CN106423269B - Unsaturated acetic acid ester catalyst and preparation method thereof - Google Patents
Unsaturated acetic acid ester catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 150000002168 ethanoic acid esters Chemical class 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 229940125782 compound 2 Drugs 0.000 claims abstract description 25
- 229940125904 compound 1 Drugs 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- -1 alkali metal acetate Chemical class 0.000 claims abstract description 11
- 239000000412 dendrimer Substances 0.000 claims abstract description 10
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001242 acetic acid derivatives Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 238000002803 maceration Methods 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002941 palladium compounds Chemical class 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 239000005977 Ethylene Substances 0.000 description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 15
- 239000011591 potassium Substances 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000004115 Sodium Silicate Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 229910052911 sodium silicate Inorganic materials 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to unsaturated acetic acid ester catalyst and preparation method thereof, mainly solve the problems, such as that the activity and selectivity of existing unsaturated acetic acid ester catalyst is low.The present invention is by using unsaturated acetic acid ester catalyst, with SiO2、Al2O3Or mixtures thereof be carrier, load active component includes Metal Palladium, metallic gold, alkali metal acetate and at least one of the compound 1 being shown below and compound 2 dendrimer compound, the content of palladium is 1~12g/L in catalyst, the content of gold is 0.1~10g/L, the content of alkali metal acetate is 10~100g/L, dendrimer compound content is 0.1~2.0g/L, wherein Et1~Et16It is independently selected from C1~C3Alkyl technical solution, preferably resolve the problem, can be used in the production of unsaturated acetate commercial plant.Compound 1
Description
Technical field
The present invention relates to unsaturated acetic acid ester catalysts and preparation method thereof.
Background technique
Common unsaturated acetate is vinyl acetate and allyl acetate.
Unsaturated acetate is important industrial chemicals, especially vinyl acetate.For example, vinyl acetate is widely used in manufacture
Polyvinyl alcohol, vinyl copolymer resin, binder, coating, textile processing, paper coating etc..The production of vinyl acetate
Process route mainly has ethylene process and two kinds of acetylene method, wherein ethylene process due to craftsmanship, good economy performance and occupy leading ground
Position, accounts for the 82% of total productive capacity using the vinyl acetate production ability of this method.The U.S. completes in nineteen eighty-three and all adopts
With the conversion of ethylene process route.Currently, the method that most countries increase vinyl acetate yield is to carry out reorganization and expansion to original device
And the update of catalyst, the development trend of ethylene process route have been summed up several aspects: (1) process units scale becomes
To enlargement.If USI company, U.S. the seventies initial stage process units scale is ten thousand tons/year of 13.6-15.9, nineteen ninety device rule
Mould reaches 360,000 tons/year, and there are also the expansion energy of the above Hoechst company VAC device；(2) although ethylene process VAC process compares
Maturation, but still improving, to reduce unit consumption and energy consumption；Current state-of-the-art ethylene process technique is the Leap technique of Amoco company
With the Vantage technique of Celanese company.Acetylene method process unit high investment, environmentally friendly difficulty is larger, but with crude oil price
Lattice it is high, comparable competitive advantage will be kept over a period to come, and directly facilitate the research and development of C1 chemical method.
It is using ethylene, oxygen and acetic acid as raw material, with palladium-gold-vinegar that the main method of vinyl acetate is produced in the world today
Sour potassium/silica makees catalyst, is produced by gas phase catalytic reaction, generates vinyl acetate, water and by-product carbon dioxide,
Also generate micro ethyl acetate, acetaldehyde and other acetoxylation product.The temperature of the reactor shell-side of the reaction can be
About 100 to about 180 DEG C, and reaction pressure is about 0.5-1.0MPa, gas volume air speed is about 500 to about 3000hr-1。
The patent of Hanchester rayon Co., Ltd (CN1226188A is used to prepare the palladium-gold catalyst of vinyl acetate)
A kind of catalyst for preparing load and having major catalyst noble metal, promoter metal and alkali or alkaline earth metal compound is provided
Preparation method.The catalyst activity and selectivity that this method obtains is all relatively low.
Summary of the invention
The first technical problem to be solved by the present invention is unsaturated acetate catalyst activity and selection in the prior art
Property low problem, provide a kind of unsaturated acetic acid ester catalyst, the feature that the catalyst is active and selectivity is high.
The second technical problem to be solved by the present invention is to provide the system of catalyst described in a kind of one of above-mentioned technical problem
Preparation Method.
The third technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem
Unsaturated acetate synthetic method.
One of to solve above-mentioned technical problem, technical scheme is as follows: unsaturated acetic acid ester catalyst, with
SiO2、Al2O3Or mixtures thereof be carrier, load active component includes Metal Palladium, metallic gold, alkali metal acetate and as follows
At least one of formula compound represented 1 and compound 2 dendrimer compound, in catalyst the content of palladium be 1~
12g/L, golden content are 0.1~10g/L, the content of alkali metal acetate is 10~100g/L, dendrimer compound
Content is 0.1~2.0g/L；
Compound 1；
Compound 2；
Wherein Et1~Et16It is independently selected from C1~C3Alkyl.
