaction, obtain dispersed catalysts.
In the above preparation method, step 2）In, the reducing condition is：It is to slowly warm up to 80-85 DEG C of constant 0.5h, then
Be warming up to 110-120 DEG C it is constant be 0.5h, be continuously heating to 120-200 DEG C and carry out reduction 0.2-5h, hydrogen gas space velocity 0.1s-1-
1s-1。
Reduction reaction of the present invention can be in the reaction unit that can realize the present invention that those skilled in the art are grasped
Carry out, the present invention again this be not specially limited.As one of preferred embodiment for the present invention, the reduction reaction can also
It is carried out in autoclave of having a rest stirred reactor, wherein Hydrogen Vapor Pressure is 0.2-1.2MPa.
The present invention also provides application of the above-mentioned catalyst system and catalyzing in preparing ethylene by selective hydrogenation of acetylene, preferably slurry bed process second
Alkynes preparing ethylene by selective hydrogenation.Catalyst system and catalyzing is directly added into slurry bed system liquid phase solvent when specifically used and is disperseed.This hair
The bright catalyst system and catalyzing can be used for but be 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 smaller are steadily scattered in slurry bed system liquid phase
In.The catalyst system and catalyzing is used in acetylene prepares ethylene process, can both reduce catalyst amount, it is cost-effective, and be conducive to carry
High conversion of alkyne avoids large granular catalyst and minute bubbles merging, blocking gas distributor and equipment attrition, acetylene is promoted to exist
In catalyst carrier the problems such as deep hydrogenation.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
It is as follows：
1）Chloroform 10g, glycerine 10g, n-methyl-2-pyrrolidone 80g are taken, is uniformly mixed and is made into dispersed phase；
N in molar ratio(Pd):n(Ag)=1:2.5 take two（Acetylacetone,2,4-pentanedione）Palladium 0.286g, co-catalyst silver nitrate are dissolved in dispersed phase
In, obtain mixed liquor；
2）Mixed liquor is to slowly warm up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, is continuously heating to 150
DEG C it is passed through hydrogen reducing 2h, obtains catalyst system and catalyzing 1；
Wherein, hydrogen gas space velocity 0.1s-1, 1 average diameter of particles of gained catalyst system and catalyzing is 13nm.
Embodiment 2
It is as follows：
1）Glycerine 10g, n-methyl-2-pyrrolidone 90g are taken, is uniformly mixed and is made into dispersed phase, in molar ratio n(Pd):n(Ni)=
1:2 take it is double（Acetonitrile）Palladium bichloride 2.44g, co-catalyst nickel acetylacetonate are dissolved in dispersed phase, obtain mixed liquor；
2）Mixed liquor is to slowly warm up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, is continuously heating to 200
DEG C it is passed through hydrogen reducing 0.2h, obtains catalyst system and catalyzing 2；
Wherein, hydrogen gas space velocity 1s-1, 2 average diameter of particles of gained catalyst system and catalyzing is 97nm.
Embodiment 3
It is as follows：
1）Chloroform 10g, ionic liquid [BMIM] [BF4] 5g, n-methyl-2-pyrrolidone 85g are taken, is uniformly mixed and matches ingredient
Dephasing；N in molar ratio(Pd):n(Ce)=1:1 takes hexafluoroacetylacetone palladium 2.61g, co-catalyst trifluoromethayl sulfonic acid cerium to be dissolved in dispersion
Xiang Zhong obtains mixed liquor；
2）Mixed liquor is to slowly warm up to 80 DEG C of constant temperature 0.5h, then is warming up to 110 DEG C of constant temperature 0.5h, is continuously heating to 120
DEG C it is passed through hydrogen reducing 5h, obtains catalyst system and catalyzing 3；
Wherein, hydrogen gas space velocity 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 take palladium bichloride and silver acetate soluble in water, by infusion process in 40 mesh γ-
Al2O3The upper 0.03% ω t Metal Palladiums of load, drying roasting, hydrogen reducing obtain solid catalyst.
Comparative example 2
N in molar ratio(Pd):n(Ce)=1:2 take palladium nitrate and nickel acetylacetonate soluble in water, are aoxidized in 40 mesh by infusion process
0.03% ω t Metal Palladiums, drying roasting are loaded on silicon, hydrogen reducing obtains solid catalyst.
