CN104549497A - Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof - Google Patents
Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof Download PDFInfo
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- CN104549497A CN104549497A CN201310512432.6A CN201310512432A CN104549497A CN 104549497 A CN104549497 A CN 104549497A CN 201310512432 A CN201310512432 A CN 201310512432A CN 104549497 A CN104549497 A CN 104549497A
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Abstract
The invention relates to a catalyst for vinyl acetate synthesis by an acetylene method and a preparation method thereof as well as a synthesis method of vinyl acetate, and aims at mainly solving the problem in the prior art that the content of byproduct benzene in a vinyl acetate product is high. The problem is well solved by adopting the technical scheme that the catalyst comprises a carrier, an active component and a cocatalyst, wherein the carrier is active carbon, the active component is zinc acetate, and the content of zinc acetate in the catalyst is 80g/L-240g/L. The catalyst is characterized in that the cocatalyst of the catalyst is acetate of main group metal elements in the periodic table of elements, wherein the main group metal elements are selected from at least one of IIA group metal elements or IVA group metal elements. The catalyst can be used for industrial production of the synthesis of vinyl acetate by the acetylene method.
Description
Technical field
The present invention relates to the preparation method of acetylene in gas phase method vinyl acetate catalyst, this catalyzer, and the synthetic method of vinyl acetate between to for plastic.
Background technology
Vinyl acetate, be called for short vinyl acetate between to for plastic (VAM), it is a kind of important Organic Chemicals, mainly for the production of derivatives such as Vinyl Acetate Copolymer (PVAc), polyvinyl alcohol (PVOH), vinyl acetate-ethylene copolymerization emulsions (VAE) or copolymer resins (EVA), polyvinyl acetate-chloride copolymers (EVC), polyacrylonitrile comonomer and Derlins, in coating, slurry, tackiness agent, polyvinyl, film, leather processing, synthon, soil improvement etc., there is value of exploiting and utilizing widely.Along with the continuous progress of production technology, its Application Areas is also in continuous expansion.
Within 2011, global vinyl acetate between to for plastic production capacity reaches 743.4 ten thousand tons/year, mainly concentrates on Asia, North America and West Europe.Add up by regional production capacity, Asia-Pacific is 398.8 ten thousand tons/year, accounts for 53.6%; North America is 206.3 ten thousand tons/year, accounts for 27.8%; West Europe is 117.1 ten thousand tons/year, accounts for 15.8%; Other areas account for 2.9%.Wherein, the production capacity of Chinese vinyl acetate between to for plastic is 216.5 ten thousand tons/year.
At present, vinyl acetate between to for plastic main production route is ethylene process and acetylene method.Wherein, acetylene method comprises again gas acetylene method and carbide acetylene method two kinds.Gas acetylene method adopts fixed-bed process, selects particulate state Zinc Acetate/activated Carbon Catalyst; And carbide acetylene method adopts fluidized-bed process, the Zinc Acetate/activated Carbon Catalyst of choice of powder shape.Because resource structures is different, North America, West Europe, the countries and regions such as Singapore of Japan and Korea S adopt ethylene process technique substantially, and Korea, and India then all adopts acetylene method technique, Chinese, Russian, the countries and regions such as Eastern Europe then two kinds of techniques depositing.The discovery of the Sweet natural gas new along with China and shale gas resource and the maturation of its production technique and perfect, at China's Devoting Major Efforts To Developing with promote gas acetylene method vinyl acetate production technique and have very good prospect.
Nineteen twenty-two, first Wacker company of Germany used acetylene in gas phase to synthesize the method for VAM, improves drop into industrial production by Hochst company.Its catalyzer is active ingredient with zinc acetate, take gac as carrier, and uses till today always.It is fast that this catalyzer shortcoming comprises activity decrease, and throughput is not high, and increase along with temperature of reaction raises by product, catalyzer is not long for work-ing life.Meanwhile, acetylene method possesses skills simply, and catalyzer is inexpensive, be easy to get, and active fair, selectivity is high, the advantages such as expense is low of founding the factory.Therefore, how effectively to improve the activity of this catalyzer and become this catalytic field important scientific issues work-ing life, various countries researchist starts with from the selection of active ingredient, promotor, carrier and the aspect such as modification, catalyst preparation process and has carried out systematic study to this problem, achieves certain phasic results.
