CN115228508B - Catalyst for synthesizing vinyl acetate by acetylene method - Google Patents
Catalyst for synthesizing vinyl acetate by acetylene method Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
The application relates to a catalyst for synthesizing vinyl acetate by an acetylene method and a preparation method thereof, and mainly solves the problem of high benzene content of byproducts in the prior art. The application provides a catalyst for synthesizing vinyl acetate by an acetylene method, which comprises the following components: the active component comprises zinc acetate, the carrier is active carbon, and the additive comprises quinone, so that the problem is well solved, and the active component can be used in industrial production of acetylene-method vinyl acetate.
Description
Technical Field
The application relates to an acetylene-method vinyl acetate catalyst, a preparation method of the catalyst and a synthesis method of vinyl acetate.
Background
Vinyl acetate, abbreviated as Vinyl Acetate (VAM), is one of important organic chemical raw materials, and is mainly used for synthesizing polyvinyl alcohol, VAE emulsion, EVA resin, vinylon and the like. At present, domestic vinyl acetate production capacity is about 320 ten thousand tons/year. The production process of VAM mainly includes ethylene method and acetylene method. Only Nanjing Selarnisi, medium petrifaction Yanshan petrifaction, medium petrifaction Shanghai petrifaction and other small factories adopt the acetylene process route in the ethylene process, and the productivity of the ethylene process accounts for about 80 percent of the total domestic productivity.
The acetylene method adopts zinc acetate/activated carbon catalyst, and the catalyst has the advantages of low cost, easy obtainment, simple preparation and the like, and has the defects of low reaction activity, short service life of the catalyst, high impurity content of products and the like. Aiming at the defects, researchers at home and abroad carry out a great deal of scientific research, great progress is made in the aspects of catalyst activity, service life and the like, and the progress of the acetylene-method vinyl acetate production technology is effectively promoted. However, the problem of more impurities in the VAM product cannot be well solved, so that the application of the acetylene method for producing the VAM in the field of downstream products with higher added values is restricted. The higher benzene content restricts the application of the catalyst in EVA, VAE and the like. Chinese patent CN1903435 (a catalyst for synthesizing vinyl acetate and a preparation method thereof) adopts active carbon as a carrier, zinc acetate as an active component and bismuth subcarbonate as a cocatalyst, so that the activity and stability of the prepared catalyst are obviously improved, and meanwhile, the content of butenal byproducts in the product is obviously reduced, but the patent does not mention whether the content of byproduct benzene is reduced or not.
Disclosure of Invention
One of the technical problems to be solved by the application is to solve the problem of high benzene content in products in the prior art, and provide a novel catalyst for synthesizing vinyl acetate by an acetylene method, which has the characteristic of low benzene content as a byproduct in the synthesis of vinyl acetate by the acetylene method.
The second technical problem to be solved by the present application is to provide a method for preparing a catalyst corresponding to one of the above technical problems.
The third technical problem to be solved by the application is to provide a method for synthesizing vinyl acetate by adopting the catalyst in one of the technical problems.
In order to solve one of the technical problems, the technical scheme of the application is as follows:
a catalyst for acetylene-process vinyl acetate synthesis, the catalyst comprising: the active component comprises zinc acetate, the carrier is active carbon, and the additive comprises quinone.
In the catalyst in the prior art, zinc acetate is used as an active component, activated carbon is used as a carrier, a part of manufacturers use bismuth salt as an additive to inhibit alkyne polymer generation, but no effective measures are taken for inhibiting byproduct benzene, and the benzene content in the obtained vinyl acetate product is relatively high. The inventor discovers that the content of benzene in the vinyl acetate product is greatly reduced due to the quinone additive added into the catalyst.
In the above technical scheme, as a non-limiting example, the content of zinc acetate in the catalyst calculated by zinc can be 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, 200g/L, 210g/L, 220g/L, 230g/L, 240g/L and the like.
In the above technical solution, the activated carbon support is not particularly limited in geometry.
In the above technical scheme, the activated carbon carrier may be cylindrical activated carbon. In this case, the diameter is more preferably 1.5 to 3.5mm, and/or the length is more preferably 3.0 to 5.0mm. For convenience of comparison, columnar activated carbon with the diameter of 2.7mm and the length of 4.0mm is adopted in the specific embodiment of the application.
In the above technical scheme, the specific surface area of the carrier is preferably 1000-2000 m 2 And/g. As a non-limiting example, the specific surface area of the support may be 1050m 2 /g，1100m 2 /g，1150m 2 /g，1200m 2 /g，1250m 2 /g，1300m 2 /g，1350m 2 /g，1400m 2 /g，1450m 2 /g，1500m 2 /g，1550m 2 /g，1600m 2 /g，1650m 2 /g，1700m 2 /g，1750m 2 /g，1800m 2 /g，1850m 2 /g，1900m 2 /g，1950m 2 /g, etc.
