CN106582872A - Catalyst used for synthesizing ethylene method produced vinyl acetate - Google Patents
Catalyst used for synthesizing ethylene method produced vinyl acetate Download PDFInfo
- Publication number
- CN106582872A CN106582872A CN201510676730.8A CN201510676730A CN106582872A CN 106582872 A CN106582872 A CN 106582872A CN 201510676730 A CN201510676730 A CN 201510676730A CN 106582872 A CN106582872 A CN 106582872A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- vinyl acetate
- acetic acid
- precarsor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst used for synthesizing ethylene method produced vinyl acetate. The problems of poor activity and low selectivity of catalysts in the prior art are mainly solved in the invention. The catalyst used for synthesizing ethylene method produced vinyl acetate comprises a carrier, an active component and a cocatalyst; and the carrier adopts SiO2 or Al2O3 or a SiO2 and Al2O3 mixture, the cocatalyst is alkali metal acetate, and the active component comprises metal Pd, metal Au, and at least one metal element selected from lanthanide metals and group IIB metals. The catalyst disclosed in the invention well solves the problems, and can be used in industrial production of the vinyl acetate.
Description
Technical field
The present invention relates to the synthetic method of the catalyst, the preparation method of catalyst and ethylene process vinyl acetate used by synthesizing ethylene method vinyl acetate.
Background technology
Vinyl acetate (VAc) is one of 50 kinds of maximum industrial chemicals of world wide production, by autohemagglutination or with other monomer copolymerizations, the derivatives such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or copolymer resins (EVA), vinyl acetate-chloride copolymer (EVC) can be generated.These derivatives are widely used in the aspects such as cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, water-solubility membrane and the soil conditioner of adhesive, building coating, paper or fabric.The main method that ethylene process vinyl acetate is produced in the world today is with ethene, oxygen and acetic acid as raw material, with Pd-Au-KOAc/SiO2System makees catalyst, is synthesized by gas phase catalytic reaction.
After the technique for finding ethene vapor phase method production vinylacetate from nineteen seventies, people are devoted to more high reaction activity with selective catalyst research.At present, people are more to concentrate on the dispersion of research precious metal palladium and gold or other elements on carrier and distribution, distribution of the active component on carrier also develops into eggshell type from protein type, the utilization rate of noble metal effectively improves, increased the reactivity of units activity component agent, the generation of side reaction is reduced, reaction selectivity is improve.
Chinese patent (CN1226188A, for preparing the palladium-gold catalyst of vinyl acetate) provide a kind of preparation method for preparing the catalyst for being loaded with major catalyst noble metal, promoter metal and alkali metal or alkaline earth metal compound.Its concrete manufacture process is as follows：1. in the dipping tank of rotation, the mixed liquor of the noble metal for having configured and co-catalyst is added, is passed through hot-air drying；2. the solution for taking the alkaline matters such as a certain amount of sodium metasilicate is made an addition in dried catalyst, and the palladium and gold of the chlorination state of original water soluble are changed into into the insoluble hydroxide state palladium of water and gold；3. the palladium and Au catalyst of hydroxide state are reduced in nitrogen atmosphere, that is, is reduced into the palladium and Au catalyst of metallic state；4. it is washed till without chlorion, is dried, soak potassium acetate, after being dried the catalyst is obtained final product.
United States Patent (USP) (US 3743607, entitled Palladium-gold catalyst) describes the preparation method of the catalyst of homogeneous impregnation, and the method includes：1. palladium, the solution impregnating carrier of gold compound are used；2. it is dried；3. palladium, gold compound are reduced to into Metal Palladium, gold；4. wash, be dried.
United States Patent (USP) (US 4048096, entitled Surface impregnated catalyst) describes the preparation method of the catalyst of shell dipping, and the method includes：1. with containing palladium, the solution impregnating carrier of gold compound；2. the carrier after impregnating is contacted with the aqueous solution containing alkali compounds sodium metasilicate, and water-soluble palladium, gold compound are precipitated as into insoluble palladium, gold compound；3. palladium, gold compound are changed into into Metal Palladium, gold with reducing agent；4. it is dried to obtain the catalyst after contacting with alkali metal acetate after washing.The space time yield of the catalyst that said method is obtained is relatively low with selective.