Acetylene method synthetic route used catalyst active ingredient is mainly zinc acetate, but researchist attempts adopting other multiple composite oxides to replace zinc acetate as active ingredient.As Japanese scholars proposes with bi component oxide (V
2o
5-ZnO, Fe
2o
3-ZnO) or three component oxide compound (16ZnO32Fe
2o
3v
2o
5and 24ZnO8Cr
2o
3v
2o
5) as the active ingredient of catalyzer, although above-mentioned catalyzer has higher than Zn (OAc) at 250 DEG C
2the activity of/C catalyst, but fail to realize industrialization because of shortcomings such as temperature of reaction are high, cost is high, activity decrease is fast.Soviet Union scholar once studied the catalyzer such as silicate and Zinc aluminate of Cd and Zn.Chinese patent (CN 86107833A, a kind of Catalysts and its preparation method for vinyl acetate synthesis) reports ZnO-ZnCl
2its space time yield of/C catalyst is higher than Zn (OAc)
2/ C catalyst about 30%, but because employing nitrate in this catalyst preparation process, during decomposition, produce a large amount of NO
xand contaminate environment, and add ZnCl in catalyzer
2, Cl
-corrodibility is produced to equipment, limits the popularization of this catalyzer.The research substituted for acetylene method vinyl acetate catalyst active ingredient does not make substantial progress, and up to the present, acetylene method vinyl acetate catalyst is still active ingredient with zinc acetate.
Meanwhile, researchist attempts at Zn (OAc)
2add promotor in/C catalyst and reach the object improving catalyst performance.As Chinese patent (CN 1903435A, a kind of Catalysts and its preparation method for vinyl acetate synthesis) selects Bismuth Subcarbonate as promotor, the space-time yield of this catalyzer is made to have 2.02 t/m
3d brings up to 2.67 t/m
3d, catalyst activity improves 32.2%.Master's thesis (University of Fuzhou, 2006, the research of acetylene method vapor-phase synthesis vinyl acetate catalyst) points out that promotor potassium, barium and lanthanum can improve Zn (OAc)
2the activity of/C catalyst.The interpolation of promotor significantly improves the activity of this catalyzer, and current Bismuth Subcarbonate has been applied in the production of industrial acetic acid catalyst for ethylene as promotor.
For a long time, domestic and international many scholars attempt to replace the experiment of absorbent charcoal carriers with silica gel, aluminum oxide, pure aluminium silicate and molecular sieve etc. and unsuccessful.Document (chemical work Games, 1962,85 (16): 1; Petrochemical complex, 1979, (8) 7:49) research finds, when silica gel, aluminum oxide, pure aluminium silicate and molecular sieve etc. are as carrier, catalyst activity specific activity high-area carbon catalyst activity is much lower.Facts have proved, gac, as acetylene method vinyl acetate catalyst carrier, up to the present can not be substituted.Meanwhile, researchist considers to modify absorbent charcoal carrier, thus reaches the object improving carrier property.As document (petrochemical complex, 2004,33 (11): 1024) research finds, the gac crossed through massfraction 15% nitric acid treatment is that the catalyzer that carrier obtains improves 5.36% than the activity that undressed gac is the catalyzer that carrier obtains.Chinese patent (CN 102029193A, a kind of make support of the catalyst gac and treatment process and application) select hydrogen peroxide to carry out pre-treatment to absorbent charcoal carrier, result shows, its catalytic activity of catalyzer raising 2 ~ 15% that the gac adopting the described method process of this invention to obtain is obtained.Chinese patent (CN 102284304A, a kind of preparation method of high-efficiency catalyst for vinyl acetate synthesis by acetylene method) except hydrogen peroxide, also, select a series of oxygenants such as sulfuric acid, potassium permanganate and ammonium persulphate to carry out the preparation for the synthesis of vinyl acetate catalyst after pre-treatment to gac, this patent only reports the percentage composition of vinyl acetate between to for plastic in product, the activity data of this catalyzer undeclared.Though select oxygenant to carry out to absorbent charcoal carrier the activity that pre-treatment can improve catalyzer to a certain extent, but the gac after acid or other oxidizer treatment need make gac be neutral through washing for a long time, extracting mostly, and time of drying is long, add production time and the cost of catalyzer.
Along with recent year is newly-built and the vinyl acetate between to for plastic device of enlarging is constantly driven, approaching to saturation in domestic vinyl acetate between to for plastic market, has even occurred superfluous sign.Therefore, how to open up vinyl acetate between to for plastic Downstream Market, the vinyl acetate between to for plastic derived product that exploitation has high added value is the task of top priority.And improve one of important prerequisite factor that vinyl acetate between to for plastic quality product is its high added value derived product of exploitation.
The purposes that vinyl acetate between to for plastic one has high added value is synthesizing vinyl acetate-ethylene copolymer (VAE) emulsion, for cigarette glue in cigarette production process, but domesticly at present ethylene process vinyl acetate between to for plastic product index is only had to reach for cigarette Industrial Coil smoked sheet specification of quality.And the vinyl acetate between to for plastic product that acetylene method is produced is because of containing a small amount of by product benzene (< 5ppmw), constrain it for the production of cigarette glue raw material VAE emulsion, the problem how reducing by product benzene in acetylene method vinyl acetate between to for plastic product becomes restriction, and it is applied to the key problem of cigarette glue raw material.And academia and industry member mainly concentrate on for the research work of acetylene method vinyl acetate catalyst and improve in the problem such as catalyst activity and catalyst life, for raising selectivity of catalyst, the problem especially reducing its by product benzene content has no report.
Summary of the invention
One of technical problem to be solved by this invention is the problem that in the vinyl acetate between to for plastic product existed in prior art, by product benzene content is high, there is provided a kind of new vinyl acetate catalyst, this catalyzer has the selectivity height by product feature that particularly by product benzene content is low less.
Technical problem two to be solved by this invention, is to provide the preparation method of the corresponding catalyzer of one of a kind of and above-mentioned technical problem.
Technical problem three to be solved by this invention, is to provide a kind of synthetic method adopting the vinyl acetate between to for plastic of the described catalyzer of one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: acetylene method vinyl acetate catalyst, described catalyzer comprises carrier, active ingredient and promotor, described carrier is gac, active ingredient is zinc acetate, and in wherein said catalyzer, zinc acetate content is 80 ~ 240 g/L; It is characterized in that the promotor of described catalyzer is the acetate of Main Group Metal Elements in the periodic table of elements, wherein said Main Group Metal Elements is selected from least one in IIA race metallic element or IVA race metallic element.Preferred described Main Group Metal Elements comprises IIA race metallic element and IVA race metallic element simultaneously; Geng Youxuan IIA race's metallic element and IVA race metallic element mass ratio are 1: (0.2 ~ 2).
In technique scheme, in described catalyzer, the acetate content of Main Group Metal Elements is preferably 0.2 ~ 2.0 g/L in Main Group Metal Elements.At least one of described IIA race metallic element preferably in magnesium, calcium, strontium or barium.At least one of described IVA race metallic element preferably in germanium, tin or lead.Described gac is preferably ature of coal column charcoal, and specific surface area is preferably 1000 ~ 1300 cm
2/ g, adsorbs total pore volume and is preferably 0.6 ~ 0.8 cm
3/ g.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the as mentioned above preparation method of catalyzer, comprises the following steps:
A the preparation of () steeping fluid: the zinc acetate of aequum and promotor are dissolved in the water, is 4.6 ~ 5.0 by acetic acid adjust ph, obtains steeping fluid;
The dipping of (b) carrier: the carrier of aequum is mixed with above-mentioned steeping fluid;
C () is dry obtains described catalyzer.
In technique scheme, the temperature preferably 105 ~ 115 DEG C that step (c) is dry.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the synthetic method of vinyl acetate between to for plastic, under catalyzer described in any one of one of technical problem technical scheme exists, with acetylene and vinyl acetate between to for plastic for raw material, is obtained by reacting vinyl acetate between to for plastic.
In technique scheme, be preferably acetic acid with molar ratio computing raw material composition: acetylene=1:(5 ~ 12).Raw material volume air speed is preferably 250 ~ 350 h
-1.Reaction pressure is preferably 0.1 ~ 0.5 atm.Temperature of reaction is preferably 160 ~ 220 DEG C.
Reaction pressure of the present invention is gauge pressure.
Catalyzer in the specific embodiment of the invention uses inductively coupled plasma spectrum generator (ICP) to measure Zn and promoter metal constituent content in catalyzer.
Zinc acetate load type active carbon is selected to obtain compared with vinyl acetate catalyst with prior art, the present invention adds and is selected from least one in IIA race metal acetate salt or IVA race metal acetate salt as promotor, to interact the better effects playing and improve catalyst selectivity with zinc acetate and absorbent charcoal carrier, especially in reduction by product benzene content, there is unusual effect.Further, when co catalysis of the present invention comprises IIA race metal acetate salt and IVA race metal acetate salt simultaneously, there is synergy improve in catalyst selectivity, and the synergy of this synergy between magnesium acetate and plumbic acetate is particularly evident.Experimental result shows, it is 0.26 ppm that catalyzer of the present invention obtains benzene content in vinyl acetate between to for plastic, and benzene content is only the acetylene method vinyl acetate between to for plastic product 6.6% of current industrial application, achieves good technique effect.
Embodiment
[embodiment 1]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 7.44 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, Mg constituent content is 1.0 g/L;
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Use fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 40 ml;
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=6: 1;
Reaction raw materials volume space velocity: 300 h
-1;
Reaction pressure: 0.3 atm;
Temperature of reaction: 180 DEG C;
Reaction times: 100 h.
React 100 hr, with the content of each component in vapor-phase chromatography (GC) analytical reaction product, by benzene content in chromatography of gases-MS (GC-MS) analysed preparation, calculate the space-time yield of this catalyzer.For ease of comparing, underlying condition is listed in table 2.
[embodiment 2]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 0.71 g calcium acetate solid (molecular formula: Ca (CH
3cOO)
2) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, Ca constituent content is 1.0 g/L;
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 3]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 0.33 g barium acetate solid (molecular formula: Ba (CH
3cOO)
2) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, Ba constituent content is 1.0 g/L;
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 4]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 0.33 g plumbic acetate solid (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, Pb constituent content is 1.0 g/L;
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 5]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 6.2 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.06 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 0.2);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 6]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 5.0 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.11 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 0.5);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 7]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.7 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 8]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.0 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.20 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1.5);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 9]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 2.5 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.22 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 2);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 10]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.0 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g barium acetate (molecular formula: Ba (CH
3cOO)
2) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and barium element total content are 1.0 g/L(m
(Mg): m
(Ba)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 11]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 0.36 g calcium acetate (molecular formula: Ca (CH
3cOO)
2), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and calcium and lead element total content are 1.0 g/L(m
(Ca): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 12]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 0.17 g barium acetate (molecular formula: Ba (CH
3cOO)
2), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and barium and lead element total content are 1.0 g/L(m
(Ba): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
[embodiment 13]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.7 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Use fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 40 ml;
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=5: 1;
Reaction raw materials volume space velocity: 250 h
-1;
Reaction pressure: 0.1 atm;
Temperature of reaction: 160
oc;
Reaction times: 100 h.
React 100 hr, with the content of each component in vapor-phase chromatography (GC) analytical reaction product, by benzene content in chromatography of gases-MS (GC-MS) analysed preparation, calculate the space-time yield of this catalyzer.For ease of comparing, underlying condition is listed in table 2.
[embodiment 14]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.7 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Use fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 40 ml;
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=8: 1;
Reaction raw materials volume space velocity: 250 h
-1;
Reaction pressure: 0.2 atm;
Temperature of reaction: 170
oc;
Reaction times: 100 h.
React 100 hr, with the content of each component in vapor-phase chromatography (GC) analytical reaction product, by benzene content in chromatography of gases-MS (GC-MS) analysed preparation, calculate the space-time yield of this catalyzer.For ease of comparing, underlying condition is listed in table 2.
[embodiment 15]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.7 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Use fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 40 ml;
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=10: 1;
Reaction raw materials volume space velocity: 350 h
-1;
Reaction pressure: 0.4 atm;
Temperature of reaction: 200
oc;
Reaction times: 100 h.
React 100 hr, with the content of each component in vapor-phase chromatography (GC) analytical reaction product, by benzene content in chromatography of gases-MS (GC-MS) analysed preparation, calculate the space-time yield of this catalyzer.For ease of comparing, underlying condition is listed in table 2.
[embodiment 16]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 3.7 ml magnesium acetate solution (molecular formula: Mg (CH
3cOO)
2, concentration: 1 mol/L), 0.17 g plumbic acetate (molecular formula: Pb (CH
3cOO)
23H
2o) and 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L, and magnesium and lead element total content are 1.0 g/L(m
(Mg): m
(Pb)=1: 1);
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
The main preparation condition of catalyzer lists in table 1, and the physical data of catalyzer lists in table 2.
(2) catalyst performance evaluation
Use fixed-bed reactor evaluation, actual conditions is:
Catalyst loading volume: 40 ml;
Reaction raw materials composition (with molar ratio computing): acetylene: acetic acid=12: 1;
Reaction raw materials volume space velocity: 350 h
-1;
Reaction pressure: 0.5 atm;
Temperature of reaction: 220
oc;
Reaction times: 100 h.
React 100 hr, with the content of each component in vapor-phase chromatography (GC) analytical reaction product, by benzene content in chromatography of gases-MS (GC-MS) analysed preparation, calculate the space-time yield of this catalyzer.For ease of comparing, underlying condition is listed in table 2.
[comparative example 1]
(1) catalyst preparing
The preparation of (a) steeping fluid: take 18.0 g zinc acetates (molecular formula: Zn (CH
3cOO)
2) solid is in 60
oc is dissolved in the water the preparation 180 ml aqueous solution, and being adjusted to pH value with acetic acid is 4.85 obtain steeping fluid; Wherein zinc acetate content is 100 g/L;
The dipping of (b) carrier: take 120 ml ature of coal column charcoal (bulk densities: 0.35 g/ml, BET specific surface: 1200 cm
2/ g, total pore volume: 0.7 cm
3/ g); Join in above-mentioned steeping fluid, under 60 DEG C of conditions, flood 4 hr;
C () is dry: in air dry oven, obtains described catalyzer in dry 4 hr of 105 DEG C of temperature.
(2) catalyst performance evaluation
Evaluation method is with embodiment 1, and table 2 lists space time yield and the selective data of catalyzer.
table 1 catalyst preparation conditions
2(is continued for table) catalyst characterization and appreciation condition data
table 2(continues) catalyst characterization and appreciation condition data
Claims (10)
1. acetylene method vinyl acetate catalyst, described catalyzer comprises carrier, active ingredient and promotor, and described carrier is gac, and active ingredient is zinc acetate, and in wherein said catalyzer, zinc acetate content is 80 ~ 240g/L; It is characterized in that the promotor of described catalyzer is the acetate of Main Group Metal Elements in the periodic table of elements, wherein said Main Group Metal Elements is selected from least one in IIA race metallic element or IVA race metallic element.
2. catalyzer as claimed in claim 1, is characterized in that the acetate content of Main Group Metal Elements in described catalyzer counts 0.2 ~ 2.0g/L with Main Group Metal Elements.
3. catalyzer as claimed in claim 1, is characterized in that described IIA race metallic element is selected from least one in magnesium, calcium, strontium or barium.
4. catalyzer as claimed in claim 1, is characterized in that described IVA race metallic element is selected from least one in germanium, tin or lead.
5. catalyzer as claimed in claim 1, it is characterized in that described gac is ature of coal column charcoal, specific surface area is 1000 ~ 1300cm
2/ g, adsorbing total pore volume is 0.6 ~ 0.8cm
3/ g.
6. the preparation method of catalyzer described in any one of claim 1 ~ 5, comprises the following steps:
A the preparation of () steeping fluid: the zinc acetate of aequum and promotor are dissolved in the water, is 4.6 ~ 5.0 by acetic acid adjust ph, obtains steeping fluid;
The dipping of (b) carrier: the carrier of aequum is mixed with above-mentioned steeping fluid;
C () is dry obtains described catalyzer.
7. the synthetic method of vinyl acetate between to for plastic, under such as catalyzer according to any one of claim 1 ~ 5 exists, with acetic acid and acetylene for raw material, is obtained by reacting vinyl acetate between to for plastic.
8. synthetic method according to claim 7, is characterized in that consisting of acetic acid with molar ratio computing raw material: acetylene=1: (5 ~ 12).
9. synthetic method according to claim 7, is characterized in that raw material volume air speed is 250 ~ 350 h
-1.
10. synthetic method according to claim 7, it is characterized in that reaction pressure is 0.1 ~ 0.5atm, temperature of reaction is 160 ~ 220 DEG C.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268945A (en) * | 2015-05-11 | 2017-01-04 | 中国石油化工股份有限公司 | For synthesizing the catalyst of acetylene method vinyl acetate |
| CN106268943A (en) * | 2015-05-11 | 2017-01-04 | 中国石油化工股份有限公司 | Synthesis catalyst used by acetylene method vinyl acetate |
| CN107774308A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Vinyl acetate catalyst |
| CN107774332A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Vinyl acetate synthesis catalyst and preparation method thereof |
| CN107774309A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | For synthesizing the catalyst used in acetylene method vinyl acetate |
| CN107774337A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst used in natural gas synthesis acetylene method vinyl acetate |
| CN107774314A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Synthesize the catalyst of acetylene method vinyl acetate |
| CN107774333A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | The catalyst of vinyl acetate synthesis |
| CN107790190A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | Produce the catalyst of acetylene method vinylacetate |
| CN107790181A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | For synthesizing the catalyst of acetylene method vinyl acetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1281433B (en) * | 1965-06-04 | 1968-10-31 | Asahi Chemical Ind | Process for the production of vinyl acetate |
| CN101391229A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院化学研究所 | Catalyst containing rare-earth metal for preparing vinyl acetate using acetylene method and preparation method and use thereof |
| CN103111325A (en) * | 2011-11-16 | 2013-05-22 | 上海浦景化工技术有限公司 | Process for synthesizing vinyl acetate catalyst through acetylene method |
-
2013
- 2013-10-28 CN CN201310512432.6A patent/CN104549497B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1281433B (en) * | 1965-06-04 | 1968-10-31 | Asahi Chemical Ind | Process for the production of vinyl acetate |
| CN101391229A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院化学研究所 | Catalyst containing rare-earth metal for preparing vinyl acetate using acetylene method and preparation method and use thereof |
| CN103111325A (en) * | 2011-11-16 | 2013-05-22 | 上海浦景化工技术有限公司 | Process for synthesizing vinyl acetate catalyst through acetylene method |
Non-Patent Citations (1)
| Title |
|---|
| 于政锡: "乙炔法气相合成醋酸乙烯催化剂的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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| CN106268945B (en) * | 2015-05-11 | 2018-11-20 | 中国石油化工股份有限公司 | For synthesizing the catalyst of acetylene method vinyl acetate |
| CN107790190A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | Produce the catalyst of acetylene method vinylacetate |
| CN107774308A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Vinyl acetate catalyst |
| CN107774337A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst used in natural gas synthesis acetylene method vinyl acetate |
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