CN107774309B - Catalyst for synthesizing vinyl acetate by acetylene method - Google Patents
Catalyst for synthesizing vinyl acetate by acetylene method Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing acetylene-method vinyl acetate, which mainly solves the problem of poor stability of acetylene gas-phase-method catalysts in the prior art. The invention adopts the technical scheme that the catalyst for synthesizing vinyl acetate by the acetylene method adopts the activated carbon as a carrier, the active component comprises zinc acetate and a cocatalyst, and the cocatalyst comprises at least one metal element selected from metalloids and at least one metal element selected from platinum group metals, so that the problem is better solved, and the catalyst can be used for industrial production of synthesizing vinyl acetate by the acetylene gas phase method.
Description
Technical Field
The invention relates to a catalyst for synthesizing acetylene-process vinyl acetate, a preparation method of the acetylene-gas-phase-process vinyl acetate catalyst and a synthesis method of the acetylene-gas-phase-process vinyl acetate.
Background
Vinyl acetate (VA C) is an important organic chemical raw material, and is widely used for manufacturing polyvinyl acetate and polyvinyl alcohol and further processing the polyvinyl acetate and polyvinyl alcohol into adhesives, coatings, vinylon fibers, fabrics, emulsions, resins, films and the like.
The acetylene method for producing vinyl acetate goes through two development stages of liquid phase and gas phase processes. Before 1940, mainly liquid phase process is adopted, reaction is carried out at 30-70 ℃ under normal pressure, and catalysts are mercuric oxide and sulfuric acid or phosphoric acid; after the 40 s of the 20 th century, acetylene gas phase method was the main method, and the catalyst was activated carbon loaded with zinc acetate.
Muqaen, Inc. of Wacker, Germany, discovered that zinc acetate impregnated on activated carbon can synthesize vinyl acetate in a vapor phase, and then proposed a method for synthesizing VAc using acetylene in a vapor phase, and then put into industrial Production through improvement of Hochst, the catalyst of which uses Zn (OAc) 2 as an active component and activated carbon as a carrier, and has been used up to now, U.S. Pat. No. 5,166482, Production of vinyl acetate, reported the use of Zn (OAc) 2/C, and vinyl acetate was synthesized, Chinese patent CN1903435 (titled: a catalyst for vinyl acetate synthesis and a method for preparing the same) provided a method for preparing a vinyl acetate catalyst using zinc oxide and acetic acid as active components, and added a small amount of bismuth carbonate, and dried by impregnating it on activated carbon to obtain the catalyst.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problems of poor stability of the acetylene method vinyl acetate catalyst and too large reduction rate of the activity of the catalyst in the prior art, and provide a novel catalyst for synthesizing acetylene method vinyl acetate, which has the characteristics of good stability, low reduction rate of the activity of the catalyst and long service life.
The second technical problem to be solved by the present invention is to adopt the method for producing the catalyst described in the first technical problem.
The invention also provides a synthesis method of vinyl acetate by using the catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for synthesizing vinyl acetate by an acetylene method adopts active carbon as a carrier, the active components comprise zinc acetate and a cocatalyst, and the cocatalyst comprises at least one metal element selected from metalloids and at least one metal element selected from platinum group metals.
In the technical scheme, the catalyst can contain or not contain alkali metal acetate, more specifically potassium acetate, and the alkali metal acetate is not favorable for improving the stability of the catalyst, so that the activity reduction rate of the catalyst is large.
When the cocatalyst comprises a metalloid element and a platinum group metal element, the two metal elements have a synergistic effect in improving the space-time yield of the vinyl acetate catalyst and reducing the reduction rate of the activity of the catalyst.
In the above technical scheme, the activated carbon is preferably selected from at least one of coal columnar carbon, coconut shell activated carbon, apricot shell activated carbon and bamboo activated carbon.
In the technical scheme, the specific surface area of the activated carbon is preferably 1000-1500 cm 2/g, and the adsorption pore volume is preferably 0.60-1.00 cm 3/g.