The dendrimer compound is published in J.Phys.Chem.B according to Robert W.J.Scott et al.
The synthesis of method provided by article gained in (109 phase P692-704 in 2005).
In above-mentioned technical proposal, Et1~Et16Methyl, ethyl, n-propyl, isopropyl can be independently selected from.The present invention is specific
Et in embodiment1~Et16For ethyl.
In above-mentioned technical proposal, the dendritic macromole preferably includes compound 1 and compound 2, and the two is urged in raising
There is synergistic effect in terms of the activity and selectivity of agent.The mass ratio of more preferable compound 1 and compound 2 be 1:(0.05~
20)。
In above-mentioned technical proposal, the alkali metal acetate is preferably potassium acetate.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the skill of one of above-mentioned technical problem
The preparation method of catalyst described in any one of art scheme, comprising the following steps:
(a) in the solution dissolved with containing palladium compound and gold-containing compound, dendrimer compound, which is added, to be soaked
Stain liquid；
(b) in above-mentioned maceration extract, carrier impregnation is added, catalyst precarsor I is made；
(c) catalyst precarsor II is obtained with alkaline compound solution processing catalytic precursor I；
(d) palladium of compound state in catalyst precarsor II and the gold of compound state are reduced to simple substance with reducing agent, are catalyzed
Agent precursor II I；
(e) alkali metal acetate solution impregnation catalyst precursor I V is used, the catalyst is made after dry.
In above-mentioned technical proposal, the containing palladium compound is preferably chlorine palladium acid or chloropalladate, gold-containing compound are preferably
Gold chloride or chloroaurate；The alkali compounds is preferably the silicate or hydroxide of alkali metal；The reducing agent is preferred
For hydrazine hydrate or hydrogen；When the reducing agent is hydrogen, reduction temperature is preferably 100~300 DEG C.
To solve above-mentioned technical problem three, technical solution of the present invention is as follows: the synthetic method of unsaturated acetate, upper
In the presence of stating catalyst described in any one of technical solution of one of technical problem, oxygen is become with molar ratio computing unstripped gas group:
C2~C3Alkene: nitrogen: acetic acid=1:(5~7): (4~8): (1~2), reaction pressure are 0.5~0.9MPa, and reaction temperature is
130~200 DEG C, feed gas volume air speed is 1600~3000hr-1.Work as C2~C3It is corresponding unsaturated when alkene uses ethylene
Acetate is vinyl acetate；Work as C2~C3When alkene uses propylene, corresponding unsaturation acetate is allyl acetate.
Catalyst causes catalyst activity and selectivity insufficient in industrial application because noble metal crystal grain activity point is very few, adopts
With the vinyl acetate catalyst of the method for the present invention, modified in noble metal grain surface using dendrimer compound,
Can increase the active point of noble metal crystal grain, and by modification after, the selectivity of catalyst is also improved.Experimental result table
Bright, reaction pressure 0.7MPa, 140 DEG C of reaction temperature, reaction gas is with molar ratio computing oxygen: ethylene: nitrogen: acetic acid=1:
When 6.8:7.2:1.7, the comparison prior art catalyst space time yield of catalyst of the invention is increased to 416g/L by 315g/L,
Selectivity is increased to 96.8% by 93.5%, achieves preferable technical effect.
Specific embodiment
[embodiment 1]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g compound 1, be prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
For the ease of comparing, the preparation condition of catalyst is listed in table 1.
(2) catalyst characterization
Using the content of each metallic element in inductively coupled plasma spectrum generator (ICP) measurement catalyst, penetrated using X
The content of dendritic macromole, income analysis characterize data are listed in table 2 in line fluorescence spectrum (XRF) analysis of catalyst.
(3) evaluating catalyst
It is evaluated with fixed bed reactors, actual conditions are as follows:
Catalyst packing volume: 400ml；
Reaction raw materials form (with molar ratio computing): oxygen: ethylene: nitrogen: acetic acid=1:6.8:7.2:1.7；
Reaction raw materials Feed space velocities: 2000hr-1；
Reaction pressure: 0.7MPa；
Reaction temperature: 140 DEG C；
Reaction time: 500hr；
With the content of each component in gas chromatography analysis reaction product, catalysts towards ethylene selectivity, institute are then calculated
It obtains test data and is listed in table 2.
