CN106582826B

CN106582826B - Produce catalyst used in ethylene process vinyl acetate

Info

Publication number: CN106582826B
Application number: CN201510676245.0A
Authority: CN
Inventors: 查晓钟; 杨运信
Original assignee: Sinopec Shanghai Research Institute of Petrochemical Technology; China Petrochemical Corp
Current assignee: Sinopec Shanghai Research Institute of Petrochemical Technology; China Petrochemical Corp
Priority date: 2015-10-19
Filing date: 2015-10-19
Publication date: 2019-11-08
Anticipated expiration: 2035-10-19
Also published as: CN106582826A

Abstract

The present invention relates to catalyst used in production ethylene process vinyl acetate, mainly solve the problems, such as that catalyst activity and selectivity is not high in the prior art.For the present invention using the catalyst for producing ethylene process vinyl acetate, the catalyst includes carrier, active component and co-catalyst；The carrier uses SiO₂、Al₂O₃Or its mixture, the co-catalyst is alkali metal acetate, the active component includes metal Pd, metal Au and selected from least one of Ferrious material and IB metal metallic element, the IB metallic element is selected from the technical solution of at least one of copper or silver, it preferably solves the problems, such as this, can be used in the industrial production of vinyl acetate.

Description

Produce catalyst used in ethylene process vinyl acetate

Technical field

The present invention relates to catalyst, the preparation method of catalyst and ethylene process vinegar used in production ethylene process vinyl acetate The synthetic method of sour ethylene.

Background technique

Vinyl acetate (VAc) is one of maximum 50 kinds of industrial chemicals of world wide production, is total to by autohemagglutination or with other monomers It is poly-, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) lotion, vinyl acetate-ethylene copolymerization emulsions (VAE) or total can be generated The derivatives such as poly resin (EVA), vinyl acetate-chloride copolymer (EVC).These derivatives are widely used in adhesive, build Cementing agent, coating, ink, leather processing, fiber process, emulsifier, water-solubility membrane and the soil for building coating, paper or fabric change Good dose etc..In the world today produce ethylene process vinyl acetate main method be using ethylene, oxygen and acetic acid as raw material, with Pd-Au-KOAc/SiO₂System makees catalyst, is synthesized by gas phase catalytic reaction.

From after the technique of nineteen seventies discovery ethylene vapor phase method production vinylacetate, people are dedicated to higher The catalyst research of reactivity and selectivity.Currently, people more concentrate on research precious metal palladium and gold or other elements exist Dispersion and distribution on carrier, distribution of the active component on carrier also develop to eggshell type, the utilization of noble metal from protein type Rate effectively improves, and increases the reactivity of units activity component agent, reduces the generation of side reaction, improves reaction choosing Selecting property.

Chinese patent (CN1226188A is used to prepare the palladium-gold catalyst of vinyl acetate), which provides, a kind of prepares load There is the preparation method of the catalyst of major catalyst noble metal, promoter metal and alkali or alkaline earth metal compound.It has Body manufacturing process is as follows: 1. in the dipping tank of rotation, the mixed liquor of configured noble metal and co-catalyst being added, is passed through Hot-air is dry；2., will be original in the catalyst after taking a certain amount of solution with alkaline matters such as sodium metasilicate to make an addition to drying The palladium and gold of the chlorination state of water soluble are converted to the insoluble hydroxide state palladium of water and gold；3. restoring hydroxide in nitrogen atmosphere The palladium and Au catalyst of state are reduced into the palladium and Au catalyst of metallic state；4. it is washed till no chloride ion, it is dry, potassium acetate is soaked, Up to the catalyst after drying.

United States Patent (USP) (US 3743607, entitled Palladium-gold catalyst) describes urging for homogeneous impregnation The preparation method of agent, this method comprises: 1. with palladium, the solution impregnating carrier of gold compound；2. drying；3. palladium, aurification are closed Object is reduced to Metal Palladium, gold；4. washing, drying.