In the above technical solution, the metalloid element is preferably at least one selected from boron, arsenic and tellurium.
In the above embodiment, the platinum group metal element is preferably at least one selected from platinum, palladium, osmium, iridium, ruthenium, and rhodium.
As one of the preferable technical means, the metalloid element comprises tellurium and the platinum group metal element comprises platinum or palladium, and at this time, the metalloid element and the platinum group metal element have a synergistic effect between them in terms of increasing the space time yield of the vinyl acetate catalyst and reducing the rate of decrease in the activity of the catalyst.
As another preferred embodiment, the metalloid element comprises tellurium or boron and the platinum group metal element comprises palladium and platinum, where palladium and platinum have a synergistic effect in increasing the space time yield of the vinyl acetate catalyst and reducing the rate of decrease in the activity of the catalyst.
As a third preferred embodiment, the metalloid elements comprise tellurium and boron and the platinum group metal elements comprise palladium and platinum, where tellurium and boron have a synergistic effect in increasing the space time yield of the vinyl acetate catalyst and reducing the rate of decrease in the activity of the catalyst.
In the technical scheme, the content of the zinc acetate in the catalyst is preferably 50-300 g/L, and more preferably 80-200 g/L.
In the technical scheme, the content of the cocatalyst in the catalyst is preferably 0.50-8.00 g/L, and more preferably 1.00-5.00 g/L.
To solve the second technical problem, the technical solution of the present invention is as follows: the method for producing the catalyst in the technical scheme of one of the technical problems comprises the following steps:
Mixing zinc acetate and a solution of a cocatalyst with a carrier according to the composition of a catalyst;
Drying.
In the above technical solution, as a non-limiting example, the metalloid element compound in the step (i) is preferably at least one selected from boric acid, ammonium pentaborate, dimethylaminoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid; more preferably at least one of ammonium pentaborate and ammonium tellurate.
In the above-mentioned embodiment, as a non-limiting example, the compound of the platinum group metal element in the step (i) is preferably at least one selected from the group consisting of rhodium chloride, rhodium acetate biligand, triphenylphosphine chlororhodium, rhodium nitrate, palladium chloride, tetraamminepalladium dichloride, palladium acetate, ammonium chloropalladite, ruthenium chloride, tetralactam perruthenate, ruthenium acetate, platinum dichloride, ammonium chloroplatinate, chloroplatinic acid, platinum acetate, osmium trichloride, osmium acetate, iridium trichloride, iridium acetate, and chloroiridic acid.
In the technical scheme, the drying temperature in the step II is preferably 80-120 ℃, and more preferably 100-120 ℃.
To solve the third technical problem, the technical scheme of the invention is as follows: the vinyl acetate synthesis method takes acetic acid and acetylene as raw materials, and the vinyl acetate is generated by reaction in the presence of the catalyst in any one of the technical schemes of the technical problems.
The key point of the invention is the selection of a catalyst, and a person skilled in the art knows how to determine a proper reaction temperature, reaction time, reaction pressure and material ratio according to actual needs, however, in the technical scheme, the reaction temperature is preferably 150-200 ℃, the reaction pressure is preferably 0.1-0.5 MPa, the raw material composition in terms of molar ratio is preferably acetylene and acetic acid (5-12): 1, and the volume space velocity of the raw material is preferably 250-350 h -1.
The contents of the components in the reaction product of the present invention were analyzed by gas chromatography, and the space-time yield of the catalyst and the rate of decrease in the activity of the catalyst were calculated.
Catalyst evaluation the reaction was run for 480h, with the catalyst start space time yield being characterized by the catalyst average space time yield for the first 10 hours of the reaction and the catalyst end space time yield being characterized by the catalyst average space time yield for the last 10 hours of the reaction. The calculation formula of the reduction rate of the catalyst activity is as follows:
The lower the activity reduction rate of the catalyst, the longer the active life of the catalyst, and the higher the activity stability of the catalyst.