Effect experiment
The solid catalyst of catalyst system and catalyzing and 1,2 gained of comparative example obtained by embodiment 1-3 is placed in slurry bed system, slurries
Middle palladium metal content is 200ppm, in hydrogen alkynes volume ratio 6:1, operation air speed is 45000ml/ (gcat.h), and temperature is 150 DEG C
Under the conditions of reacted, it is as a result as follows by reaction end gas through chromatography：
As seen from the above table, catalyst system and catalyzing of the present invention is in operation air speed in acetylene prepares ethylene slurry bubble bed
In use, catalyst system and catalyzing of the present invention is equal in terms of conversion of alkyne, yield of ethene in the case of 45000ml/ (gcat.h)
It is apparently higher than comparative example；Illustrate that catalyst system and catalyzing obtained by the embodiment of the present invention effectively prevents diffusion, ethylene in large granular catalyst
Further plus the problem of hydrogen；And reduce the problems such as blocking gas distributor and equipment attrition during the reaction.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (5)
1. a kind of preparation method of high dispersive catalyst system and catalyzing, which is characterized in that include the following steps：
1) organic palladium salt, co-catalyst are dispersed in dispersed phase, form homogeneous solution；
2) it after solution being warming up to reduction temperature, is passed through hydrogen and carries out reduction reaction, obtain dispersed catalysts；
In step 2), the reduction step is：It is to slowly warm up to 80-85 DEG C of constant 0.5h, then is warming up to 110-120 DEG C and constant is
0.5h is continuously heating to 120-200 DEG C and carries out reduction 0.2-5h, hydrogen gas space velocity 0.1s-1-1s-1；
The catalyst system and catalyzing average grain diameter is between 7nm-97nm；Metal Palladium accounts for the 0.01-1% of catalyst system and catalyzing gross mass；
The co-catalyst is one or more in oil-soluble silver salt, nickel salt, ruthenium salt or cerium salt；
Ionic liquid is added in dispersed phase；The ionic liquid accounts for the 0.01-5% of mass of the dispersed phase score；
The high dispersive catalyst system and catalyzing carrier-free, when use, which is directly added into slurry bed system liquid phase solvent, disperses.
2. the preparation method of high dispersive catalyst system and catalyzing according to claim 1, which is characterized in that organic palladium salt is selected from
Two (acetylacetone,2,4-pentanedione) palladiums, hexafluoroacetylacetone palladium, tetrakis triphenylphosphine palladium, bis- (acetonitrile) palladium bichlorides and (2,2- bipyridyls) dichloro
It is one or more in palladium.
3. the preparation method of high dispersive catalyst system and catalyzing according to claim 1, which is characterized in that the dispersed phase is selected from sweet
Oil, benzene, toluene, chloroform, acetone, paraffin, dimethyl sulfoxide (DMSO), ethylenediamine, pyridine, n-methyl-2-pyrrolidone, dimethyl formyl
It is one or more in amine, tetrahydrofuran, cyclohexanone.
4. the preparation method of high dispersive catalyst system and catalyzing according to claim 3, which is characterized in that the dispersed phase is selected from sweet
One or more of oil, chloroform or n-methyl-2-pyrrolidone；
Wherein, in the dispersed phase containing n-methyl-2-pyrrolidone, n-methyl-2-pyrrolidone quality accounts for the total matter of dispersed phase
80% or more of amount.
5. high dispersive catalyst system and catalyzing is in acetylene made from the preparation method of any high dispersive catalyst system and catalyzings of claim 1-4
Application in preparing ethylene by selective hydrogenation, which is characterized in that the application is in slurry bed process preparing ethylene by selective hydrogenation of acetylene
In application.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484803.3A CN105126914B (en) | 2015-08-07 | 2015-08-07 | A kind of high dispersive catalyst system and catalyzing and its preparation method and application |
Applications Claiming Priority (1)
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| CN101898133A (en) * | 2009-05-25 | 2010-12-01 | 代斌 | Catalyst for selective hydrogenation of acetylene for preparing ethylene by calcium carbide process |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
| CN104043841A (en) * | 2014-06-06 | 2014-09-17 | 苏州创科微电子材料有限公司 | Method for preparing metal nano material by utilizing hydrogen |
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| CN101402541A (en) * | 2008-11-21 | 2009-04-08 | 清华大学 | Fluidized bed process and apparatus for producing ethylene with acetylene hydrogenation |
| CN101898133A (en) * | 2009-05-25 | 2010-12-01 | 代斌 | Catalyst for selective hydrogenation of acetylene for preparing ethylene by calcium carbide process |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
| CN104043841A (en) * | 2014-06-06 | 2014-09-17 | 苏州创科微电子材料有限公司 | Method for preparing metal nano material by utilizing hydrogen |
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