United States Patent (USP) (US 4048096, entitled Surface impregnated catalyst) describes shell leaching The preparation method of the catalyst of stain, this method comprises: 1. with the solution impregnating carrier containing palladium, gold compound；2. the load after dipping Body is contacted with the aqueous solution of the sodium metasilicate containing alkali compounds, water-soluble palladium, gold compound is precipitated as insoluble palladium, aurification is closed Object；3. palladium, gold compound are changed into Metal Palladium, gold with reducing agent；4. dry after being contacted after washing with alkali metal acetate To the catalyst.The space time yield and selectivity of catalyst obtained by the above method are lower.

Summary of the invention

The first technical problem to be solved by the present invention is the vinyl acetate catalyst activity and choosing synthesized in the prior art The not high problem of selecting property.Provide it is a kind of produce catalyst used in ethylene process vinyl acetate, which has high activity high The feature of selectivity.

The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of technical problem.

The third technical problem to be solved by the present invention is using catalyst synthesizing ethylene method vinegar described in one of technical problem The method of sour ethylene.

One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: production ethylene process vinyl acetate Catalyst used, the catalyst include carrier, active component and co-catalyst；The carrier uses SiO₂、Al₂O₃Or Its mixture, the co-catalyst be alkali metal acetate, the active component include metal Pd, metal Au and selected from iron series gold Belong to and the compound of at least one of IB metal metallic element, the IB metallic element are selected from least one of copper or silver.

At least one of the preferred iron of Ferrious material element described in above-mentioned technical proposal, cobalt and nickel；The alkali metal vinegar Hydrochlorate is preferably potassium acetate.

In above-mentioned technical proposal, as most preferred technical solution, the catalyst includes simultaneously Pd, Au, potassium acetate, iron It is the compound of metallic element and the compound of IB metallic element；Such as the catalyst includes Pd, Au, potassium acetate, cobalt element With copper (or silver element), perhaps including Pd, Au, potassium acetate, cobalt element (or ferro element), copper and silver element or Including Pd, Au, potassium acetate, cobalt element, ferro element, copper and ferro element.

In above-mentioned technical proposal, the content of activity component metal Pd is preferably 1.0~12.0g/L in the catalyst；Institute The content for stating activity component metal Au in catalyst is preferably 0.1~10.0g/L；The active component is selected from Ferrious material and IB At least one metal element content of middle metal is preferably 0.5~7.0g/L；The content of potassium acetate is preferably in the catalyst 10~90g/L.

To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem Method for preparing catalyst described in case, includes the following steps:

(1) compound solution of the compound of palladium and gold is mixed with carrier by the composition of catalyst, before obtaining catalyst Body I；

(2) so that compound containing Pd and compound containing Au is converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；

(3) compound state Pd in catalyst precarsor II and compound state Au are reduced to metal Pd and before metal Au obtains catalyst Body III；

(4) composition for pressing catalyst, metallic compound in Ferrious material compound and/or IB is supported on using infusion process Catalyst precarsor III obtains catalyst precarsor IV after dry, roasting；

(5) co-catalyst liquor kalii acetici and catalyst precarsor IV are sufficiently mixed, are dried to obtain the catalyst.

In above-mentioned technical proposal, the reducing agent of the understanding step (3) based on those skilled in the art is not specially required, also Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；Step (4) and step (5) are dry Temperature is preferably 80~120 DEG C, and drying time is preferably 1~5 hour；Step (4) roasting condition with by Ferrious material compound, IB compound, which is converted into oxide, to be advisable, such as maturing temperature is preferably 300~500 DEG C, and calcining time is preferably 1~5 hour.

In above-mentioned technical proposal, the compound and nickel of the compound of step (4) the preferred iron of Ferrious material compound, cobalt Compound (such as, but not limited to ferric acetate, ferric nitrate, iron chloride, cobalt acetate, cobalt nitrate, cobalt chloride, nickel acetate, nitric acid At least one of nickel and nickel chloride)；The compound of step (4) the preferred copper of IB metallic compound is (such as, but not limited to Cupric tartrate, copper chloride, copper nitrate, copper acetate, copper citrate) or silver-colored compound (such as, but not limited to silver acetate, nitric acid At least one of silver, silver ammino solution, actol).

To solve above-mentioned technical problem three, technical scheme is as follows: the synthetic method of ethylene process vinyl acetate, Using ethylene, acetic acid and oxygen as raw material, reaction obtains vinyl acetate in the presence of above-mentioned catalyst.