Compared with the prior art, the key of the invention is that the active component of the catalyst comprises zinc acetate, at least one metal element selected from metalloids and at least one metal element selected from platinum group metals, which is beneficial to improving the stability of the catalyst and reducing the activity reduction rate of the catalyst, thereby achieving the purpose of prolonging the service life of the catalyst of vinyl acetate.
The experimental result shows that when the catalyst provided by the invention is used, the activity reduction rate of the catalyst is only 3.81% after the catalyst reacts for 480 hours, a good technical effect is achieved, and particularly when the active component in the catalyst simultaneously comprises zinc acetate, at least one metal element selected from metalloids and at least one metal element selected from platinum group metals, a more outstanding technical effect is achieved, and the catalyst can be used in the industrial production of vinyl acetate. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2) and 3.38g of Te-containing ammonium tellurate ((NH 4) 2 TeO 4) and dissolving the mixture in 10 wt% acetic acid water solution to obtain 350ml of impregnation liquid, impregnating 1L of coal cylindrical active carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h and drying at 100 ℃ to obtain the catalyst, and measuring or converting the zinc acetate content of the catalyst into 105g/L and the Te content of 3.38g/L by ICP.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 162.43 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 156.24 g/L.multidot.h, and the activity reduction of the catalyst was 3.81%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 2 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 105g of zinc acetate (Zn (OAc) 2) and 3.38g of Pt-containing ammonium chloroplatinite ((NH 4) 2 PtCl 4) in 10 wt% of acetic acid aqueous solution to obtain 350ml of impregnation liquid, immersing 1L of coal-based cylindrical active carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h, and drying at 100 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 105g/L through ICP measurement or conversion, and the Pt content is 3.38 g/L.
and (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 162.22 g/L.h, the end space-time yield of the catalyst after 480h was 155.71 g/L.h, and the activity reduction rate of the catalyst was 4.01%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ COMPARATIVE EXAMPLE 1 ]
Are comparative examples of [ example 1 ] and [ example 2 ].
The preparation of the catalyst comprises the steps of fully dissolving 105g of zinc acetate (Zn (OAc) 2) in 10 wt% acetic acid aqueous solution to obtain 350ml of impregnation liquid, impregnating 1L of coal cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h and drying at 100 ℃ to obtain the catalyst, and measuring or converting the zinc acetate content of the catalyst by ICP to 105 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
the initial space-time yield of the catalyst was calculated to be 120.14 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 107.30 g/L.multidot.h, and the activity reduction rate of the catalyst was 10.69%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
Compared with the embodiment 1-2, the catalyst adopted by the invention has the advantages that the performance of the catalyst simultaneously containing the active components of zinc acetate and ammonium tellurate and simultaneously containing the active components of zinc acetate and ammonium platinochloride is better than that of the catalyst only containing the active component of zinc acetate, the stability of the vinyl acetate catalyst is good, and the reduction rate of the activity of the catalyst is lower, so that the service life of the vinyl acetate catalyst is prolonged. This is sufficient to demonstrate that the stability of the vinyl acetate catalyst is improved and the rate of decrease in the activity of the catalyst is reduced when the active component in the catalyst of the present invention comprises zinc acetate, at least one metal element selected from the group consisting of metalloids and at least one metal element selected from the group consisting of platinum group metals.