The content of the invention
One of the technical problem to be solved is the not high problem of the vinyl acetate catalyst activity and selectivity synthesized in prior art.There is provided the catalyst used by a kind of synthesizing ethylene method vinyl acetate, the characteristics of the catalyst has high-activity high-selectivity.
The two of the technical problem to be solved are the preparation methods of one of technical problem catalyst.
The three of the technical problem to be solved are the methods using one of the technical problem catalyst synthesizing ethylene method vinyl acetate.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：Catalyst used by synthesizing ethylene method vinyl acetate, the catalyst includes carrier, active component and co-catalyst；The carrier adopts SiO2、Al2O3Or its mixture, the co-catalyst is alkali metal acetate, and the active component includes the compound of metal Pd, metal Au and at least one metallic element in lanthanide series metal and IIB metals.
At least one in the preferred lanthanum of lanthanide element described in above-mentioned technical proposal, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
At least one in above-mentioned technical proposal, in the preferred zinc of the IIB metallic elements, cadmium and mercury.
In above-mentioned technical proposal, the alkali metal acetate is preferably potassium acetate.
In above-mentioned technical proposal, used as most preferred technical scheme, the catalyst includes Pd, Au, potassium acetate, lanthanide element and IIB metallic elements simultaneously；Such as described catalyst includes Pd, Au, potassium acetate, samarium element and cadmium element (or Zn-ef ficiency), or the catalyst includes Pd, Au, potassium acetate, samarium element (or lutetium element), cadmium element and Zn-ef ficiency, or the catalyst includes Pd, Au, potassium acetate, samarium element, lutetium element, cadmium element and Zn-ef ficiency.
In above-mentioned technical proposal, the content of activity component metal Pd is preferably 1.0～12.0g/L in the catalyst.
In above-mentioned technical proposal, the content of activity component metal Au is preferably 0.1～10.0g/L in the catalyst.
In above-mentioned technical proposal, the active component at least one metal element content of metal in lanthanide series metal and IIB is preferably 0.5～7.0g/L.
In above-mentioned technical proposal, the content of potassium acetate is preferably 10～90g/L in the catalyst.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Method for preparing catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps：
(1) compound solution of the compound of palladium and gold is mixed with carrier by the composition of catalyst, obtains catalyst precarsor I；
(2) make compound containing Pd and compound containing Au be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd and compound state Au in catalyst precarsor II are reduced to into metal Pd and metal Au obtains catalyst precarsor III；
(4) by the composition of catalyst, metallic compound in lanthanide metal compound and/or IIB is supported on into catalyst precarsor III using infusion process, after dry, roasting catalyst precarsor IV is obtained；
(5) co-catalyst liquor kalii acetici is sufficiently mixed with catalyst precarsor IV, is dried to obtain the catalyst.
In above-mentioned technical proposal, do not specially required based on the reducing agent of the understanding step (3) of those skilled in the art, reducing agent can be gas or liquid, at least one in the preferred hydrogen of reducing agent, hydrazine hydrate；Step (4) and step (5) baking temperature are preferably 80～120 DEG C, and drying time is preferably 1～5 hour；Step (4) roasting condition is advisable so that lanthanide metal compound and IIB compounds are converted into into oxide, and such as sintering temperature is preferably 300～500 DEG C, and roasting time is preferably 1～5 hour.
At least one in above-mentioned technical proposal, in the compound (such as, but not limited to lanthanum acetate, cerous acetate, praseodymium acetate, acetic acid neodymium, acetic acid europium, acetic acid samarium, acetic acid ytterbium and acetic acid lutetium) of the compound of the preferred lanthanum of step (4) lanthanide metal compound, the compound of cerium, the compound of praseodymium, the compound of neodymium, the compound of europium, the compound of samarium, the compound of ytterbium and lutetium；The preferred zinc of step (4) the IIB metallic compounds compound (such as, but not limited to zinc citrate, zinc gluconate, zinc acetate, zinc nitrate), at least one in the compound (such as, but not limited to mercuric acetate) of the compound (such as, but not limited to cadmium nitrate, cadmium acetate) of cadmium and mercury.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of ethylene process vinyl acetate, with ethene, acetic acid and oxygen as raw material, the reaction in the presence of above-mentioned catalyst obtains vinyl acetate.