In the technical proposal, the total pore volume of the adsorption of the carrier is preferably 0.2 cm to 1.0cm 3 And/g. As a non-limiting example, the total pore volume of the carrier adsorption may be 0.25cm 3 /g，0.30cm 3 /g，0.35cm 3 /g，0.40cm 3 /g，0.45cm 3 /g，0.50cm 3 /g，0.55cm 3 /g，0.60cm 3 /g，0.65cm 3 /g，0.70cm 3 /g，0.75cm 3 /g，0.80cm 3 /g，0.85cm 3 /g，0.90cm 3 /g，0.95cm 3 /g, etc.
In the above technical scheme, preferably, the quinone comprises p-benzoquinone and/or 2,3, 5-trimethyl-1, 4-p-benzoquinone. 2,3, 5-trimethyl-1, 4-p-benzoquinone is abbreviated as TMQ.
In the above technical scheme, more preferably, the quinone comprises p-benzoquinone and 2,3, 5-trimethyl-1, 4-p-benzoquinone, and the p-benzoquinone and the 2,3, 5-trimethyl-1, 4-p-benzoquinone have interaction promotion effect in reducing benzene content in products.
The weight ratio of p-benzoquinone to 2,3, 5-trimethyl-1, 4-p-benzoquinone is preferably 1 to 10, such as, but not limited to, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc. the weight ratio of p-benzoquinone to 2,3, 5-trimethyl-1, 4-p-benzoquinone is preferably 1.5, 2, 2.5, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
In the above embodiments, the additive content is preferably 0.1 to 1.0g/L, for example, but not limited to, 0.15g/L, 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L, 0.4g/L, 0.45g/L, 0.5g/L, 0.55g/L, 0.6g/L, 0.65g/L, 0.7g/L, 0.75g/L, 0.8g/L, 0.85g/L, 0.9g/L, 0.95g/L, and the like.
In order to solve the second technical problem, the technical scheme is as follows:
a method for preparing a catalyst comprising the steps of:
(1) Mixing the quinone-containing solution with activated carbon, and drying to obtain a catalyst precursor;
(2) And mixing the aqueous solution containing zinc acetate with the catalyst precursor, and drying to obtain the catalyst finished product.
In the above technical solution, the drying operation in step (1) is preferably a forced air drying mode.
In the technical scheme, the activated carbon can be selected from coal activated carbon, wood activated carbon and coconut activated carbon. Among them, coconut shell activated carbon is preferable.
In the above-mentioned embodiment, the drying temperature in the step (1) is preferably 50 to 65℃such as, but not limited to, 51℃52℃53℃54℃55℃56℃57℃58℃59℃60℃61℃62℃63℃64 ℃.
In the above technical solution, the drying time in step (1) is preferably 1 to 3 hours, for example, but not limited to, treatment time is 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.0 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, etc.
In the above technical solution, the drying operation in step (2) is preferably a forced air drying mode.
In the above technical scheme, the drying temperature in the step (2) is preferably 60 to 80 ℃, such as, but not limited to, 65 ℃, 70 ℃, 75 ℃, and the like.
In the above technical solution, the drying time in step (2) is preferably 3-8 h, for example, but not limited to, treatment time is 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, etc.
In order to solve the third technical problem, the technical scheme of the application is as follows: the synthesis method of vinyl acetate comprises the steps of taking acetic acid and acetylene as raw material gases, and reacting in the presence of the catalyst according to any one of the technical schemes of the technical problems or the catalyst obtained by the preparation method according to any one of the technical schemes of the second technical problems of the technical problems.
The technical key of the application is the catalyst, and for the specific process conditions adopted by the synthesis method, the technical key can be reasonably selected by the skilled in the art and can obtain comparable technical effects. However:
in the above technical scheme, the molar ratio of acetylene to acetic acid is preferably 4-10, such as but not limited to 5, 6, 7, 8, 9, etc.
In the above technical scheme, the reaction pressure is preferably 0.1 to 0.5atm, such as, but not limited to, 0.15atm, 0.2atm, 0.25atm, 0.3atm, 0.35atm, 0.4atm, 0.45atm, and the like.
In the above technical scheme, the reaction temperature is preferably 160-200 ℃, such as, but not limited to, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, and the like.
In the technical proposal, the volume space velocity of the raw material gas is 250 to 350h -1 For example, but not limited to, a feed gas volume space velocity of 260h -1 、270h -1 、280h -1 、290h -1 、300h -1 、310h -1 、320h -1 、330h -1 、340h -1 Etc.
The reaction pressures are gauge pressures.