[ example 3 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 80g of zinc acetate (Zn (OAc) 2) and 1.00g of Rh-containing rhodium acetate (Rh 2 (OAc) 4) in 10 wt% acetic acid aqueous solution to obtain 350ml of impregnation liquid, impregnating 1L of cylindrical coconut shell activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.60cm 3/g and the specific surface area of 1000cm 2/g in the impregnation liquid, standing for 3h, and drying at 80 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 80g/L and the Rh content is 1.00g/L by ICP measurement or conversion.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 102.32 g/L.h, the terminal space-time yield of the catalyst after 480h was calculated to be 98.25 g/L.h, and the activity reduction rate of the catalyst was calculated to be 3.98%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 4 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 200g of zinc acetate (Zn (OAc) 2) and 5.00g of Ru-containing ruthenium acetate (Ru (OAc) 3.3H 2 O) in 10 wt% of acetic acid aqueous solution to obtain 350ml of impregnation liquid, impregnating 1L of a cylindrical apricot shell activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 1.00cm 3/g and the specific surface area of 1500cm 2/g in the impregnation liquid, standing for 3H, and drying at 120 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 200g/L through ICP measurement or conversion, and the Ru content is 5.00 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 163.36 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 156.87 g/L.multidot.h, and the activity reduction rate of the catalyst was 3.97%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 5 ]
The preparation of the catalyst comprises the steps of fully mixing and dissolving 105g of zinc acetate (Zn (OAc) 2) and 3.38g of Pd acetate (Pd (OAc) 2) in 10 wt% acetic acid aqueous solution to obtain 350ml of impregnation liquid, impregnating 1L of cylindrical bamboo activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h, and drying at 120 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 105g/L and the Pd content of the catalyst is 3.38g/L through ICP measurement or conversion.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 162.27 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 155.84 g/L.multidot.h, and the activity reduction rate of the catalyst was 3.96%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 6 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2) and 3.38g of Os-containing chloroosmium ammonium ((NH 4) 2 OsCl 6 & 3H 2 O) and dissolving the mixture in 10 wt% acetic acid water solution to obtain 350ml of impregnation liquid, immersing 1L of coal cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3H and drying at 100 ℃ to obtain the catalyst, wherein the zinc acetate content of the catalyst is 105g/L through ICP measurement or conversion, and the Os content is 3.38 g/L.
and (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, testing leakage by using N 2, fully purging the system by using N 2, heating the system, closing N 2, sequentially switching in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 162.25 g/L.h, the end space-time yield of the catalyst after 480h was 155.74 g/L.h, and the activity reduction rate of the catalyst was 4.01%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 7 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2) and 3.38g of Ir acetate (Ir (OAc) 3.3H 2 O) and dissolving in 10 wt% acetic acid water solution to obtain 350ml of impregnation liquid, immersing 1L of coal-based cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3H and drying at 100 ℃ to obtain the catalyst, and measuring or converting the ICP content of the catalyst into 105g/L of zinc acetate and the Ir content of 3.38 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 150 ℃, the reaction pressure to be 0.10MPa, and the volume space velocity of the raw material to be 250h -1, wherein the molar ratio of acetylene to acetic acid is 5:1, and after the reaction is continuously carried out for 480h, stopping the reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 151.88 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 145.77 g/L.multidot.h, and the activity reduction rate of the catalyst was 4.02%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 8 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2) and 3.38g B ammonium pentaborate ((NH 4) B 5 O 8.8H 2 O) and dissolving the mixture in 10 wt% acetic acid water solution to obtain 350ml of impregnation liquid, immersing 1L of coal cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3H and drying at 100 ℃ to obtain the catalyst, and measuring or converting the zinc acetate content of the catalyst into 105g/L and the B content of 3.38g/L by ICP.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 200 ℃, the reaction pressure to be 0.50MPa, and the volume space velocity of raw materials to be 350h -1, wherein the molar ratio of acetylene to acetic acid is 12:1, and after the reaction is continuously carried out for 480h, stopping the reaction.
and (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 163.01 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 156.69 g/L.multidot.h, and the activity reduction rate of the catalyst was 3.88%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 9 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2), 1.63g of Te containing ammonium tellurate ((NH 4) 2 TeO 4) and 1.75g of Pt containing ammonium chloroplatinate ((NH 4) 2 PtCl 4) and dissolving the mixture in 10 wt% acetic acid water solution to obtain 350ml of impregnation liquid, immersing 1L of coal cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h and drying at 100 ℃ to obtain the catalyst, and measuring or converting the zinc acetate content of 105g/L, the Te content of 1.63g/L and the Pt content of 1.75g/L by ICP.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 164.44 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 159.31 g/L.multidot.h, and the activity reduction rate of the catalyst was 3.12%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
From the comparison between example 9 and examples 1 and 2, it is seen that in the catalyst used in the present invention, the metal element Te in the metalloid and the metal element Pt in the platinum group metal have a better synergistic effect in improving the stability of the vinyl acetate catalyst and reducing the reduction rate of the activity of the catalyst, indicating that there is a better synergistic effect between zinc acetate, ammonium tellurate and ammonium chloroplatinate in improving the stability of the catalyst and reducing the reduction rate of the activity of the catalyst.