The key of the present invention is the selection of catalyst, skilled person will know how determining the proportioning of suitable reaction temperature, reaction time, reaction pressure and material according to actual needs.But, in above-mentioned technical proposal, the temperature of reaction be preferably 130～150 DEG C, the pressure of reaction be preferably 0.1～1.0MPa, with molar ratio computing ethene:Acetic acid:Oxygen is preferably 1:(0.1～0.3):(0.05～0.2), raw material volume air speed is preferably 1500～2500h-1。
Compared with prior art, the key of the present invention is that catalyst includes metal Pd, metal Au, potassium acetate and at least one metallic element in lanthanide series metal and IIB metals, be conducive to improving the activity of catalyst and stability, so as to improve yield and the selectivity of vinyl acetate.
The catalyst of said method synthesis with evaluating apparatus with comparative catalyst to be evaluated respectively and is calculated the activity of catalyst and and selective.Evaluation method is to load 900ml catalyst in the reactor, using nitrogen leak test, after guaranteeing system without leak source, the flow of ethene is adjusted to into 64.4mol/h, while heating up, when reaction bed temperature reaches 120 DEG C, the acetic acid of input 9.30mol/h, starts to throw oxygen after 20 minutes, and sufficient oxygen is thrown after 120 minutes, the amount of oxygen is 3.88mol/h, and air speed is 2000h-1, controlling reaction temperature is 142 DEG C in course of reaction, reaction pressure 0.78MPa, and controlling raw material ratio is：Ethene/acetic acid/oxygen=83.0/12.0/5.0 (mol ratio).
The content of each component in gas chromatography analysis product, and calculate activity (space-time yield) and the selectivity of catalyst by following equation：
Test result indicate that, during using catalyst of the present invention, the activity of catalyst reaches 376.15g/Lh, the selectivity of Dichlorodiphenyl Acetate ethene is 95.18%, achieve preferable technique effect, when especially including at least one metallic element in metal Pd, metal Au, potassium acetate, lanthanide series metal and at least one metallic element in IIB in catalyst simultaneously, more prominent technique effect is achieved, in can be used for the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid samarium (Sm (OA containing 1.39gSmC)3·6H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Sm contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.15g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.18%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 2】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the cadmium acetate (Cd (OA containing 1.39gCdC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Cd contents are 1.48g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.97g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.24%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) the solution 300ml containing 33g potassium acetates is weighed, is immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.85g/L, Au contents 1.87g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 365.51g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 94.20%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with embodiment 1～2, the catalyst that the present invention is adopted, using simultaneously containing metal Pd, metal Au, potassium acetate and samarium element or while the catalyst performance ratio containing metal Pd, metal Au, potassium acetate and cadmium element is more excellent containing only the performance of metal Pd, metal Au, potassium acetate catalyst, the space-time yield of vinyl acetate catalyst and it is selective will be high.
【Embodiment 3】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical Al of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2O3Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the lanthanum acetate (La (OA containing 1.39gLaC)3·5H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, La contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.08g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.17%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 4】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the cerous acetate (Ce (OA containing 1.39gCeC)3·6H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Ce contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.12g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.21%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 5】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the praseodymium acetate (Pr (OA containing 1.39gPrC)3·5H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Pr contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.93g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.23%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 6】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid neodymium (Nd (OA containing 1.39gNdC)3·5H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Nd contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.96g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.16%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 7】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid europium (Eu (OA containing 1.39gEuC)3·6H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Eu contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.94g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.22%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 8】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid ytterbium (Yb (OA containing 1.39gYbC)3·6H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Yb contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.95g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.15%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 9】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid lutetium (Lu (OA containing 1.39gLuC)3·6H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Lu contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 376.17g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.19%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 10】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the zinc acetate (Zn (OA containing 1.39gZnC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Zn contents are 1.39g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.98g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.25%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 11】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid samarium (Sm (OA containing 0.79gSmC)3·6H2) and (Cd (OA of the cadmium acetate containing 0.60gCd OC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Sm contents are 0.79g/L, and Cd contents are 0.60g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 379.81g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.53%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 1 and embodiment 2 by embodiment 11, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, metal Sm in lanthanide series metal and metal Cd in IIB metals has preferably synergy, illustrates that metal Pd, metal Au, potassium acetate, samarium element and cadmium element have preferable cooperative effect in terms of the activity and selectivity of catalyst is improved.