Key of the invention is the selection of catalyst, and skilled person will know how suitable determine according to actual needs Reaction temperature, the reaction time, reaction pressure and material proportion.But in above-mentioned technical proposal, the temperature of reaction is preferably 130~150 DEG C, reaction pressure be preferably 0.1~1.0MPa, with molar ratio computing ethylene: acetic acid: oxygen be preferably 1:(0.1~ 0.3): (0.05~0.2), raw material volume air speed are preferably 1500~2500h^-1。

Compared with prior art, key of the invention be include metal Pd, metal Au, potassium acetate and selected from iron in catalyst It is at least one of metal and IB metal metallic element, is conducive to the activity and stability that improve catalyst, to improve The yield and selectivity of vinyl acetate.

The catalyst of above method synthesis with comparative catalyst with evaluating apparatus to be evaluated respectively and calculate catalyst Activity and and selectivity.Evaluation method be in the reactor loading 900ml catalyst, using nitrogen leak test, it is ensured that system without After leak source, the flow of ethylene is adjusted to 64.4mol/h, is heated up simultaneously, when reaction bed temperature reaches 120 DEG C, investment The acetic acid of 9.30mol/h, starts to throw oxygen after twenty minutes, sufficient oxygen is thrown after 120 minutes, the amount of oxygen is 3.88mol/h, and air speed is 2000h^-1, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa in reaction process, controls raw material ratio are as follows: and ethylene/acetic acid/ Oxygen=83.0/12.0/5.0 (molar ratio).

The content of each component in gas chromatography analysis reaction product, and be calculated according to the following formula catalyst activity (when Empty yield) and selectivity:

The experimental results showed that the activity of catalyst reaches 375.30g/Lh, Dichlorodiphenyl Acetate second when using catalyst of the present invention The selectivity of alkene is 95.12%, achieve in preferable technical effect, especially catalyst include simultaneously metal Pd, metal Au, At least one of potassium acetate, Ferrious material metallic element and when selected from least one of IB metallic element, achieves more Technical effect outstanding, can be used in the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.

Specific embodiment

[embodiment 1]

The preparation of catalyst:

(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd's and 1.87gAu Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot Shape SiO₂Catalyst precarsor I is obtained on carrier；

After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml₂SiO₃·9H₂The solution of O is sufficiently mixed, and ageing obtains for 24 hours Catalyst precarsor II；

It (3) is 12% (with N with solubility₂H₄·H₂O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine Ion, 90 DEG C are dried to obtain catalyst precarsor III；

(4) by the cobalt acetate (Co (OA containing 1.32gCo_C)₂·4H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；

(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C It is dry, obtain the catalyst.

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Co content is 1.32g/L, acetic acid Potassium content 33g/L.

The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used₂After leak test, N is used₂ System is sufficiently purged, after system heating, closes N₂, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h^-1；Raw material composition: Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.

Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The activity for being computed the catalyst is 375.30g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.12%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 2]

The preparation of catalyst:

(4) by the copper acetate (Cu (OA containing 1.32gCu_C)₂·H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Cu content is 1.32g/L, acetic acid Potassium content 33g/L.

The activity for being computed the catalyst is 375.12g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.35%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[comparative example 1]

For the comparative example of [embodiment 1] and [embodiment 2].

The preparation of catalyst:

(4) the solution 300ml for weighing the potassium acetate containing 33g, is immersed on precursor I V, in 100 DEG C of dryings, obtains the catalysis Agent.

The Pd content for measuring the catalyst through ICP is 3.85g/L, Au content 1.87g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 365.52g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.29%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing metal Pd, metal Au, potassium acetate and cobalt element or simultaneously the catalyst performance ratio containing metal Pd, metal Au, potassium acetate and copper are containing only metal Pd, metal Au, the performance of potassium acetate catalyst are more excellent, and the space-time yield and selectivity of vinyl acetate catalyst will be high.

[embodiment 3]

The preparation of catalyst:

(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd's and 1.87gAu Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot Shape Al₂O₃Catalyst precarsor I is obtained on carrier；

(4) by the cobalt nitrate (Co (NO containing 1.32gCo₃)₂·6H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；

The activity for being computed the catalyst is 375.22g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.14%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 4]

The preparation of catalyst:

(4) by the cobalt chloride (CoCl containing 1.32gCo₂·6H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C Vacuum drying, 400 DEG C of roastings, obtains catalyst precarsor IV；

The activity for being computed the catalyst is 375.27g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.12%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 5]

The preparation of catalyst:

(4) by the ferrous acetate (Fe (OA containing 1.32gFe_C)₂·4H₂O) aqueous solution 150ml is immersed on precursor II I, warp 110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Fe content is 1.32g/L, acetic acid Potassium content 33g/L.

Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography- Mass spectrometer (GC-MASS) analysis.

The activity for being computed the catalyst is 375.20g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.21%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 6]

The preparation of catalyst:

(4) by the nickel acetate (Ni (OA containing 1.32gNi_C)₂·4H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ni content is 1.32g/L, acetic acid Potassium content 33g/L.

The activity for being computed the catalyst is 375.25g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.16%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 7]

The preparation of catalyst:

(4) by the copper chloride (CuCl containing 1.32gCu₂·2H₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C Vacuum drying, 400 DEG C of roastings, obtains catalyst precarsor IV；

The activity for being computed the catalyst is 375.14g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.33%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 8]

The preparation of catalyst:

(4) by the copper nitrate (Cu (NO containing 1.32gCu₃)₂) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C of vacuum Dry, 400 DEG C of roastings obtain catalyst precarsor IV；

The activity for being computed the catalyst is 375.16g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.27%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 9]

The preparation of catalyst:

(4) by the silver ammino solution ([Ag (NH containing 1.32gAg₃)₂]OH·XH₂O) aqueous solution 150ml is immersed in precursor II I On, it is dried in vacuo through 110 DEG C, 400 DEG C of roastings obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ag content is 1.32g/L, acetic acid Potassium content 33g/L.

The activity for being computed the catalyst is 375.18g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.32%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 10]

The preparation of catalyst:

(4) the silver nitrate aqueous solution 150ml containing 1.32gAg is immersed on precursor II I, is dried in vacuo through 110 DEG C, 400 DEG C roasting, obtain catalyst precarsor IV；

The activity for being computed the catalyst is 375.23g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.29%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 11]

The preparation of catalyst:

(4) by the cobalt acetate (Co (OA of the Co containing 0.64g_C)₂·4H₂) and the copper acetate (Cu (OA of the Cu containing 0.68g O_C)₂· H₂O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Co content is 0.64g/L, and Cu contains Amount is 0.68g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 379.35g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.57%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2, improve vinyl acetate catalyst space-time yield and In terms of selectivity, in the catalyst that the present invention uses, Ni metal has preferable association in the metal Co and IB metal in Ferrious material Same-action illustrates metal Pd, metal Au, potassium acetate, cobalt element and copper in the activity and selectivity side for improving catalyst Face has preferable synergistic effect.

[embodiment 12]

The preparation of catalyst:

(4) by the cobalt acetate (Co (OA of the Co containing 0.64g_C)₂·4H₂) and the silver ammino solution ([Ag of the Ag containing 0.68g O (NH₃)₂]OH·XH₂O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings are catalyzed Agent precursor I V；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Co content is 0.64g/L, and Ag contains Amount is 0.68g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 379.43g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.48%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 13]

The preparation of catalyst:

(4) by the cobalt acetate (Co (OA of the Co containing 0.64g_C)₂·4H₂O), the copper acetate (Cu (OA of the Cu containing 0.25g_C)₂· H₂) and the silver ammino solution ([Ag (NH of the Ag containing 0.43g O₃)₂]OH·XH₂O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Co content is 0.64g/L, and Cu contains Amount is 0.25g/L, and Ag content is 0.43g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 379.91g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.13%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

Found out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, is improving vinyl acetate catalyst space-time yield In the catalyst used with selective aspect, the present invention, in Ferrious material in metal Co and IB metal Ni metal, metal Ag have compared with Good synergistic effect illustrates metal Pd, metal Au, potassium acetate, cobalt element, copper and silver element in the work for improving catalyst Property and selectivity aspect have preferable synergistic effect.

[embodiment 14]

The preparation of catalyst:

(4) by the ferrous acetate (Fe (OA of the Fe containing 0.64g_C)₂·4H₂O), the copper acetate (Cu (OA of the Cu containing 0.25g_C)₂· H₂) and the silver ammino solution ([Ag (NH of the Ag containing 0.43g O₃)₂]OH·XH₂O) aqueous solution 150ml is immersed on precursor II I, warp 110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Fe content is 0.64g/L, and Cu contains Amount is 0.25g/L, and Ag content is 0.43g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 379.85g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.19%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

[embodiment 15]

The preparation of catalyst:

(4) by the cobalt acetate (Co (OA of the Co containing 0.41g_C)₂·4H₂O), the ferrous acetate (Fe (OA of the Fe containing 0.23g_C)₂· 4H₂O), the copper acetate (Cu (OA of the Cu containing 0.25g_C)₂·H₂) and the silver ammino solution ([Ag (NH of the Ag containing 0.43g O₃)₂]OH· XH₂O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；

The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Co content is 0.41g/L, and Fe contains Amount is 0.23g/L, and Cu content is 0.25g/L, and Ag content is 0.43g/L, acetic acid potassium content 33g/L.

The activity for being computed the catalyst is 381.32g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.62%.In order to just In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.

Found out on year-on-year basis by embodiment 15 and embodiment 13 and embodiment 14, is improving vinyl acetate catalyst space-time yield In the catalyst used with selective aspect, the present invention, metal Co in Ferrious material, Ni metal, gold in metal Fe and IB metal Belonging to Ag has preferable synergistic effect, illustrates metal Pd, metal Au, potassium acetate, cobalt element, ferro element, copper and silver element There is preferable synergistic effect in terms of the activity and selectivity for improving catalyst.

Table 1

Table 2

Claims

1. producing catalyst used in ethylene process vinyl acetate, the catalyst includes carrier, active component and co-catalyst；

The carrier uses SiO₂、Al₂O₃Or its mixture, the co-catalyst are alkali metal acetate, the active component It is selected from including metal Pd, metal Au, Ferrious material and selected from least one of IB metal metallic element, the IB metallic element At least one of copper or silver；

The preparation method of the catalyst, includes the following steps:

(1) compound solution of the compound of palladium and gold is mixed by the composition of catalyst with carrier, obtains catalyst precarsor I；

(3) compound state Pd in catalyst precarsor II and compound state Au are reduced to metal Pd and metal Au obtains catalyst precarsor III；

(4) metallic compound in Ferrious material compound and IB is supported on catalyst using infusion process by the composition for pressing catalyst Precursor II I obtains catalyst precarsor IV after dry, roasting；

2. catalyst used in production ethylene process vinyl acetate according to claim 1, it is characterised in that the iron series gold Belong to element and is selected from least one of iron, cobalt and nickel.

3. catalyst used in production ethylene process vinyl acetate according to claim 1, it is characterised in that the alkali metal Acetate is potassium acetate.

4. catalyst used in production ethylene process vinyl acetate according to claim 1, it is characterised in that living in catalyst Property component metals Pd content be 1.0~12.0g/L, the content of activity component metal Au is 0.1~10.0g/L.

5. catalyst used in production ethylene process vinyl acetate according to claim 1, it is characterised in that institute in catalyst At least one content for stating activity component metal metal in Ferrious material and IB is 0.5~7.0g/L.

6. catalyst used in production ethylene process vinyl acetate according to claim 3, it is characterised in that vinegar in catalyst The content of sour potassium is 10~90g/L.

7. the synthetic method of ethylene process vinyl acetate, using ethylene, acetic acid and oxygen as raw material, in any one of claim 1~6 institute Reaction obtains vinyl acetate in the presence of stating catalyst.

8. synthetic method according to claim 7, it is characterized in that the temperature of reaction is 130~150 DEG C, the pressure of reaction is 0.1~1.0MPa, with molar ratio computing ethylene: acetic acid: oxygen=1:(0.1~0.3): (0.05~0.2), raw material volume air speed are 1500~2500h^-1。