[ example 10 ]
The preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2), 1.63g of Te containing ammonium tellurate ((NH 4) 2 TeO 4) and 1.75g of Pd acetate (Pd (OAc) 2) and dissolving the mixture in 10 wt% aqueous solution of acetic acid to obtain 350ml of impregnation liquid, immersing 1L of coal-based cylindrical activated carbon carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h and drying at 100 ℃ to obtain the catalyst, wherein the content of zinc acetate of the catalyst is 105g/L, the content of Te is 1.63g/L and the content of Pd is 1.75g/L through ICP measurement or conversion.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 164.35 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 159.14 g/L.multidot.h, and the activity reduction rate of the catalyst was 3.17%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 11 ]
the preparation of the catalyst comprises the steps of fully mixing 105g of zinc acetate (Zn (OAc) 2), 1.63g of Te ammonium tellurate ((NH 4) 2 TeO 4), 1.13g of Pt ammonium chloroplatinite ((NH 4) 2 PtCl 4) and 0.62g of Pd acetate (Pd (OAc) 2) in 10 wt% of acetic acid aqueous solution to obtain 350ml of impregnation liquid, impregnating 1L of coal cylindrical carrier with the diameter of 3mm, the length of 2cm, the pore volume of 0.80cm 3/g and the specific surface area of 1200cm 2/g in the impregnation liquid, standing for 3h and drying at 100 ℃ to obtain the catalyst ICP, measuring or converting the zinc acetate content of the catalyst to 105g/L, the Te content to 1.63g/L, the Pt content to 1.13g/L and the Pd content to 0.62 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 167.29 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 163.17 g/L.multidot.h, and the activity reduction rate of the catalyst was 2.46%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
As can be seen from the comparison between example 11 and examples 9 and 10, in the catalyst used in the present invention, the metal element Te in the metalloid and the metal elements Pt and Pd in the platinum group metal have a synergistic effect with each other in terms of improving the stability of the vinyl acetate catalyst and reducing the rate of decrease in the activity of the catalyst. The method shows that the zinc acetate, the ammonium tellurate, the ammonium platinochloride and the palladium acetate have good synergistic effect in the aspects of improving the stability of the catalyst and reducing the activity reduction rate of the catalyst.
[ example 12 ]
The catalyst is prepared by mixing and dissolving 105g of zinc acetate (Zn (OAc) 2), 1.63g B g of ammonium pentaborate ((NH 4) B 5 O 8.8H 2 O), 1.13g of Pt ammonium chloroplatinite ((NH 4) 2 PtCl 4) and 0.62g of Pd acetate (Pd (OAc) 2) in 10 wt% aqueous acetic acid solution to obtain 350ml of impregnation solution, and immersing 1L of coal cylindrical active carbon carrier with a diameter of 3mm, a length of 2cm, a pore volume of 0.80cm 3/g and a specific surface area of 1200cm 2/g in the impregnation solution, standing for 3H and drying at 100 ℃ to obtain the catalyst, wherein ICP content of the catalyst is 105g/L, B content of 1.63g/L, Pt content of 1.13g/L and Pd content of 0.62 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 167.42 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 163.17 g/L.multidot.h, and the activity reduction rate of the catalyst was 2.54%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
[ example 13 ]
The catalyst is prepared by mixing and dissolving 105g of zinc acetate (Zn (OAc) 2), 1.18g of Te containing ammonium tellurate ((NH 4) 2 TeO 4), 0.45g B containing ammonium pentaborate ((NH 4) B 5 O 8.8H 2 O), 1.13g of Pt containing ammonium chloroplatinite ((NH 4) 2 PtCl 4) and 0.62g of Pd (OAc) 2) in 10 wt% aqueous acetic acid solution to obtain 350ml of impregnation solution, impregnating 1L of coal-based cylindrical activated carbon carrier with diameter of 3mm, length of 2cm, pore volume of 0.80cm 3/g and specific surface area of 1200cm 2/g in the above impregnation solution, standing for 3H at 100 ℃ and drying at ICP temperature to obtain the catalyst, and measuring or calculating the content of zinc acetate 105g/L, Te content of 1.18g/L, B content of 0.45g/L, and Pd content of 0.13 g/L.
And (2) synthesizing vinyl acetate, namely filling 30ml of catalyst in a miniature fixed bed reactor, after leakage test of N 2, fully purging the system by using N 2, after the temperature of the system is raised, closing N 2, sequentially cutting in acetylene and starting an acetic acid pump, controlling the reaction temperature to be 175 ℃, the reaction pressure to be 0.25MPa, the volume space velocity of raw materials to be 280h -1, keeping the molar ratio of acetylene to acetic acid to be 6:1, and stopping reaction after 480h of continuous reaction.
And (3) product analysis: the reaction mixture obtained by the above reaction was cooled, decompressed, separated, and the liquid phase was analyzed by gas chromatography-MASS spectrometer (GC-MASS).
The initial space-time yield of the catalyst was calculated to be 168.90 g/L.multidot.h, the end space-time yield of the catalyst after 480h was 165.99 g/L.multidot.h, and the activity reduction rate of the catalyst was 1.72%. For convenience of illustration and comparison, the catalyst preparation conditions, reaction conditions, feed amounts, catalyst start-up and end-up space-time yields, and catalyst activity reduction rates are shown in tables 1 and 2, respectively.
It is seen from the comparison between example 13 and examples 11 and 12 that the catalyst used in the present invention has a synergistic effect between the metal elements Te, B in the metalloid and the metal elements Pt, Pd in the platinum group metal in terms of improving the stability of the vinyl acetate catalyst and reducing the rate of decrease in the activity of the catalyst. The method shows that the zinc acetate, the ammonium tellurate, the ammonium pentaborate, the ammonium platinochloride and the palladium acetate have good synergistic effect on the aspects of improving the stability of the catalyst and reducing the activity reduction rate of the catalyst.
TABLE 1
TABLE 2
Claims (6)
1. The catalyst for synthesizing vinyl acetate by an acetylene method adopts active carbon as a carrier, the active components comprise zinc acetate and a cocatalyst, and the cocatalyst comprises at least one element of boron and arsenic and metal elements of platinum and palladium; wherein, the content of zinc acetate in the catalyst is as follows: 50-300 g/L, and the content of the cocatalyst is as follows: 0.50-8.00 g/L.
2. The catalyst according to claim 1, characterized in that the activated carbon is at least one of coal columnar carbon, coconut shell activated carbon, apricot shell activated carbon, and bamboo activated carbon.
3. The catalyst according to claim 1, wherein the activated carbon has a specific surface area of 1000 to 1500m 2/g and an adsorption pore volume of 0.60 to 1.00cm 3/g.
4. A method for producing the catalyst of claim 1, comprising the steps of:
Mixing zinc acetate and a solution of a cocatalyst with a carrier according to the composition of a catalyst;
Drying.
5. A method for synthesizing vinyl acetate, which takes acetic acid and acetylene as raw materials and synthesizes the vinyl acetate under the catalyst of any one of claims 1 to 3.
6. The synthesis method according to claim 5, wherein the raw material composition comprises acetylene, acetic acid ═ 1 (5-12) in molar ratio.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056563A (en) * | 1975-01-31 | 1977-11-01 | Boyadzhian Varazdat Karapetovi | Method of producing allylacetate |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| CN105498778A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Acetylene process vinyl acetate catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056563A (en) * | 1975-01-31 | 1977-11-01 | Boyadzhian Varazdat Karapetovi | Method of producing allylacetate |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| CN105498778A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Acetylene process vinyl acetate catalyst |
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