Detailed Description
[ example 1 ]
(I) Catalyst preparation
a) A sample containing 0.25g of TMQ (C) 9 H 10 O 2 ) And 0.25g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare methanol solution of 1LTMQ and p-benzoquinone as impregnating solution X, wherein TMQ concentration is 0.25g/L, and p-benzoquinone concentration is 0.25g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 2 ]
(I) Catalyst preparation
a) A sample containing 0.10g of TMQ (C) 9 H 10 O 2 ) And 0.40g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.10g/L, and the p-benzoquinone concentration is 0.40g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 3 ]
(I) Catalyst preparation
a) Weighing a sample containing 0.05g TMQ (C) 9 H 10 O 2 ) And 0.45g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.05g/L, and the p-benzoquinone concentration is 0.45g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 4 ]
(I) Catalyst preparation
a) Weighing a sample containing 0.05g TMQ (C) 9 H 10 O 2 ) And 0.05g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.05g/L, and the p-benzoquinone concentration is 0.05g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) Taking 100ml of zinc acetate aqueous solution containing 5.0g of Zn, mixing with 100ml of catalyst precursor, soaking for 3h at 80 ℃, and drying for 5h at 70 ℃ by blowing to obtain a catalyst finished product. The zinc content of the catalyst was 50.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=4:1;
raw material gas volumetric space velocity: 250h -1 ；
Reaction pressure: 0.1atm;
reaction temperature: 160 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 5 ]
(I) Catalyst preparation
a) A sample containing 0.10g of TMQ (C) 9 H 10 O 2 ) And 0.90g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.10g/L, and the p-benzoquinone concentration is 0.90g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 25.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 250.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=10:1;
raw material gas volumetric space velocity: 350h -1 ；
Reaction pressure: 0.5atm;
reaction temperature: 200 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 6 ]
(I) Catalyst preparation
a) A sample containing 0.10g of TMQ (C) 9 H 10 O 2 ) And 0.40g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.10g/L, and the p-benzoquinone concentration is 0.40g/L; mixing 1L of coconut shell activated carbon with the impregnating solution, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) Taking 100ml of zinc acetate aqueous solution containing 5.0g of Zn, mixing with 100ml of catalyst precursor, soaking for 3h at 80 ℃, and drying for 5h at 70 ℃ by blowing to obtain a catalyst finished product. The zinc content of the catalyst was 50.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
feed gasVolume space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 7 ]
(I) Catalyst preparation
a) A sample containing 0.10g of TMQ (C) 9 H 10 O 2 ) And 0.40g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.10g/L, and the p-benzoquinone concentration is 0.40g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 25.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 250.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 8 ]
(I) Catalyst preparation
a) Weighing a sample containing 0.01g TMQ (C) 9 H 10 O 2 ) And 0.09g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.01g/L, and the p-benzoquinone concentration is 0.09g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 9 ]
(I) Catalyst preparation
a) A sample containing 0.50g of TMQ (C) 9 H 10 O 2 ) And 0.50g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ and p-benzoquinone as an impregnating solution X, wherein the TMQ concentration is 0.50g/L, and the p-benzoquinone concentration is 0.50g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 10 ]
(I) Catalyst preparation
a) A sample containing 0.50g of TMQ (C) 9 H 10 O 2 ) Dissolving in 1L of methanol to prepare 1L of methanol solution of TMQ as impregnating solution X, wherein the concentration of TMQ is 0.5g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ example 11 ]
(I) Catalyst preparation
a) Weighing a liquid containing 0.50g of p-benzoquinone (C) 6 H 4 O 2 ) Dissolving in 1L methanol to obtain 1L methanol solution of p-benzoquinoneIs impregnating solution X, wherein the concentration of the p-benzoquinone is 0.50g/L; mixing 1L of coconut shell activated carbon with 1L of impregnating solution X, impregnating for 3 hours at 50 ℃, and drying for 2 hours at 60 ℃ by blowing to obtain a catalyst precursor;
b) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of catalyst precursor, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ comparative example 1 ]
(I) Catalyst preparation
a) 100ml of zinc acetate aqueous solution containing 15.0g of Zn is taken and mixed with 100ml of coconut shell activated carbon, immersed for 3 hours at 80 ℃, and dried for 5 hours at 70 ℃ by blowing, thus obtaining the catalyst finished product. The zinc content of the catalyst was 150.0g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
[ comparative example 2 ]
(I) Catalyst preparation
According to the preparation method of the acetylene-method vinyl acetate catalyst mentioned in Chinese patent CN1903435 (a catalyst for vinyl acetate synthesis and a preparation method thereof), zinc acetate, bismuth subcarbonate and pure water are adopted to prepare an impregnating solution, and then the impregnating solution is mixed with activated carbon. And (5) soaking and drying to obtain a catalyst finished product. The catalyst prepared by the method is used as a comparative example for comparison, and the preparation process is as follows:
a) Zinc acetate ((CH) 3 COO) 2 Zn) 42.09g, bismuth subcarbonate (CBi) 2 O 5 ) 0.122g, mixing with pure water to prepare 100ml mixed solution (wherein Zn content is 150.0g/L, bi content is 0.5 g/L), mixing 100ml coconut shell activated carbon with the 100ml mixed solution, soaking for 3h at 80 ℃, and drying for 5h by blowing at 70 ℃ to obtain the catalyst finished product. The content of zinc in the catalyst was 150.0g/L and the content of Bi was 0.5g/L by ICP-AES analysis.
(II) characterization of physical Properties
The Zn element as an active ingredient in the catalyst was quantitatively analyzed by using a Thermo iCAP 6300 type inductively coupled plasma spectrometer (ICP-AES).
The preparation conditions of the catalyst are shown in Table 1.
(III) evaluation of catalyst Performance
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
feed gas composition (in mole ratio): acetylene acetic acid=5:1;
raw material gas volumetric space velocity: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The reaction product was analyzed for the content of each component by gas chromatography, the space-time yield of the catalyst was calculated, and the reaction product was analyzed for the benzene content by GC-MS.
The main reaction conditions and the reaction results are listed in Table 2 for comparison.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
Table 1 catalyst formulation
a: comparative example 2 used Bi salt as additive, bi content was 0.5g/L.
Table 2 catalyst evaluation
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Claims (17)
1. A catalyst for acetylene-process vinyl acetate synthesis, the catalyst comprising: the active component comprises zinc acetate, the carrier is active carbon, and the additive comprises quinone; the zinc acetate content is 50-250 g/L; the quinone comprises p-benzoquinone and 2,3, 5-trimethyl-1, 4-p-benzoquinone, and the weight ratio of the p-benzoquinone to the 2,3, 5-trimethyl-1, 4-p-benzoquinone is 1-10; the content of the additive is 0.1-1.0 g/L.
2. The catalyst of claim 1, wherein the support is cylindrical activated carbon.
3. The catalyst according to claim 2, wherein the diameter of the cylindrical activated carbon is 1.5-3.5 mm.
4. The catalyst according to claim 2, wherein the cylindrical activated carbon has a length of 3.0 to 5.0mm.
5. The catalyst according to claim 1, wherein the specific surface area of the carrier is 1000 to 2000m 2 /g。
6. The catalyst according to claim 1 or 5, wherein the adsorption total pore volume of the carrier is 0.2 to 1.0cm 3 /g。
7. The catalyst preparation method of the catalyst according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing the quinone-containing solution with activated carbon, and drying to obtain a catalyst precursor;
(2) And mixing the aqueous solution containing zinc acetate with the catalyst precursor, and drying to obtain the catalyst finished product.
8. The method for preparing the composite material according to claim 7, wherein: the drying operation in the step (1) is a forced air drying mode.
9. The preparation method according to claim 7 or 8, characterized in that: the drying temperature in the step (1) is 50-65 ℃.
10. The preparation method according to claim 7 or 8, characterized in that: and (3) drying in the step (1) for 1-3 hours.
11. The method for preparing the composite material according to claim 7, wherein: the drying operation in the step (2) is a forced air drying mode.
12. The preparation method according to claim 7 or 11, characterized in that: the drying temperature in the step (2) is 60-80 ℃.
13. The preparation method according to claim 7 or 11, characterized in that: and (3) drying in the step (2) for 3-8 hours.
14. A method for synthesizing vinyl acetate, comprising the step of reacting acetic acid and acetylene as raw material gases in the presence of the catalyst according to any one of claims 1 to 6 or the catalyst obtained by the preparation method according to any one of claims 7 to 13 to obtain vinyl acetate.
15. The method of synthesis according to claim 14, wherein: the molar ratio of acetylene to acetic acid is 4-10.
16. The method of synthesis according to claim 14, wherein: the reaction pressure is 0.1 to 0.5atm.
17. The method of synthesis according to claim 14, wherein: the reaction temperature is 160-200 ℃, and the raw material gas volume space velocity is 250-350 h -1 。
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| CN104437623A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acetylene-method vinyl acetate and synthesis method of vinyl acetate |
| CN105944757A (en) * | 2016-05-12 | 2016-09-21 | 石河子大学 | Catalyst for synthesizing vinyl acetate with acetylene process, preparation method and vinyl acetate synthesizing method |
| CN112439455A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
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| CN104437623A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acetylene-method vinyl acetate and synthesis method of vinyl acetate |
| CN105944757A (en) * | 2016-05-12 | 2016-09-21 | 石河子大学 | Catalyst for synthesizing vinyl acetate with acetylene process, preparation method and vinyl acetate synthesizing method |
| CN112439455A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
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