[embodiment 2]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 2, be prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 3]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 4]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:0.05, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 5]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:20, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 6]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 0.92g/L, gold in solution
Content be 0.105g/L, in the above solution be added quality be 0.092g attached drawing shown in compound 1 and 2 mixture,
The mass ratio of middle compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 7]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 11g/L in solution, golden
Content is 10.5g/L, the mixture of compound 1 and 2 shown in the attached drawing that quality is 1.84g is added in the above solution, wherein changing
The mass ratio for closing object 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 8]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium hydroxide and be added in catalyst precarsor I, is uniformly mixed, and stands
Catalyst precarsor II is made then in 80 DEG C of dry 8hr in r for 24 hours；
Step (d): catalyst precarsor II is restored in hydrazine hydrate solution, and the concentration of hydrazine hydrate solution is 450g/L, is obtained
To catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 9]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 100 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 10]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, in the above solution be added quality be 0.36g attached drawing shown in compound 1 and 2 mixture, wherein
The mass ratio of compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 300 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[embodiment 11]
(1) catalyst preparation
Step (a): the solution 1200ml containing potassium chloropalladate and potassium chloroaurate is taken, wherein the content of palladium is in solution
2.75g/L, golden content are 0.625g/L, and compound 1 and 2 shown in the attached drawing that quality is 0.36g is added in the above solution
Mixture, wherein the mass ratio of compound 1 and 2 is 1:1, is prepared into maceration extract；
It is the preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm that volume, which is added, in step (b) in above-mentioned maceration extract,
Obtain catalyst precarsor I；
Step (c): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (d): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (e): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
[comparative example 1]
(1) catalyst preparation
Step (a): taking chlorine palladium acid gold chloride mixed aqueous solution 1200ml, and wherein the content of palladium is 2.75g/L, gold in solution
Content be 0.625g/L, dipping volume is preparing spherical SiO 2 carrier that 1100ml diameter is 4~6mm, before obtaining catalyst
Body I；
Step (b): being made into 100ml aqueous solution for 27.5g sodium silicate nanahydrate and be added in catalyst precarsor I, is uniformly mixed,
R for 24 hours is stood, then in 80 DEG C of dry 8hr, catalyst precarsor II is made；
Step (c): catalyst precarsor II is restored in hydrogen atmosphere, hydrogen flow rate 0.2ml/min, and pressure is
0.5MPa, reduction temperature are 200 DEG C, obtain catalyst precarsor III；
Step (d): dipping acetic acid aqueous solutions of potassium makes acetic acid potassium content 30g/L, dry finished product catalyst.
Catalyst characterization and evaluation condition are same as Example 1, for the ease of comparing the preparation condition of catalyst, catalysis
Physical data, the catalysts towards ethylene of agent are selectively listed in Tables 1 and 2.
Through the foregoing embodiment and comparative example, discovery use the mixture and palladium of dendritic macromole 1 and 2 shown in the drawings
Dipping co-precipitation can preferably improve the activity and selectivity of catalyst to gold together.
1. catalyst preparation conditions of table
2 catalyst physical property of table and evaluation data
Claims (8)
1. unsaturated acetic acid ester catalyst, with SiO2、Al2O3Or mixtures thereof be carrier, load active component include Metal Palladium,
The dendrimer compound of metallic gold, alkali metal acetate and the compound 1 and compound 2 that are shown below, chemical combination
The mass ratio of object 1 and compound 2 is 1:(0.05~20), in catalyst the content of palladium be 1~12g/L, the content of gold be 0.1~
10g/L, alkali metal acetate content be 10~100g/L, dendrimer compound content is 0.1~2.0g/L；
Wherein Et1~Et16It is independently selected from C1~C3Alkyl.
2. unsaturated acetic acid ester catalyst according to claim 1, it is characterised in that Et1~Et16For ethyl.
3. unsaturated acetic acid ester catalyst according to claim 1, it is characterised in that the alkali metal acetate is potassium acetate.
4. the preparation method of catalyst described in any one of claims 1 to 3, comprising the following steps:
(a) in the solution dissolved with containing palladium compound and gold-containing compound, dendrimer compound is added and obtains maceration extract；
(b) in above-mentioned maceration extract, carrier impregnation is added, catalyst precarsor I is made；
(c) catalyst precarsor II is obtained with alkaline compound solution processing catalyst precarsor I；
(d) palladium of compound state in catalyst precarsor II and the gold of compound state are reduced to simple substance with reducing agent, before obtaining catalyst
Body III；
(e) alkali metal acetate solution impregnation catalyst precursor I V is used, the catalyst is made after dry.
5. the preparation method according to claim 4, it is characterised in that the containing palladium compound be chlorine palladium acid or chloropalladate,
Gold-containing compound is gold chloride or chloroaurate.
6. the preparation method according to claim 4, it is characterised in that the reducing agent is hydrazine hydrate or hydrogen.
7. the preparation method according to claim 4, it is characterised in that when the reducing agent is hydrogen, reduction temperature 100
~300 DEG C.
8. the synthetic method of unsaturated acetate, in the presence of the catalyst as described in any one of claims 1 to 3, with mole
Become oxygen: C2~C3 alkene: nitrogen: acetic acid=1:(5~7 than meter unstripped gas group): (4~8): (1~2), reaction pressure are
0.5~0.9MPa, reaction temperature are 130~200 DEG C, and feed gas volume air speed is 1600~3000hr-1, react and obtain unsaturation
Acetate.
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