【Embodiment 12】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid samarium (Sm (OA containing 0.79gSmC)3·6H2) and (Zn (OA of the zinc acetate containing 0.60g Zn OC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Sm contents are 0.79g/L, and Zn contents are 0.60g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 379.56g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 95.74%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 13】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid samarium (Sm (OA containing 0.79gSmC)3·6H2O cadmium acetate (Cd (OA), containing 0.32gCdC)2·2H2) and (Zn (OA of the zinc acetate containing 0.28g Zn OC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Sm contents are 0.79g/L, and Cd contents are 0.32g/L, and Zn contents are 0.28g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 381.36g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 96.17%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 11 and embodiment 12 by embodiment 13, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, metal Sm has preferably synergy with metal Cd, metal Zn in IIB metals in lanthanide series metal, illustrates that metal Pd, metal Au, potassium acetate, samarium element, cadmium element and Zn-ef ficiency have preferable cooperative effect in terms of the activity and selectivity of catalyst is improved.
【Embodiment 14】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid lutetium (Lu (OA containing 0.79gLuC)3·6H2O cadmium acetate (Cd (OA), containing 0.32gCdC)2·2H2) and (Zn (OA of the zinc acetate containing 0.28g Zn OC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Lu contents are 0.79g/L, and Cd contents are 0.32g/L, and Zn contents are 0.28g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 381.28g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 96.30%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 15】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium acid carbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.85gPd and 1.87gAu, aqueous solution of chloraurate obtain maceration extract 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chlorion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid samarium (Sm (OA containing 0.44gSmC)3·6H2O), the acetic acid lutetium (Lu (OA containing 0.35gLuC)3·6H2O cadmium acetate (Cd (OA), containing 0.32gCdC)2·2H2) and (Zn (OA of the zinc acetate containing 0.28g Zn OC)2·2H2O) aqueous solution 150ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetates will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and be immersed in precursor I V, 100 DEG C of dryings of Jing will obtain the catalyst.
It is 3.85g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Sm contents are 0.44g/L, and Lu contents are 0.35g/L, and Cd contents are 0.32g/L, and Zn contents are 0.28g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 382.59g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethene is 96.63%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 13 and embodiment 14 by embodiment 15, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, metal Cd, metal Zn have preferably synergy in metal Sm, metal Lu and IIB metal in lanthanide series metal, illustrate that metal Pd, metal Au, potassium acetate, samarium element, lutetium element, cadmium element and Zn-ef ficiency have preferable cooperative effect in terms of the activity and selectivity of catalyst is improved.
Table 1
Table 2
Claims (10)
1. the catalyst used by synthesizing ethylene method vinyl acetate, the catalyst includes carrier, active component and co-catalyst；
The carrier adopts SiO2、Al2O3Or its mixture, the co-catalyst be alkali metal acetate, the active component
At least one metallic element including metal Pd, metal Au and in lanthanide series metal and IIB metals.
2. the catalyst used by synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that the lanthanide series metal
At least one of the element in lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
3. the catalyst used by synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that the IIB metals
At least one of the element in zinc, cadmium and mercury.
4. the catalyst used by synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that the alkali metal vinegar
Hydrochlorate is potassium acetate.
5. the catalyst used by synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that activity in catalyst
The content of component metals Pd is 1.0～12.0g/L, and the content of activity component metal Au is 0.1～10.0g/L.
6. the catalyst used by synthesizing ethylene method 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 lanthanide series metal and IIB is 0.5～7.0g/L.
7. the catalyst used by synthesizing ethylene method vinyl acetate according to claim 4, it is characterised in that vinegar in catalyst
The content of sour potassium is 10～90g/L.
8., by the preparation method of the catalyst described in claim 1, comprise the steps：
(1) compound solution of the compound of palladium and gold is mixed with carrier by the composition of catalyst, obtains catalyst precarsor I；
(2) make compound containing Pd and compound containing Au be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd and compound state Au in catalyst precarsor II are reduced to into metal Pd and metal Au obtains catalyst precarsor III；
(4) by the composition of catalyst, metallic compound in lanthanide metal compound and/or IIB is supported on into catalysis using infusion process
Agent precursor II I, after dry, roasting catalyst precarsor IV is obtained；
(5) co-catalyst liquor kalii acetici is sufficiently mixed with catalyst precarsor IV, is dried to obtain the catalyst.
9. the synthetic method of ethylene process vinyl acetate, with ethene, acetic acid and oxygen as raw material, in any one of claim 1～7 institute
State reaction in the presence of catalyst and obtain vinyl acetate.
10. synthetic method according to claim 9, it is characterized in that the temperature reacted be 130～150 DEG C, the pressure of reaction be
0.1～1.0MPa, with molar ratio computing ethene:Acetic acid:Oxygen=1:(0.1～0.3):(0.05～0.2), raw material volume air speed is
1500～2500h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510676730.8A CN106582872B (en) | 2015-10-19 | 2015-10-19 | Catalyst used in synthesizing ethylene method vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510676730.8A CN106582872B (en) | 2015-10-19 | 2015-10-19 | Catalyst used in synthesizing ethylene method vinyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582872A true CN106582872A (en) | 2017-04-26 |
| CN106582872B CN106582872B (en) | 2019-09-06 |
Family
ID=58554438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510676730.8A Active CN106582872B (en) | 2015-10-19 | 2015-10-19 | Catalyst used in synthesizing ethylene method vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582872B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425444A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268395A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Catalyst for producing vinyl acetate |
| US20050234262A1 (en) * | 2004-04-14 | 2005-10-20 | N. E. Chemcat Corporation | Production process for catalyst |
| WO2011104170A1 (en) * | 2010-02-24 | 2011-09-01 | Evonik Degussa Gmbh | Thermally and mechanically stable precious metal-loaded catalysts |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103121953A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing vinyl acetate from ethylene by gas-phase oxidation |
-
2015
- 2015-10-19 CN CN201510676730.8A patent/CN106582872B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268395A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Catalyst for producing vinyl acetate |
| US20050234262A1 (en) * | 2004-04-14 | 2005-10-20 | N. E. Chemcat Corporation | Production process for catalyst |
| WO2011104170A1 (en) * | 2010-02-24 | 2011-09-01 | Evonik Degussa Gmbh | Thermally and mechanically stable precious metal-loaded catalysts |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103121953A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing vinyl acetate from ethylene by gas-phase oxidation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425444A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
| CN114425444B (en) * | 2020-10-14 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582872B (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549517B (en) | vinyl acetate catalyst and application thereof | |
| CN102218345B (en) | Catalyst for synthesizing vinylacetate and preparation method thereof | |
| CN103121952B (en) | Vinyl acetate preparation method | |
| CN103120958B (en) | Vinyl acetate catalyst and preparation method thereof | |
| CN106582820B (en) | Catalyst used in ethylene process vinyl acetate synthesis | |
| CN106423269A (en) | Unsaturated acetic ester catalyst and preparing method thereof | |
| CN106423284A (en) | Vinyl acetate catalyst and preparing method thereof | |
| CN106582872B (en) | Catalyst used in synthesizing ethylene method vinyl acetate | |
| CN106582823A (en) | Catalyst for preparing vinyl acetate by ethylene method | |
| CN106582873A (en) | Catalyst for producing vinyl acetate by ethylene process | |
| CN106582866B (en) | Prepare catalyst used in ethylene process vinyl acetate | |
| CN106582869A (en) | Catalyst for preparing vinyl acetate by ethylene method | |
| CN106582868B (en) | Allyl acetate preparation catalyst used | |
| CN106582822B (en) | For synthesizing the catalyst of allyl acetate | |
| CN106582824B (en) | Catalyst for synthesizing ethylene method vinyl acetate | |
| CN106582854B (en) | Allyl acetate catalyst and its application | |
| CN106582826B (en) | Produce catalyst used in ethylene process vinyl acetate | |
| CN105642290A (en) | Preparation method of catalyst for reforming of methane and carbon dioxide to prepare syngas | |
| CN106582821B (en) | Catalyst for preparing allyl acetate | |
| CN105642288A (en) | Preparation method of catalyst for partial oxidation of methane to prepare syngas | |
| CN105585494B (en) | The method of methyl acetate carbonylation production vinyl acetate | |
| CN106582870B (en) | Synthesize the catalyst of allyl acetate | |
| CN106582856B (en) | Synthesize catalyst used in allyl acetate | |
| CN106582877B (en) | Produce the catalyst of allyl acetate | |
| CN112517065B (en) | Preparation method of catalyst for vinyl acetate process by ethylene gas phase method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |