CN1036377C - Production of alkenyl alkanoate catalysts - Google Patents

Production of alkenyl alkanoate catalysts Download PDF

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CN1036377C
CN1036377C CN92103424A CN92103424A CN1036377C CN 1036377 C CN1036377 C CN 1036377C CN 92103424 A CN92103424 A CN 92103424A CN 92103424 A CN92103424 A CN 92103424A CN 1036377 C CN1036377 C CN 1036377C
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catalyst
potassium
sodium
palladium
carrier
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CN1077140A (en
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W·J·巴特利
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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Priority claimed from US07/793,129 external-priority patent/US5179057A/en
Priority to US07/793,129 priority Critical patent/US5179057A/en
Application filed by Union Carbide Chemicals and Plastics Technology LLC filed Critical Union Carbide Chemicals and Plastics Technology LLC
Priority to MX9201440A priority patent/MX9201440A/en
Priority to CN92103424A priority patent/CN1036377C/en
Priority to AU13900/92A priority patent/AU643132B2/en
Priority to NZ242166A priority patent/NZ242166A/en
Priority to HU9201054A priority patent/HU212447B/en
Priority to US07/952,280 priority patent/US5342987A/en
Priority to CA002081937A priority patent/CA2081937C/en
Priority to CA002081942A priority patent/CA2081942C/en
Publication of CN1077140A publication Critical patent/CN1077140A/en
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Abstract

The present invention provides a processing method for producing improved catalyst. The catalyst can be used for preparing alkenyl alkanoate through the reaction among alkene, alkanoic acid and oxygen-containing gas, and comprises a palladium, gold and potassium co-catalyst. The present invention is characterized in that the content of sodium is reduced so that the activity of the catalyst is enhanced. The present invention is composed of three implementation examples (i.e. an implementation example A, an implementation example B and an implementation example C).

Description

The alkenyl alkanoate catalysts manufacture method
The present invention relates to a kind of production catalyst technology of (claiming that from now on they are ＂ alkenyl alkanoate catalysts ＂), produce alkenyl alkanoate with raw materials such as cause olefine, alkanoic acid and a kind of oxygen-containing gas.
Known at present the technology of some production alkenyl alkanoate catalysts.
For example, disclose a kind of catalyst in the U.S. Pat 4048096 of Bissot, the specific activity of this catalyst is measured under 150 ℃ and per hour is at least about every gram precious metal catalyst generation 83 gram vinylacetates.The vingl acetate catalyst of Bissot is made up of following material basically: (1) a kind of particle diameter from about 3 to about 7mm, porosity is from about catalyst carrier of 0.2 to 1.5ml/g, the pH value of this catalyst carrier 10% weight water slurry is about 3.0 to about 9.0; (2) be dispersed in a kind of Polarium in the superficial layer of catalyst carrier, this superficial layer is distributed in the following about 0.5mm of carrier surface, to about 5.0 grams, gold content is from every liter of extremely about 2.25 grams of about 0.5 gram of catalyst from every liter of about 1.5 grams of catalyst for palladium content in the alloy; (3) contain the alkali-metal acetate of 5 grams of having an appointment in every liter of catalyst to 60 grams.It is active catalytic metals that Bissot has also disclosed palladium, and gold is a kind of co-catalyst.
Bissot also discloses a kind of technology of the Bissot of preparation catalyst.With people's such as Kronig resemble process, the technology of Bissot also comprises metal salt precipitate on catalyst carrier.Bissot technology is made up of the following step: (1) is immersed catalyst carrier in the aqueous solution of the water miscible palladium and the compound of gold, (2) contact to form the mode of the water-fast palladium and the compound of gold with a kind of aqueous solution of the compound (preferably sodium metasilicate) that can react by the catalyst carrier that makes dipping with the compound of water-soluble palladium and gold, water-fast palladium and the gold compound precipitation on catalyst carrier, (3) after a kind of reducing agent is handled, with above-mentioned water-fast palladium and the gold compound be transformed on the carrier palladium and the gold these two kinds of metals, (4) water cleaning catalyst, (5) make catalyst drying (seeing the example 1 of Bissot), (6) with alkali-metal acetate co-catalyst (as a kind of potassium promoter) impregnated catalyst, and (7) make the catalyst drying.
The disclosed improvement of Bissot comprises that the palladium of alloy morphology and the golden superficial layer that disperses to advance catalyst carrier, this superficial layer is distributed in the following about 0.5mm of carrier surface.Impregnation steps is to be finished by the aqueous solution of a kind of palladium and gold compound, and the cumulative volume of solution is about 95 to 100% of a catalyst carrier adsorption capacity.Settling step in the Bissot method is by finishing with the wet catalyst carrier of a kind of alkali-metal silicate solutions dipping, the definite of alkali silicate amount should make when alkali metal silicate solutions contacts about 12 to 24 hours with catalyst carrier after, and the pH value of described solution is about 6.5 to about 9.5.
Bissot does not report the sodium content of catalyst in the Bissot example.According to embodiment 1 report of Bissot, the catalyst of this embodiment has the per hour activity of every liter of catalyst generation 560 gram vinylacetates.In the EXAMPLE III below, discovery is respectively 0.32 and 0.38% weight with the sodium content of two kinds of catalyst of the embodiment 1 disclosed method manufacturing of Bissot, and its activity reaches per hour every liter of catalyst generation 551 and 535 gram vinylacetates respectively.
Although the level of prior art technology is very high, people still wish further to improve the activity of alkenyl alkanoate catalysts.
On the whole, the invention provides a kind of technology, this technology is by the reaction between a kind of olefine, a kind of alkanoic acid and a kind of oxygen-containing gas, produce be used for improvement that alkenyl alkanoate produces catalyst.These catalyst contain palladium, gold and a kind of potassium promoter, and cause having the characteristics that improved catalytic activity owing to sodium content reduces.
In embodiments of the invention A, the reduction of sodium content is by using the starting material that is substantially free of sodium to realize in the technology of producing catalyst.
In embodiments of the invention B, the reduction of sodium content is by the water cleaning catalyst, perhaps realizes with a kind of aqueous solution cleaning catalyst of potassium promoter after with a kind of potassium promoter impregnated catalyst.
In embodiments of the invention C, the reduction of sodium content is by realizing with the specific intermediate point cleaning catalyst of a kind of cation exchange solution in the Catalyst Production process.
Embodiments of the invention A is based in part on following discovery: in the process of producing catalyst, if employing is substantially free of the starting material of sodium and reduce its sodium content, then therefore the activity of alkenyl alkanoate catalysts will improve.
More particularly, embodiments of the invention A provides a kind of technology of producing catalyst, this catalyst can be used for the reaction of a kind of olefine of catalysis, a kind of alkanoic acid and a kind of oxygen-containing gas and produces a kind of alkenyl alkanoate, and described catalyst is made of carrier granular, and these carrier granulars energy exchange cations and process dipping contain the acetate of palladium, gold and potassium.
Described technology comprises the steps:
(a) with the solution impregnating carrier particle of water-soluble palladium with the compound of gold;
(b) with a kind of precipitating reagent from above-mentioned solution with water-fast palladium and the gold compound precipitation to carrier granular;
(c) change the compound of the water-fast palladium that precipitated and gold on the carrier granular palladium and gold with a kind of reducing agent;
(d) water cleans carrier granular;
(e) make the carrier granular drying;
(f) use a kind of potassium promoter impregnated support particles again, and
(g) make impregnated particle drying to make catalyst; And what described technology adopted basically in step (b) with (c) is not contain the starting material of sodium so that reduce the amount of sodium in the catalyst, and then strengthens activity of such catalysts.
Fig. 1 shows the anticipated impact of the vingl acetate catalyst performance that sodium produced foundation embodiment of the invention A.
When implementing embodiments of the invention A technology, in general can use the water-soluble palladium and/or the golden compound that contain sodium, just its consumption is generally not big to causing the degree that contains a large amount of sodium in the catalyst.Sodium in the alkenyl alkanoate catalysts mainly comes the precipitating reagent (for example sodium metasilicate) of self-contained sodium and/or contains the co-catalyst or the activator (as sodium acetate) of sodium.On lesser extent, some carriers and some reducing agents (as sodium borohydride) also can be introduced catalyst with a large amount of sodium.Therefore, in this process of enforcement, the precipitating reagent (as potassium hydroxide), co-catalyst (as potassium acetate), reducing agent (as hydrazine) and the carrier thereof that are substantially free of sodium have correspondingly been adopted.When adopting potassium hydroxide as precipitating reagent, can also in settling step, use a kind of suitable sylvite (as potassium acetate), replace the sodium that is strapped on the carrier to promote potassium.Preferably adopt the aqueous solution of potassium hydroxide and sylvite.The consumption of salt should be 1% to 10% in the total solution weight potassium content.Need during operation carefully with the unlikely height of potassium content in the catalyst that guarantees to be generated to making catalyst activity be reduced to degree below the desired value.
Used carrier granular is a solid particulate materials in the embodiment of the invention A technology, these materials energy exchange cations (as under the condition that has SiOH or AlOH base), can contain palladium, gold and a kind of potassium promoter with dipping, and be inertia being used for producing under the condition of alkenyl alkanoate.For example, such carrier granular can be granular silica, alumina and silica-alumina.Silica is a carrier preferably.The surface area of carrier is preferably 100 to 800 square metres of every grams.
The aqueous solution of the compound of used water-soluble palladium and gold comprises the aqueous solution of the compound of any suitable palladium or gold in the embodiment of the invention A technology, and these compounds can be palladium bichloride (H), the sour sodium (Na of tetrachloro palladium (II) 2PdCl 4), palladium nitrate (II), palladium sulfate (II), chlorauride (III) or tetrachloro gold (III) acid (HAuCl 4).Liquor capacity is the 95 to 100% relatively good of carrier void content, is 98 to 99% better.
Used precipitating reagent comprises the silicate and the hydroxide of lithium and potassium in the embodiment of the invention A technology.Precipitating reagent preferably adopts the aqueous solution that contains excessive 1.6 to 1.8 moles precipitating reagent.The volume of used solution preferably can just not have carrier granular.For avoiding the contingent degraded of carrier, the weight ratio of precipitating reagent and carrier can not be too high.For instance, the weight ratio of potassium hydroxide and carrier is not cause carrier that significant degraded takes place at about 0.08: 1 o'clock.
The reducing agent that is adopted in the embodiment of the invention A technology comprises ethene, hydrazine, formaldehyde and hydrogen.Reducing agent preferably adopts the aqueous solution that contains by the excessive reducing agent of the molal quantity of 50: 1 (perhaps 10: 1 better).If what adopt is hydrogen, need be heated to 100 to 300 ℃ to catalyst to finish reduction process usually.
The potassium promoter that is adopted in the embodiment of the invention A technology comprises alkanoic acid potassium and any compound that can change a kind of potassium of alkanoic acid potassium in the reaction that generates alkenyl alkanoate into (described reaction is meant that promptly ethene, a kind of alkanoic acid and a kind of oxygen-containing gas under the effect at catalyst generate a kind of reaction of alkenyl alkanoate).The potassium compound that is suitable for comprises potassium acetate, saleratus, potassium nitrate, and can also be potassium hydroxide when using a kind of stable carrier.Preferably the form with the aqueous solution adds co-catalyst.
Cleaning step in the embodiment of the invention A technology can intermittently carry out, and also can carry out continuously.Continuous wash efficient is higher, but is not the Catalyst Production that is suitable for extensive (for example plant layout) most.In the continuous wash process, rinse water slowly and is continuously passed catalyst in a period of time (as 8 to 24 hours) lining.In interrupted cleaning process, mixture is stayed for some time (for example 0.5 to 2.0 hour), and then water and catalyst separation are opened.When interrupted the cleaning, usually need to carry out for several times (as 2 to 10 times, perhaps more preferably 4 to 6 times) such cleaning, so that impurity (as halide) content is reduced to below the aspiration level.No matter be interrupted the cleaning or continuous wash, its temperature range can be 20 ℃ to 80 ℃, and the volume ratio of rinse water and catalyst all can be 2: 1 to 100: 1.By cleaning step, can from catalyst, remove some impurity, particularly chloride.
The drying work to catalyst corresponding to step (e) and step (g) in the embodiment of the invention A technology of producing alkenyl alkanoate catalyst can any suitable mode be carried out.For instance, drying can carried out in a kind of forced ventilation baking oven 15 to 30 hours under 40 ℃ to 120 ℃ the temperature.
The example of embodiment A
In following example, used following abbreviation meaning is as follows:
Abbreviation meaning carrier I average diameter is 5 to 6 millimeters, contain about 0.1 percent by weight sodium
Silica beads.The surface area of these pearls is 150 to 200m 2/ g,
Pore space is 0.6-0.7ml/g.Carrier I contains and can exchange
Cationic SiOH base.Carrier I is gone out by Sud Chemie AG
Sell, trade mark is ＂ KA-160 ＂.STY *Generate vinylacetate with every liter of catalyst per hour
The gram number is space time yield (a kind of catalyst activity of unit
Measure).% selectivity optionally computational methods is as follows: selectivity=100 * (ethene
The yl acetate molal quantity)/(vinylacetate molal quantity+1/2
* Co 2Molal quantity).AA analyzes the gram of the atomic absorption spectrum ICP inductively coupled plasma atomic emission determination method g VA/l cat/hr vinylacetate that per hour every liter of catalyst produced
Number.* all that reported in the example that occurs below are active all to be based on activity and the selectivity numerical value of being surveyed in 26 hours with following catalyst test method with selectivity numerical value after reaching sufficient oxygen supply.VA vinylacetate KOAc potassium acetate ECOAc ethyl acetate NaOAc sodium acetate % percentage by weight g gram ml milliliter mm millimeter hrs hour min minute
In following example, adopted following process:
Catalyst preparation process
Carrier I (15g) is added Na 2PdCl 4(35.86%Pd, 0.258g) and HAuCl 4(48.95%Au 0.094g) is dissolved in the 9.0ml deionized water in the formed solution.Slowly stir the mixture that forms in this way and all be absorbed into carrier, make it at room temperature in an air-tight bottle, to leave standstill about 1 hour then, so that make palladium and golden salt on the carrier band up to all moisture.The potassium hydroxide solution (being dissolved with 0.371g in the 28ml water) that is used as a kind of precipitating reagent floods wet catalyst.In the settling step of a preferred embodiment of the invention, potassium acetate and potassium hydroxide are united use.After mixing several seconds, make mixture at room temperature keep being submerged and no longer be stirred and reach 23 hours, so that the compound of water-fast palladium and gold is deposited on the carrier.Then the hydrazine hydrate of 1.0g85% is added in the said mixture, palladium and gold just are reduced out.Stir the mixture several seconds, and make mixture at room temperature keep being covered and no longer be stirred to reach 23 hours again.Supernatant liquor is outwelled from catalyst, and with water rinse several times catalyst to remove the residual metal that exists on a small quantity.With the following thorough cleaning catalyst of post cleaning procedure to remove chloride and residual agent.Catalyst place send on the stainless steel sift forced air draft oven 60 ℃ dry 20-24 hours down.With the potassium content in the AA analytic approach analysis of catalyst.Then with the above-mentioned impregnation technology of palladium and golden salt that is used for the aqueous solution of catalyst soakage at the potassium acetate of institute's required amount.Make impregnated catalyst drying 20-24 hours at 60 ℃ then.Measure the content of middle palladium, gold, sodium and the potassium make with the icp analysis method,, also determine the content of sodium and potassium with the AA analytic approach simultaneously for for the purpose of accurate.Handle the catalyst of making in this way with outer infusion process (promptly all basically palladiums and gold all are in the layer of 0.5mm under the carrier I bead surface).
The post cleaning procedure
Catalyst is placed 1.24 inches high glass columns of 24 inches of a diameter, and (this chromatographic column is furnished with a Teflon TMPlug valve) cleans in or clean again.Usually the 15g catalyst is added in the post, and then inject water.Regulate hanging plug valve to such an extent that make the amount of the liquid that from post, flows out be: at room temperature in about 24 hours time, have 1 liter of liquid to pass catalyst approximately.During this period of time,, catalyst is removed, and be dried by above-mentioned Preparation of Catalyst program with excess liquid emptying from post.
The catalyst test method
Glass microballoon dilute catalyst (2.5g 5 to 6mm catalyst spheres samples) with 10.5ml 0.5mm advances the mixture uniform distribution in two arms of 316 stainless steel U type pipe reactors.3/8 inch of reactor external diameter, about 6 inches of total height.After the heatable catalyst and make system be in 115 pounds/square inch following time of pressure simultaneously, the ethene air-flow of 151ml/min begins to pass reactor when be controlled at 150 ℃ stove in temperature in.After keeping above-mentioned these conditions to reach 1.5 hours, acetic acid vapor is added in the ethene, make mixture pass catalyst and reach 45 minutes.Air added in the unstrpped gas with a speed that slowly increases in 45 fens clock times reach 105ml/min up to total flow rate.Before the beginning image data, catalyst was stablized 2 hours.Final gas componant is an ethene: acetate: oxygen: nitrogen=52.9: 10.7: 7.7: 28.7, and total gas phase hourly space velocity is about 3800hr -1, the hourly space velocity of acetic acid liquid is about 1hr -1With gas chromatographic analysis method assay products.The circular regeneration rate of used microreactor is about ± 10STY unit in these experiments.
Example 1
Carrier I just contains the sodium of 0.1% weight of having an appointment when manufactory buys.When adopting NaOH or sodium metasilicate, also can introduce 0.4% to 0.8% sodium in addition as precipitating reagent.As 3 parts of catalyst of precipitating reagent preparation, can reduce the sodium content in the final catalyst with potassium hydroxide like this.The potassium acetate of variable concentrations is added precipitant solution, the equalization point of ion-exchange further is offset to potassium.Catalyst is used with a collection of masterbatch and is prepared from, and the specified palladium loading of this batch masterbatch is 0.58 weight %, and the Au/Pd ratio is 0.46.After having cleaned catalyst with the hydrazine reduction and with the post cleaning procedure, sodium in the analysis of catalyst and potassium content.Need in addition then to add potassium acetate so that final potassium acetate content reaches about 5.3 weight %.Given result shows that the sodium content in the catalyst has been lowered in the Table A.Along with the increase of potassium content in the precipitant solution, the sodium content in the catalyst reduces without exception, and its catalytic activity also improves.
Table A
Preparation %KOAC (a) %Na (b) the STY % selectivity of low sodium catalyst
0 0.186 576 93.4
2.5 0.121 603 93.2
5.0 0.091 597 93.4 (a) adds the Wt% (percentage by weight) of potassium acetate in the precipitant solution.(b) the Wt% calculated value of sodium in the catalyst of Sheng Chenging, they are analyzed based on the preceding AA of KOAc dipping, and have considered the amount of added KOAc.
Do with sodium metasilicate that precipitating reagent (replacement potassium hydroxide) is prepared to go out similar catalyst, its STY is 544, and selectivity is 93.6, and sodium content is 0.44Wt%.In settling step, do not add any potassium acetate.
Example II
With studying sodium to the vingl acetate catalyst Effect on Performance by the experiment of statistical law design, and resulting model can be used for prediction with the performance of the made vingl acetate catalyst of the technology of any embodiment of the present invention (being embodiment A, B and C), and with above mentioned, and the performance of the vingl acetate catalyst of the technology manufacturing of two U.S. Patent applications submitting to simultaneously of the present patent application.The functional relation of weight ratio, potassium content and the catalyst weight of measurable catalyst activity of these models and selectivity thereof and sodium content, palladium loading, gold and palladium.Table B and C show these models respectively and reach data by it produced.
Because conversion ratio is to influence the two principal element of catalyst production and selectivity, so can only carry out under constant conversion the significant comparison of catalyst variable.Be the influence of prediction catalyst component under constant conversion, the oxygen transformation model among the rearrangement table B is to express catalyst weight and palladium content, gold/palladium ratio, the functional relation between potassium content, sodium content and the conversion ratio thereof.Replace catalyst weight item in STY and the selective model with this catalyst weight item then.Fig. 1 drawn sodium content increase to vingl acetate catalyst active with anticipated impact optionally.Used abbreviation meaning is as follows among table B and the C: in the Wt%Au/Pd catalyst of Pd palladium in catalyst weight ratio Cat, the Wt of gold and palladium with Wt%Na sodium the Wt%STY in catalyst of catalyst weight K potassium in catalyst of gram expression with every liter of vinylacetate that catalyst generates per hour
The empty time yield R2 characterization data that shows of gram numerical table and the molal quantity that generates with every kg catalyst catalysis per hour of the correction coefficient RSD relative standard deviation EtOAc By-of the model match quality output %Heavies that expresses the ethyl acetate of Product Rate use the percentage by weight of the vinylacetate that is generated to represent the byproduct of heavy By-Product.Heavy byproduct is restricted in gas-chromatography and divides in VA to analyse all products that elution goes out after acetate in the program.
Table D represents with the influence of the change of showing the sodium content that model prediction goes out among the B to catalyst activity.
Table B
Performance-relevant model (a) O with catalyst component A part 2Conversion ratio=100/ (1+e with vinylacetate Z1)
Z1=0.507-1.907 (%Pd-0.743)-0.863 (Au/Pd-0.584)+0.109 (%K-2.43)+0.459 (%Na-0.502) wherein
(19.6) (8.1) (4.5) (7.0)
-.913(Cat.Wt.-1.91)+1.438(％Pd-0.743)(Au/Pd-0.584)+0.551(Au/Pd-0.584)(Cat.Wt.-1.91)
(29.8) (3.9) (5.1)
+1.438(％Pd-0.743) 2+2.779(Au/Pd-0.584) 2+1.384(％K-2.43) 2+0.284(Cat?Wt.-1.91) 2
(3.1) (4.2) (4.4) (6.5) R 2＝0.988
Active (the STY)=e of RSD=0.103B part Z2
Z2=6.707+0.942 (%Pd-0.743)+0.334 (Au/Pd-0.584)-0.194 (%Na-0.502)-0.123 (Cat.Wt.-1.91) wherein
(13.6) (5.6) (8.0) (8.1)
-1.438(％Pd-0.743) 2-0.128(％K-2.43) 2
(4.3) (5.6) R 2＝0.922
The RSD=0.079C part is to the selectivity=100-e of vinyl acetic acid fat Z3
Z3=1.9+0.457 (%Pd-0.743)-0.118 (%K-2.43)-0.095 (%Na-0.502)+0.121 (Cat.Wt.-1.91) wherein
(17.4) (12.7) (3.5) (14.8)
+0.186(％Pd-0.743)(Cat.Wt.-1.91)-0.254(Au/Pd-0.584)(％K-2.43)-0.0525(K-2.43)(Cat.Wt.-1.91)
(5.9) (6.3) (4.6)
-0.164(％Na-0.502)(Cat.Wt.-1.91)+0.038(％K-2.43) 2
(4.1) (3.2) R 2＝0.956
RSD＝0.034
Table B (continuation)
The D part
EtOAc byproduct rate=e Z4
Z4=-3.640+0.9175 (%Pd-0.743)-1.135 (Au/Pd-0.584)-0.2189 (Cat.Wt.-1.91)-0.3743 (%Na-0.502) wherein
(7.5) (10.7) (8.1) (6.4)
-0.267(％K-2.43) 2-2.428(％Pd-0.743) 2
(7.2) (4.1) R 2＝0.872
RSD＝0.142
The %=e of the byproduct of the weight that E part is represented with VA Z5(b)
Z5=0.280+0.441 (Au/Pd-0.584)-0.254 (%K-2.43)-0.0694 (Cat.Wt.-1.91) wherein
(5.2) (10.5) (3.1) R 2＝0.797
RSD＝0.119
(a) value in the bracket is the T ratio that observes under the regression equation
(b) based on the amount of the vinylacetate that is produced
Table C
Numerical value (a) the No. %Pd Au/Pd %K %Na Cat Wt. %O of design 2 STY ％ 1 0.80 0.70 2.23 0.51 1.64 34.4 897.6 93.2 2 0.80 0.70 2.23 0.51 1.65 37.1 941.5 92.9 3 0.80 0.70 2.23 0.51 1.65 34.8 923.3 93.2 4 1.05 0.91 3.67 0.26 0.73 16.1 1181.7 94.4 5 0.57 0.46 2.33 0.14 0.73 7.1 759.2 94.6 6 0.54 0.89 2.27 0.16 2.50 44.9 727.4 92.5 7 1.13 0.96 2.35 0.18 0.75 21.0 1262.4 94.1 8 0.52 0.44 3.51 0.17 0.76 5.8 553.2 94.5 9 1.14 0.46 2.35 0.19 2.50 66.1 912.3 89.710 0.53 0.91 3.64 0.14 2.51 32.7 595.0 94.411 1.05 0.47 3.68 0.18 2.50 55.7 847.4 92.112 1.08 0.87 2.80 0.73 0.76 17.5 1158.0 93.813 0.52 0.46 1.50 0.37 0.72 6.6 569.0 94.014 0.52 0.85 1.40 0.50 2.50 38.4 587.4 91.515 1.08 0.94 1.40 0.54 0.74 19.3 1111.7 92.116 0.55 0.42 2.70 0.44 0.76 5.9 617.2 94.317 1.10 0.45 1.40 0.59 2.54 57.7 769.9 89.718 0.55 0.91 2.90 0.40 2.54 34.7 629.5 94.119 1.09 0.47 2.80 0.50 2.52 56.6 865.0 91.520 0.82 0.70 2.12 0.49 1.63 35.2 901.9 93.021 0.82 0.70 2.12 0.49 1.62 35.7 925.7 92.922 0.78 0.65 2.12 0.53 2.52 50.6 793.2 92.223 0.78 0.65 2.12 0.53 1.63 33.3 884.2 93.424 1.07 0.83 2.93 0.69 2.53 51.8 822.1 92.525 0.53 0.36 2.96 0.44 2.52 28.5 506.7 93.426 1.07 0.82 1.47 0.56 2.50 54.3 709.7 88.727 1.07 0.82 1.47 0.56 2.51 52.4 701.7 89.328 0.56 0.82 3.02 0.42 0.75 7.7 733.8 95.029 1.02 0.46 2.88 0.48 0.75 14.1 966.6 93.830 0.54 0.44 1.51 0.36 2.50 29.6 483.5 92.7
Table C (continuation) No. %Pd Au/Pd %K %Na Cat Wt. %O 2Conversion ratio STY % selective 31 0.54 0.80 1.48 0.50 0.75 10.8 763.7 94.032 1.08 0.43 1.47 0.63 0.75 13.1 889.6 93.233 0.80 0.66 2.12 0.92 1.64 33.0 871.5 93.234 0.80 0.66 2.12 0.92 1.62 32.3 866.6 93.535 1.13 0.62 2.10 0.59 1.62 43.1 1066.2 92.436 0.41 0.61 2.20 0.37 1.64 21.3 621.8 94.237 0.76 0.87 2.10 0.55 1.62 33.3 881.8 93.738 0.76 0.34 2.10 0.45 1.65 27.5 734.0 93.439 0.77 0.61 2.10 0.52 0.43 9.9 1246.7 93.740 0.77 0.61 2.10 0.52 2.86 56.9 745.8 91.7
( b ) 41 0.56 0.39 2.19 0.44 2.54 36.0 607.8 93.542 0.57 0.39 2.19 0.15 2.54 38.4 612.0 92.743 0.54 0.39 3.38 0.68 2.54 25.8 482.8 94.144 0.55 0.39 3.38 0.28 2.54 30.9 545.9 93.545 0.56 0.39 2.79 0.28 2.54 36.4 605.5 93.446 0.56 0.39 2.79 0.16 2.54 37.2 610.9 92.947 0.54 0.39 2.79 0.96 2.54 27.4 493.2 93.848 0.54 0.39 3.62 0.36 2.54 27.2 492.4 93.749 0.57 0.39 1.95 0.20 2.54 35.3 571.0 92.950 0.54 0.39 3.70 0.39 2.54 27.1 483.8 93.951 0.55 0.39 2.12 1.25 2.54 27.4 494.1 94.152 0.50 0.39 3.95 2.39 2.54 13.4 283.9 94.353 0.56 0.39 2.25 0.50 2.54 33.6 609.3 93.554 0.57 0.39 2.25 0.12 2.54 34.9 641.5 93.155 0.55 0.39 2.25 1.01 2.54 28.7 540.0 94.1 ( a ) ； It is to record with the ICP method that palladium and gold contain value, and sodium and potassium value then are to record with atomic absorption analysis. (b) catalyst is to be prepared into by sodium acetate and potassium acetate being added among the catalyst I I that cleans again by the described method of embodiment of the invention A.The composition of being reported is that basis is to the analysis of this catalyst and calculating of added sodium acetate and potassium acetate.
Table D sodium is to the percentage % of the anticipated impact %Na STY improvement of catalyst * activity *0.1 665 0.00.2,649 2.50.3,633 5.10.4,618 7.60.5,603 10.30.6,581 14.50.7,574 15.90.8,560 18.80.9,546 21.8* are set at 0.58%Pd at one, Au/Pd 0.45 and 2.2%k catalyst
Form and be set at 35% oxygen conversion.The * sodium content is reduced to the expection percentage of 0.1% STY that causes by the amount shown in first hurdle
Than changing.
Example III
The program of routine I is repeated below in the United States Patent (USP) 4048096 (Bissot): prepare two samples (control group 1 and 2), each all adopts 15g carrier I, 0.315g Na 2PdCl 4, 0.085g HAuCl 4, 0.585g Na 2SiO 39H 2The hydrazine hydrate of O, 0.59g 85% and 0.823g potassium acetate.Owing to not disclose definite cleaning procedure in the example 1 of Bissot, so the catalyst of control group 1 is an employing post cleaning procedure with every gram catalyst 23ml H 2The ratio of O is cleaned, the cleaning way of the catalyst of control group 2 similarly, that just adopt is every gram catalyst 31ml H 2This ratio of O.With the palladium and the gold content of ICP method analysis of control group 1 and 2 catalyst, with AA method analysis potassium and sodium content wherein.The experimental error that sodium content is measured is estimated as pact ± 0.01 relative percentage.Catalyst in the control group 1 is divided in duplicate to be analyzed.The results are shown in Table E.
Table E
%Pd %Au %K %Na STY selectivity control group 1 0.544 0.201 2.34 0.32 550 93.9 control groups 1 0.556 0.204 2.35 0.32 control groups 2 0.552 0.195 2.34 0.38 535 93.7Bissot 0.578 *0.242 *2.08 *---560 *93 ** go out in the * * Bissot example 1 disclosed according to the Bissot data computation
Example IV
The measurement activity value of 3 kinds of commercial catalysts (catalyst X, Y and Z) has been shown among the table F.In table F, the catalyst (＂ model catalyst ＂) that has identical component among the activity of catalysis X agent and Y and any embodiment of the present invention is compared.The expection activity value is according to the model of table B and supposes that sodium content is 0.15% to determine.The expection activity value of model catalyst is relatively high.Because the composition of catalyst Z is in beyond the table B model scope, so can not similarly compare it.
Catalyst X is prepared from by this Preparation of Catalyst program.The difference of the preparation of the preparation of catalyst X and catalyst Y is in the preparation of catalyst Y: (1) carries out the drying processing to catalyst before precipitation, and (2) used precipitating reagent is NaOH rather than sodium metasilicate.The reduction of two kinds of catalyst, cleaning, drying and potassium acetate impregnation steps are all identical.
As for catalyst Y, nominally suffix A, the B of table among the F and C refer to the different sample (＂ criticizes ＂) of catalyst identical for catalyst Y and Z, suffix 1 and 2 refers to from the duplicate analysis result of doing of different samples with a collection of catalyst.
Palladium content is higher among the catalyst Z, and adopt a kind of cadmium co-catalyst rather than with the gold.The toxicity of cadmium is much larger than gold.In addition, catalyst Z is that utilization and technology of the present invention technology inequality basically prepares, and that is to say, catalyst Z is by being prepared into the acetate solution impregnated carrier of a kind of palladium, cadmium, potassium is then dry.The technology of preparation catalyst Z need not precipitate, reduction or cleaning step.
Table F
%Pd %Au %Cd %K %Na STY catalyst x *0.53 0.22 0 2.36 0.54 272 model catalyst, 0.53 0.22 0 2.36 0.15 589 catalyst YA-1 *0.49 0.19 0 2.29 0.60 360 model catalyst, 0.49 0.19 0 2.29 0.15 546 catalyst YA-2 *0.49 0.19 0 2.31 0.60 360 model catalyst, 0.49 0.19 0 2.31 0.15 545 catalyst YB *0.63 0.24 0 2.27 0.70 386 model catalyst, 0.63 0.24 0 2.27 0.15 669 catalyst YC-1 *0.61 0.24 0 2.24 0.69 395 model catalyst, 0.61 0.24 0 2.24 0.15 653 catalyst YC-2 *0.61 0.26 0 2.18 0.70 395 model catalyst, 0.61 0.26 0 2.18 0.15 658 catalyst Z-1 *2.16 0 1.88 1.89 0.08 685 model catalysts are catalyst Z-2 beyond model scope *2.16 0 1.89 1.92 0.09 685 model catalysts are beyond model scope *Compare catalyst
Embodiment of the invention B general introduction
Embodiments of the invention B part is based on following discovery: if reduced the sodium content in the catalyst by water or with a kind of aqueous solution cleaning catalyst of potassium promoter afterwards in the step (7) of United States Patent (USP) 4048096 technologies, then the activity with the alkenyl alkanoate catalysts of this patent technology manufacturing is improved.
More particularly, embodiment of the invention B provides a kind of technology of producing a kind of catalyst, this catalyst can be used for the reaction of a kind of olefine of catalysis, a kind of alkanoic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, this catalyst is made of carrier granular, and these particles can also contain gold, palladium and a kind of potassium promoter through dipping by exchange cation.Described technology comprises the following steps:
(a) with the solution impregnating carrier particle of water miscible palladium and gold compound;
(b) be deposited on the carrier granular from above-mentioned solution with the compound of a kind of precipitating reagent water-fast palladium and gold;
(c) change the compound of the water-fast palladium that precipitated and gold on the carrier granular palladium and gold with a kind of reducing agent; And
(d) water cleans the carrier that is flooded;
(e) make the impregnated carrier drying of being cleaned;
(f) with the further impregnated support particles of a kind of potassium promoter;
(g) carrier drying that makes dipping like this is to generate dry catalyst, and this catalyst contains sodium owing to there being sodium to exist in one or more used in step (a) to (f) materials;
(h) water or with the aqueous solution cleaning-drying that contains a kind of potassium promoter catalyst reducing the amount of the sodium in the catalyst, and then improved activity of such catalysts, and
(i) make the catalyst drying.
When the technology of embodiment embodiment of the invention B, be preferably in and use a kind of aqueous solution that contains potassium promoter in the step (h), be reduced to below the aspiration level with the concentration of avoiding potassium promoter (carrier floods with it exactly) in step (f).If make water after this manner in step (h), undesirable cocatalyst concentration will take place reduce phenomenon.Therefore but,, then also can follow a step (j) of flooding potassium promoter the second time after the step (i) if in step (h), used water and caused cocatalyst concentration to reduce fallaciously, and step of dry catalyst (k) for the third time then.In some cases, can use excessive potassium promoter in initial potassium promoter impregnation steps (step (f)), to guarantee both to have made water clean (step (h)), potassium promoter also can reach aspiration level in the product of step (i).The program in back also can avoid adopting step (j) and (k).
Owing to do not wish to be limited to any specific theory, it is believed that the potassium promoter that is adopted in the Preparation of Catalyst program of Bissot has been replaced at least partly to be bound by the sodium on the ion exchange site on the catalyst carrier.Sodium derives from the starting material (especially precipitating reagent) that is adopted in the Preparation of Catalyst program of Bissot (US4048096).Though replaced by potassium promoter, such sodium still is retained in the catalyst of Bissot technology manufacturing as a kind of impurity that suppresses activity.In technology of the present invention, only need water or a kind of aqueous solution cleaning catalyst (step (h)) that contains potassium promoter can from catalyst, dispose the sodium that those are replaced at an easy rate.By before the potassium promoter displacement,, can not from catalyst, dispose sodium effectively in step (f) with simple water ablution (promptly as step (d) as described in) because sodium very closely is combined on the carrier.But, step (d) can effectively be removed the impurity of nonbonding, particularly from step (a) to the chloride of (c) and excessive reagent.
Brief description to the Embodiment B schematic diagram
Fig. 1 shows sodium to the anticipated impact according to the made vingl acetate catalyst performance of embodiment of the invention B.
The description of most preferred embodiment B
Used carrier granular is the solid granular material in the embodiment of the invention B technology, and these materials can exchange cation, can flood with palladium, gold and a kind of potassium promoter, and be inertia being used to make under the condition of alkenyl alkanoate.The example of these carrier granulars can be graininess silica, alumina and silica alumina.Silica is best carrier, the best 100-800m of the surface area of carrier 2/ g.
The used water-soluble palladium and the aqueous solution of gold compound comprise any suitable palladium and the aqueous solution of gold compound in the embodiment of the invention B technology, and these compounds can be palladium bichloride (II), the sour sodium (Na of tetrachloro palladium (II) 2PdCl 4), palladium nitrate (II), palladium sulfate (II), chlorauride (III) or tetrachloro gold (III) acid (HAuCl 4).The volume of solution is the 95-100% of suitable carrier porosity preferably, and certainly, 98-99% is better.
Used precipitating reagent comprises the silicate and the hydroxide of sodium, lithium, potassium in the Embodiment B of catalyst process of the present invention.Precipitating reagent preferably adopts the aqueous solution form of the precipitating reagent that contains excessive 1.6-1.8 mole.The amount of used above-mentioned solution preferably just enough there be not carrier granular.
Used reducing agent comprises hydrazine, ethene, formaldehyde, hydrogen and sodium borohydride in the embodiment of the invention B technology.Reducing agent preferably adopts the aqueous solution form that contains by the excessive reducing agent of the molal quantity of 50: 1 (10: 1 better).If usefulness is hydrogen, must be heated to 100 to 300 ℃ to catalyst usually and just can finishes reduction process.
The used potassium promoter of Embodiment B technology that the present invention is used for making alkenyl alkanoate catalyst comprises alkanoic acid potassium and can change a kind of compound of any potassium of alkanoic acid potassium in the reaction that forms alkenyl alkanoate (promptly existing ethene, a kind of alkanoic acid and a kind of oxygen-containing gas under the condition of catalyst to generate a kind of reaction of alkenyl alkanoate) process.The potassium compound that is suitable for comprises potassium acetate, sodium acid carbonate, potassium nitrate, and can also be potassium hydroxide when using stable carrier.Preferably adopt the co-catalyst of aqueous solution form.
Cleaning step (d) among the implementation of processes of the present invention example B and (h) can carry out intermittently or continuously.Continuous wash efficient is higher, but is not the Catalyst Production that is suitable for extensive (as plant layout) most.In the continuous wash process, washing lotion slowly and is continuously passed catalyst in a period of time (as 8-24 hour) lining.In interrupted cleaning process, catalyst is contacted with washing lotion, mixture is stayed for some time (as from 0.5-2.0 hour), again liquid and catalyst separation are opened.In interrupted cleaning process, often need carry out so several times cleaning (such as 2-10 time, 4-6 time better).Interrupted clean or the continuous wash process in all can to adopt temperature be that the volume ratio of 20-80 ℃ and cleaning fluid and catalyst is 2: 1-100: 1 such condition.
In the step (h) of implementation of processes of the present invention example B, water or with a kind of work of the aqueous solution flushing catalyst that contains potassium promoter and to be used for making the potassium promoter impregnation steps of prior art technology of alkenyl alkanoate catalysts completely different.What the impregnation steps of above-mentioned prior art adopted is early stage wet processing or decant technology.In early days in the wet processing (seeing the example 5 in the BP 1215210 of National Distillers), catalyst contacts with the minimum potassium promoter aqueous solution, these aqueous solution are only enough filled the hole of carrier and catalyst are flooded, and make it to contain the potassium promoter of desired quantity.Then water evaporates is fallen.This technology can not be removed the sodium of a tiny bit from catalyst.In decant technology, catalyst (preferably dry) be immersed in than in the bigger potassium promoter aqueous solution of amount used in the early stage wet processing.After hole is filled with solution, outwell excessive solution, again catalyst is carried out drying and handle.Only carry out the operation of a submergence and decant, and time of contact is shorter.Like this, can only from catalyst, remove a spot of sodium with decant technology.Example 9 in people's such as sennewald the United States Patent (USP) 3743607 shows the decant technology that adopts a kind of moist catalysis.
The implementation of processes example B step (e), (g), (i) or the drying to catalyst (k) that are used for making alkenyl alkanoate catalysts according to the present invention are handled available any suitable mode and are carried out.For instance, drying can carried out 15-30 hour in a forced ventilation baking oven under 40 ℃ to 120 ℃.
The example of Embodiment B is described
In the example of following explanation Embodiment B, used abbreviation is identical with the abbreviation meaning of the above example defined that is used to illustrate embodiment A.
At the following example that is used for illustrating Embodiment B, adopted follow procedure: the Preparation of Catalyst program
A, carrier I (15g) is added Na 2PdCl 4(35.86%Pd, 0.258g) and HAucl 4(48.95%Au 0.094g) is dissolved in the formed solution of 9.0ml deionized water.Slowly stir formed mixture, all absorb into carrier, mixture was stopped about 1 hour in the bottle of a sealing, so that make palladium and golden salt energy impregnated carrier up to all moisture.The NaOH (containing 0.236g in the 28ml water) or the sodium metasilicate that are used as precipitating reagent (contain Na in the 28ml water 2SiO 30.837g) solution do not have wet catalyst.After mixing several seconds, make mixture be submerged and not by the state of disturbance under at room temperature kept 23 hours, do not amass to carrier with compound water-fast palladium and gold with.In said mixture, add the hydrazine hydrate of 1.0g85% then to restore palladium and gold.Mixture is stirred several seconds, and then make it at room temperature to keep to be covered and not by the state of disturbance 23 hours.From catalyst, outwell supernatant liquor and water flushing catalyst 4 times to remove remaining little metal.With post cleaning procedure or the following thorough cleaning catalyst of interrupted cleaning procedure.Catalyst placed send into a forced ventilation baking oven on the stainless steel sift, 60 ℃ of oven dry 20-24 hours down.With the potassium content in the AA analytic approach analysis of catalyst.Then with the above-mentioned impregnation technology that is used for palladium and golden salt, with the solution impregnating catalyst of a certain amount of potassium acetate.Then, make impregnated catalyst following dry 20-24 hours at 60 ℃.The technology of the prior art in the United States Patent (USP) 4048096 of Bissot (be above-mentioned step (e) to (g)) is so far.And the technology of embodiment of the invention B then also has other step (h) and (i), also (j) and (k) in steps if necessary, the narrations below these are visible.
B, measure the content of palladium, gold, sodium and potassium in the catalyst make with the icp analysis method.In most of the cases, for the purpose of more accurate, also use the content of AA assay sodium and potassium.
C, except as otherwise noted, said procedure will be used for preparing the related all catalyst of following example.When adopting the carrier I of different amounts, the amount of other used starting material is respective change also.
D, with a layer infusion process (promptly all basically palladiums and gold all concentrate in the layer within the following 0.5mm of carrier I bead surface) flood just like the such catalyst of making described in following examples.Catalyst cleaning procedure (identical) with the example of top explanation embodiment A.The catalyst method of inspection (identical) with the example of top explanation embodiment A.
Example I
A, comparative example
An important step in the alkenyl alkanoate catalysts preparation process is exactly the chloride that discharges of the known removing of people and the water cleaning step of remaining starting material.In the laboratory, can place catalyst one post to clean 20-24 hours easily with the ratio of the about 60-80ml water of every gram catalyst.For reality and reason economically, the interrupted mode of cleaning in the time of a much shorter that extensive (as pilot plant) preparation is adopted, the used water yield of the catalyst that unit volume is cleaned also significantly reduces.Have now found that the activity of such catalysts that the activity of such catalysts that large-scale equipment is produced is produced than laboratory scale is low.According to conjecture, its activity difference is because the cleaning efficiency in the large-scale equipment is lower.
The typical results of property of the catalyst that the catalyst that Table I has compared prepared in laboratory and the large-scale equipment of United States Patent (USP) 4048096 technologies of following Bissot are prepared.Say that exactly all catalyst are all made as precipitating reagent with sodium metasilicate according to the Preparation of Catalyst program, difference is that the amount of starting material used in the mass preparation process increases in proportion, and the cleaning procedure of the two also has difference.Use to such an extent that be post cleaning procedure and mass preparation is used to such an extent that be interrupted cleaning procedure in the bench scale preparation.The prepared catalyst of large-scale equipment comprises 80 liters of scale pilot plant samples and is entirely 260 liters of samples that equipment is produced commercially producing and design.The prepared catalyst of large-scale equipment contains about palladium of 5 to 10Wt% than the catalyst of prepared in laboratory usually, thereby large-scale equipment prepares the also correspondingly low approximately 5-10% of STY value of catalyst.
Table I
The catalyst S TY of the active comparative example of laboratory scale and extensive catalyst samples, (a) specific activity, (b) %Pd, (c) %Au, (c) laboratory scale sample I-1 571, (3) 197.0 0.516 0.198I-2 546, (3) 188.5 0.516 0.208I-3 543 191.6 0.505 0.198I-4 556, (2) 181.9 0.510 0.200I-5 547 194.4 0.500 0.190I-6 567 198.0 0.510 0.200 mean values 555 191.9
The empty time yield of extensive sample I-7 (d) 521 165.4 0.558 0.231I-8 (d) 532 (2) 172.0 0.554 0.248I-9 (d) 534 (2) 172.7 0.553 0.238I-10 (d) 521 (2) 168.5 0.552 0.237I-11 (e) 495 (6) 163.0 0.543 0.214I-12 (e) 484 156.5 0.553 0.223I-13 (e) 485 156.9 0.554 0.222I-14 (e) 528 173.9 0.589 0.226I-15 (e) 525 172.8 0.568 0.217I-16 (e) 468 154.1 0.536 0.204I-17 (e) 489 (2) 155.5 0.562 0.213I-18 (e) 520 165.1 0.564 0.212I-19 (e) 479 149.6 0.568 0.203 mean value 497 160.6 (a) STY=; G VA/l cat/hr, the value in the bracket is the average test number (TN) of institute; (b) specific activity, g VA/g Pd/hr; (c)
The Wt% of determined Pd of icp analysis method and Au; (d) 80 liters of pilot plant's tests; (e) 260 liters of plant layout tests.
B, embodiments of the invention B
Data in the Table I show that the activity of such catalysts of large-scale equipment preparation is lower than the activity of such catalysts of bench scale preparation.For whether the reduction of the catalyst activity of determining extensive manufactured is because clean the catalyst sample (being sample I-7, I-9, I-12 and the I-17 in the Table I) that insufficient employing post cleaning procedure water cleans (by the step (h) of technology of the present invention) 4 large-scale equipment preparations again, then it is carried out dry processing the (pressing the step (i) in the embodiment of the invention B technology).The 5th catalyst sample is to adopt Preparation of Catalyst program and interrupted cleaning procedure to be prepared from a laboratory scale, and a part of this sample adopts the post cleaning procedure to clean again by step (h) water in the technology of embodiment of the invention B, and then in addition dry by the step (i) of embodiment of the invention B technology.These five clean again and dry again catalyst in each all flood again with 5% potassium acetate by the step (j) in the embodiment of the invention B technology so that replenish those supposition clean again with the process of drying again (step in the embodiment of the invention technology (k), in the potassium acetate that has been removed.The results are shown in Table 2, these results show to clean again can both make the active 5-10% of raising
Table II
Again whether the influence catalyst that cleans catalyst activity cleans STY % change amount again
Extensive sample 1 *I-7 not 521-2 I-7 is 557+73 *I-9 not 534 (2)-4 I-9 is 566+65 *I-12 not 484-6 I-12 is 537+117 *I-17 not 489 (2)-8 I-17 is 524+5 laboratory scale samples 9 *508-10 is not 561+10 *Comparative example
Example 11
In the described experiment of routine I, suppose that cleaning (step of technology of the present invention (h)) has more also removed whole potassium acetates.So, in those experiments, added potassium acetate (step of technology of the present invention (j)) again after cleaning again, used amount when the amount of adding equals catalyst flooded first.8 hypothesis that the different catalyst sample of potassium loading checks this and routine I to link with another series.The analysis result done of these 8 catalyst (catalyst I I-1 to II-8) before Table III shows and to clean and afterwards.Analysis result shows, above the cleaning step again described in the routine I in fact do not dispose all potassium acetates.Result in the Table III shows that the potassium of the 0.9Wt% that still has an appointment after cleaning again remains in the catalyst.It is believed that potassium is attached on the carrier by ion-exchange mechanism.
Table III
Clean removing again with KOAc
Difference II-1 2.80 3.67 0.86II-2 1.50 2.33 0.83II-3 1.40 2.27 0.87II-4 1.40 2.35 0.95II-5 2.70 3.51 0.81II-6 1.40 2.35 0.95II-7 2.90 3.64 0.73II-8 2.80 3.68 0.87 that clean again that the Wt%K catalyst is original
Mean value 0.86
％RSD(b) 8.30
A) use with raw catalyst in after the KOAc of existing identical Wl% floods again.
B) RSD is a relative standard deviation.
Example III
As seen, two shown in the Table II are cleaned sample again before replenishing potassium acetate, analyze in the data from Table III.Result (as follows) result general and in the Table III conforms to.
The residual quantity of cleaning catalyst %K again
I-12 0.88
I-17 1.19
As a result, the potassium loading of cleaning catalyst may be all than the high about 0.8-1.2% of desired value again for all that reported in the Table II.Potassium content may cause catalyst activity to reduce than anticipation value height.The given enlightenment of these data is that with suitable (lower) final potassium loading, catalyst activity may improve manyly than the 5-10% shown in the Table II.When cleaning the added potassium amount in back only for the initial filling aequum shown in the comparative test III-1 to III-7 below realizing again, this point has obtained confirmation.
Comparative test III-1: measure a 2.5g and be used for the catalyst that vinylacetate is produced, the given Table IV that the results are shown in.Some part this catalyst are pressed III-2 is tested in interview and the described step of III-3 is cleaned again.
Test III-2: clean 3 parts from each part in the catalyst of the 50g of test III-1 with the post cleaning procedure, analyze its potassium content again, recording the potassium content value is 0.92Wt%.The aqueous solution that is dissolved in the 9.0ml water with the 0.469g potassium acetate floods the such catalyst sample of 15g again, and is following dry 18 hours at 60 ℃ then.Analysis and test result that catalyst is done see Table IV.
Test III-3: the program of test III-2 above adopting, different is only to have used 4 catalyst I I samples, and every duplicate samples (200g) is cleaned 48 hours with 2 gallons waters with the post cleaning procedure.After will being cleaned material and combining, the potassium content of being measured is 0.86%.With the aqueous solution dipping 15g sample that contains 0.556g potassium acetate and 9.0ml water, then 60 ℃ of dryings 24 hours.Analysis and test result that catalyst is done see Table IV.
Comparative test III-4: prepare this catalyst sample with the Preparation of Catalyst program, different is to regulate palladium and the concentration of golden salt in dipping solution and other starting material, makes loading as shown in Table IV.With catalyst method of inspection evaluate catalysts, just catalyst amount only is 0.75g.Analysis and assay see Table IV.
Test III-5: adopt the post cleaning procedure, will clean 24 hours from the catalyst of a 2.75g that tests III-4 with 500ml water.After the drying, the potassium acetate impregnated catalyst with capacity makes to contain potassium 3% in the catalyst of making approximately.With catalyst method of inspection evaluate catalysts, be that used catalyst only is 0.75g.Analysis and assay see Table IV.
Comparative test III-6: use interview and test the III-4 method and prepare this catalyst sample, different is to regulate palladium and the concentration of golden salt in dipping solution and other starting material, makes loading as shown in Table IV.With catalyst method of inspection evaluate catalysts, be that used catalyst only is 0.75g.Analysis and assay see Table IV.
Test III-7: adopt the post cleaning procedure, water cleans the catalyst sample from test III-6 again.With above-mentioned catalyst method of inspection evaluate catalysts, be that used catalyst only is 0.75g.Analysis and assay see Table IV.
Table IV
At constant potassium loading (a)
The effect test %Pd %Au %KOAc %Na that cleans again cleans STY % variable quantity III-1 down *0.55 0.22 5.8 0.45 No 565-
III-2 0.55 0.22 5.3 0.14 Yes 615 +9
III-3 0.5 0.22 5.8 0.12 Yes 642 +14
III-4 * 0.56 0.46 7.6 0.42 No 734(b) -
III-5 0.56 0.46 7.6 0.17 Yes 850(b) +15
III-6 * 1.02 0.46 7.2 0.48 No 967(b) -
III-7 1.02 0.47 7.7 0.17 Yes 1141(b) +18
(a) the post cleaning procedure is used for initial preparation and cleaning process again.
(b) this catalyst is tested under low-conversion, and this low-conversion is to cause this
Plant the measured especially high reason of STY value under the metal filled level.
Comparative example
On the basis of The above results, study, also can cause above-mentioned effect to determine whether other impurity.To original catalyst and the icp analysis data of the distortion after cleaning again done comparison shows that the sodium content difference of the two is bigger, and the content of other impurity does not have marked difference.
Example IV
For of the influence of check sodium, a series of experiments (test) have been done to catalyst activity.In these trials, sodium content differs from one another, and potassium content remains unchanged.In the experiment of another series, the ratio of sodium and potassium changes, and alkali-metal total molal quantity remains unchanged.These two groups of experimental results see Table V, and these results confirm: sodium content improves can cause catalyst activity to reduce really.
In the test 2 of Table V, it is more high that the catalyst of crossing with the sodium content solution impregnation suitable with initial not cleaning catalyst (test 4 in the Table V) that cleaned again demonstrates activity.This provides an enlightenment, and another kind of objectionable impurities may also be eliminated in cleaning again.
Table V
Sodium is to the impact of the catalyst performance test % %K selective K content constant of %Na STY and Na contains and quantizes to change, (a) the constant and Na/k of 1 2.24 0.117 642 93.12 2.22 0.457 609 93.53 2.18 0.912 540 94.14 2.31 0.453 563 93.4 alkali metal molal quantitys changes, (b) 1 2.21 0.435 616 93.62 1.77 0.705 584 94.03 0.77 1.300 501 94.2, (a) carrying out the catalyst I I that post cleans again floods with KOAc and NaOAc solution again. (b) in the sub-sample of catalyst I masterbatch, suitably add KOAc and NaOAc and be prepared into.
Embodiment of the invention C general introduction
Embodiment of the invention C is partly based on following discovery: reduce its sodium content by the some specific intermediate point in Catalyst Production with a kind of cation exchange solution cleaning catalyst, then therefore the activity of alkenyl alkanoate catalysts can increase.
More particularly, embodiments of the invention C provides a kind of technology of making a kind of catalyst.This catalyst can be used for the reaction of a kind of olefine of catalysis, a kind of alkanoic acid and a kind of oxygen-containing gas and generates a kind of alkenyl alkanoate, and this catalyst is made of carrier granular, and these carrier granular exchangeable cations also carried out impregnation process with the acetate of palladium, gold and potassium to it.Described technology may further comprise the steps:
(a) the solution impregnating carrier particle of usefulness water-soluble palladium and gold compound;
(b) with a kind of precipitating reagent from above-mentioned solution water-fast palladium and the gold compound precipitation on carrier granular;
(c) with a kind of reducing agent the water-fast palladium and the golden compound that are deposited on the carrier granular are converted into palladium and gold, so that prepare the impregnated carrier that contains sodium, containing sodium in the carrier is owing to there being sodium to exist in one or more used in step (a) to (c) materials;
(d) clean impregnated carrier granular with a kind of cation exchange solution,, and improve activity of such catalysts so that reduce the amount of sodium in the catalyst; And
(e) handle carrying out drying, to produce catalyst through the carrier granular that cleans with dipping.
If think further to improve activity of such catalysts with the manufacturing of embodiment of the invention C technology, also can be succeeded by the following step after the above-mentioned steps:
(f) carrier granular of crossing with a kind of potassium promoter impregnation drying; And
(g) to carry out dry handle (test I-2A and Fig. 1 of face as follows) through the catalyst that floods once more.
But, as above preferably by what realize below in conjunction with the described mode of most preferred embodiment of the present invention, this most preferred embodiment comprises that the specific ion exchanged soln (being potassium promoter solution) that uses specific concentrations and amount is to realize above-mentioned purpose (being also shown in following routine VII to XII and Fig. 3) in the further raising of catalyst activity.
Embodiments of the invention C also provides sodium content to reduce alkenyl alkanoate catalysts and with the technology of these Catalyst Production alkenyl alkanoates.
Owing to do not wish to be confined to any concrete theory, it is believed that the sodium impurity in the alkenyl alkanoate catalysts can reduce activity of such catalysts, and the cation in the used cation exchange solution can be replaced sodium (perhaps can carry out other impurity of ion-exchange in addition) from carrier in the step (d) of embodiment of the invention C technology, and the result is (d) impurity on can the flush away carrier set by step.The result that sodium content reduces is that activity of such catalysts is improved.
The concise and to the point description of schematic diagram to the explanation Embodiment C
Fig. 1 shows the anticipated impact of sodium to the vingl acetate catalyst performance made with the inventive method.
Fig. 2 shows the various interrupted cleaning experiment of being done according to embodiment of the invention C.
Fig. 3 shows the Preparation of Catalyst program in the most preferred embodiment of the preparation procedure of vingl acetate catalyst of United States Patent (USP) 4048096 and embodiment of the invention C.
Fig. 4 shows the influence of cleaning procedure to catalyst activity among the embodiment of the invention C.
Description to the most preferred embodiment of Embodiment C
The technology of preparation catalyst
In the technology of the embodiment of the invention C that is used for making alkenyl alkanoate catalysts, used cation exchange solution be those contain a kind of can with the solution of sodium exchange on the carrier, this cation can not weaken and preferably can improve activity of such catalysts.The cation exchange solution that is suitable for includes, but is not limited to the solution of potassium promoter.Best cation exchange solution contains the aqueous solution of a kind of compound (this compound contains a kind of suitable cation) of 0.01 to 20Wt% for those.These compounds include, but is not limited to potassium acetate, lithium acetate, potassium nitrate, potash, ammonium carbonate, ammonium acetate and magnesium acetate.Preferable solution is those solution that contain having of 0.1-10Wt% (0.5-7Wt% is the most desirable) of a kind of cationic compound suitably.
For saving the consumption that in cation exchange solution (these solution are used for making the technology of the embodiments of the invention C of alkenyl alkanoate catalysts), contains cationic compound, before with cation exchange solution cleaning catalyst, elder generation's water cleans one or many, combines not tight impurity (as the sodium of chloride and nonbonding) with carrier to remove those.
The optium concentration that is used for producing the used ion exchanged soln of the embodiment of the invention C technology of alkenyl alkanoate catalysts depends on many factors, amount as the sodium content in the catalyst, used cleaning solution, total scavenging period or the like is preferably determined by experiment.Contain a kind of suitable cationic compound concentrations and be about 10% or comparatively inadvisable when higher, because can waste these compounds like this and catalyst activity is reduced.
Be used for making used potassium promoter in the embodiment of the invention C technology step (d) of alkenyl alkanoate catalysts or the step (f) and comprise alkanoic acid potassium and any potassium compound that in the reaction that forms alkenyl alkanoate (promptly a kind of olefine, a kind of alkanoic acid and a kind of oxygen-containing gas generate a kind of reaction of alkenyl alkanoate under the condition that catalyst exists) process, is converted into a kind of alkanoic acid potassium.The potassium compound that is suitable for comprises potassium acetate, saleratus, potassium nitrate, and can also be potassium hydroxide when a kind of stable carrier of employing.Preferably use the co-catalyst of the aqueous solution.
When the cation in the used cation exchange solution of the step (d) of the embodiment of the invention C technology that is used for producing alkenyl alkanoate catalysts was potassium ion, therefore potassium just be introduced in the catalyst.In these cases, carry out dry to catalyst and analyze wherein potassium content with determining step (f)) in add into how much potassium on earth.This program is necessary, and it can avoid the potassium content of the catalyst produced excessive or not enough, and each in the both of these case can both make catalyst activity reduce.
The step (d) that is included in the most preferred embodiment that is used for making the embodiment of the invention C technology of alkenyl alkanoate catalysts adopts a kind of potassium promoter solution as cation exchange solution and what adopt in this step is concentration and all enough potassium promoter solution of amount, so just no longer need to adopt potassium acetate impregnation steps (step (f)) and the second time drying steps (step (g)).Fig. 3 shows present embodiment.
More particularly, the most preferred embodiment that is used to make the embodiment of the invention C technology of alkenyl alkanoate catalysts comprises the following steps:
(a) with the solution impregnating carrier particle of water miscible palladium and gold compound;
(b) with a kind of precipitating reagent from above-mentioned solution water-fast palladium and the gold compound precipitation to carrier granular;
(c) with a kind of reducing agent the compound of water-fast palladium that is precipitated and gold is converted into palladium and gold on the carrier granular, described impregnated carrier is owing to there is the sodium existence to contain sodium in one or more used in step (a) to (c) materials;
(d) clean carrier granular with a kind of potassium promoter solution, the concentration of described potassium promoter solution and amount all are enough to: the amount that (I) reduces sodium in the catalyst is to improve activity of such catalysts, and (II) further impregnated catalyst, to the potassium that wherein is injected to the necessary quantity of this activity of such catalysts of further raising;
(e) handle carry out drying through the carrier granular that cleans and further flood, to produce catalyst.
Suitable potassium promoter concentration will depend on many factors among the used cation exchange solution in the cleaning step (d) of the most preferred embodiment of embodiment of the invention C, as the expection activity of ion-exchange performance and the pore space and the catalyst of carrier material.For this reason, desirable concentration is preferably determined by normal experiment.Have now found that 5% potassium acetate solution can draw result preferably.
When the catalyst preparation process described in the United States Patent (USP) 4048496 that adopts Bissot, the palladium and the gold that have some colloidal state when cleaning are rinsed down from catalyst carrier.Implementing another benefit of the present invention is, in the Preparation of catalysts process, metal can more effectively be utilized when adopting potassium acetate solution as cation exchange solution.Beat all is that in implementing process of the present invention, when adopting potassium acetate solution as cation exchange solution, the palladium of not discovery amount on detectability and gold are cleaned from catalyst carrier.Below routine I-1A and I-2A show, with Bissot technology from catalyst flush away palladium and the gold of 1Wt%, do not measure these metals on detectability but found flush away with technology of the present invention.This advantage has not only improved the efficient of metal deposition, and has reduced the cost that reclaims noble metal from washing lotion.
Being used for making the carrier granular that the embodiment of the invention C technology of alkenyl alkanoate catalysts adopted is the solid granular material, these materials energy exchange cations, impregnated mistake contains palladium, gold and a kind of potassium promoter, and is inertia being used to make under the condition of alkenyl alkanoate.The example of above-mentioned carrier can be granular silica, alumina and silica alumina.Silica is best carrier.The surface area of carrier is preferably 100-800m 2/ g.
Be used for making the used water-soluble palladium of the embodiment of the invention C technology of alkenyl alkanoate catalyst and the aqueous solution of gold compound and comprise any suitable palladium or the aqueous solution of gold compound, these compounds such as palladium bichloride (II), the sour sodium (Na of tetrachloro palladium (II) 2PdCl 4), palladium nitrate (II), palladium sulfate (II), chlorauride (III) or tetrachloro gold (III) acid (HAuCl 4).The amount of solution preferably is equivalent to the 95-100% (98-99% is better) of carrier pore space.
The used precipitating reagent of embodiment of the invention C technology that is used for producing alkenyl alkanoate catalysts comprises the silicate and the hydroxide of sodium, lithium and potassium.Precipitating reagent preferably adopts the aqueous solution form of the precipitating reagent that contains excessive 1.6-1.8 mole.The amount of used above-mentioned solution preferably just enough there be not carrier granular.
The used reducing agent of embodiment of the invention C technology that is used for making alkenyl alkanoate catalysts comprises hydrazine, ethene, formaldehyde, hydrogen and sodium borohydride.Reducing agent preferably adopts the aqueous solution form that contains by the excessive reducing agent of the molal quantity of 50: 1 (perhaps 10: 1 better).If what adopt is hydrogen, need be heated to 100 ℃ to 300 ℃ to catalyst to finish reduction process usually.
Being used for making the cleaning step (step (d)) that the embodiment of the invention C technology of alkenyl alkanoate catalysts adopted can intermittently also can carry out continuously.Continuous wash efficient is higher but be not the Catalyst Production that is suitable for extensive (as plant layout) most.In the continuous wash process, cation exchange solution slowly and continuously passes catalyst in a period of time (as 8-24 hours) lining.In interrupted cleaning process, catalyst is contacted with cation exchange solution, mixture is stayed for some time (as from 0.5-2.0 hours), again solution and catalyst separation are opened.In interrupted cleaning process, often need carry out so several times cleaning (such as 2-10 times, 4-6 times better), so that the sodium content in the catalyst is reduced to aspiration level.Interrupted clean or the continuous wash process in all can to adopt temperature be 20-80 ℃ and cation exchange solution and the ratio of catalyst is 2: 1-100: 1 such condition.
Completely different with the potassium promoter impregnation steps of the prior art technology that is used for making alkenyl alkanoate catalysts according to the embodiment of the invention C technology step (d) that is used for making alkenyl alkanoate catalysts with a kind of step of cation exchange solution cleaning catalyst.What the impregnation steps of above-mentioned prior art adopted is early stage wet processing or decant technology.In early days in the wet processing (seeing the example 5 in the BP 1215210 of National Distillers), catalyst contacts with the minimum potassium promoter aqueous solution, these aqueous solution are only enough filled the hole of carrier and catalyst are flooded, and make it to contain desired quantity potassium promoter.Then water evaporates is fallen, this technology can not be removed the sodium of a tiny bit from catalyst.In decant technology, catalyst (preferably doing) is immersed in than in the bigger potassium promoter aqueous solution of amount used in the early stage wet processing.After hole is filled with solution, outwell excessive solution, again catalyst is carried out drying and handle.Only carried out the operation of a submergence and decant, and time of contact is shorter.Like this, can only from catalyst, remove a spot of sodium with decant technology.Example 9 in people's such as Sennewald the United States Patent (USP) 3743607 shows the decant technology that adopts a kind of moist catalysis.
According to step (e) among the embodiment of the invention C that makes alkenyl alkanoate catalysts the drying of catalyst being handled available any usual manner carries out.For instance, drying can carried out 15-30 hours in a forced ventilation baking oven under 40 ℃ to 120 ℃.
The example of Embodiment C is described
In the example of following explanation Embodiment C, used abbreviation is identical with the abbreviation meaning of used those regulations of example of explanation embodiment A.
In following example, adopted follow procedure:
The Preparation of Catalyst program
A, carrier I (15g) is added Na 2PdCl 4(35.86%Pd, 0.258g) and HAuCl 4(48.95%Au 0.094g) is dissolved in the formed solution of 9.0ml deionized water.Slowly stir formed mixture, all absorb into carrier, mixture is sealed in the bottle one stopped about 1 hour, so that impregnated carrier makes it contain the salt of palladium and gold up to all moisture.The NaOH (containing 0.236g in the 28ml water) or the sodium metasilicate that are used as precipitating reagent (contain Na in the 28ml water 2SiO 30.837g) solution floods wet catalyst.After mixing several seconds, make mixture be submerged and not by the state of disturbance under at room temperature kept 23 hours, with water-fast palladium and the gold compound deposit on the carrier.In said mixture, add the hydrazine hydrate of 1.0g 85% then to restore palladium and gold.Mixture is stirred several seconds, and then make it at room temperature to keep being submerged and not by the state of disturbance 23 hours.From catalyst, outwell supernatant liquor and water flushing catalyst 4 times to remove remaining little metal.With post cleaning procedure or the following thorough cleaning catalyst of interrupted cleaning procedure.Catalyst placed send into a forced ventilation baking oven on the stainless steel sift, 60 ℃ of oven dry 20-24 hours down.When implementing the most preferred embodiment of embodiment of the invention C, the Preparation of Catalyst program is so far.
B, at other embodiment that implements embodiment of the invention C and when implementing prior art program and following comparative example, the Preparation of Catalyst program also comprises following additional step: with the potassium content in the AA analytic approach analysis of catalyst.Adopt the above-mentioned dipping technique that is used for palladium and golden salt then, impregnated catalyst makes it to contain the potassium acetate (being dissolved in the water) of desired quantity.Then that the catalyst that is flooded is following dry 20-24 hours at 60 ℃.
C, measure palladium, gold, sodium and potassium content in the catalyst generated with the ICP method.Under most of situations, for the purpose of accurately, also use AA assay sodium and potassium content.
D, except as otherwise noted, said procedure will be used for preparing all catalyst of following example.When adopting the carrier of different amounts, the amount of other used starting material is respective change also.
E, flood catalyst that all are made by the method described in the example that occurs below with outer infusion process (promptly all basically palladiums and gold all concentrate in the layer within the carrier I bead surface 0.5mm).
Method used in the example of catalyst cleaning procedure and the catalyst method of inspection and top explanation embodiment A is identical.
Example 1
Comparative test I-1A: as precipitating reagent, flood 90g carrier I sample by method described in the Preparation of Catalyst journey with sodium metasilicate.After reduction step, remove supernatant liquor, wet microballon is divided into three equal parts, represent with sample A, B, C.Keeping sample B and C are provided with the back and use.With sample A not drying directly send into cleaning device, clean by post cleaning procedure water.Take from the palladium and the gold content of the black cleaning solution of the muddiness in the post with the analysis of ICP method.The result shows that every kind of metal in the catalyst all has 1% to run off approximately in cleaning process.Catalyst is sent into a forced ventilation baking oven, and drying is 4.5 hours under 60 ℃, analyzes potassium content (0.31Wt%) wherein then.According to the described program of Preparation of Catalyst program, be dissolved in formed solution impregnation catalyst (30.4g) in the 18.3ml water more than utilizing with the 1.62g potassium acetate.After under 60 ℃ dry 24 hours, the activity of detecting catalyst.The results are shown in Figure 1.
Test I-1B: adopt the post cleaning procedure, water is to being cleaned by the made a catalyst of sample A described in the above-mentioned test I-1B again, and carries out drying.And then add a certain amount of potassium acetate, to increase the content of potassium acetate, make it be returned to initial level.The results are shown in Figure 1.
Test I-2A: the still catalyst sample B of humidity for preparing among the test I-1A above cleaning with above-mentioned post cleaning procedure, difference is to adopt is 1% potassium acetate solution (a kind of cation exchange solution) rather than water.Cleaning solution is colourless, and can not detect palladium and gold with the ICP method.With said method the catalyst that cleaned is carried out drying and handle, and analyze its potassium content (1.41%).With 0.608g potassium acetate formed solution impregnation catalyst in 17.8ml water, following dry 24 hours at 60 ℃ then.Test result is seen Fig. 1.
Test I-2B: adopt the post cleaning procedure, water cleans a catalyst from top test I-2A again, carries out drying then.Add a certain amount of potassium acetate then to increase the content of potassium acetate, make it to be returned to its initial level.The results are shown in Figure 1.
Test I-3: press the sample C that handles the top I-1A of test with the method that test I-2A sample B method is identical above the processing, just the potassium hydroxide with 1% has substituted 1% potassium acetate solution in cleaning step.After static 12 hours, find that silica carrier is badly damaged, have to catalyst is thrown away.This experiment shows under the condition that is adopted, and when the carrier that adopts the highly basic sensitivity, potassium hydroxide is unsuitable for being used as cation exchange solution of the present invention.
Result among Fig. 1 shows, by adopting the potassium acetate washing lotion at the very start, or water cleans then water cleaning again after with the potassium acetate dipping during beginning, can improve activity of such catalysts equally.These results have confirmed a theory: when having objectionable impurities on catalyst and the carrier, add potassium and help to remove this impurity.
Example II
It is believed that having the part chloride at least is to test the impurity of being removed described in the routine I above utilizing.But, the chloride analysis (see figure 4) that the catalyst for preparing among the routine I is done shows that the chloride content before and after cleaning again only has faint difference subsequently.Other experiment that adds varying number potassium chloride in catalyst also shows only has atomic weak influence (seeing Table G) to activity of such catalysts.
Table G
Add muriatic influence
Chloride (ppm) STY % selectivity
0 605 93.7
50 601 93.7
100 598 93.5
Be used for the catalyst of result shown in the acquisition table G with the Preparation of Catalyst program from the preparation of a collection of masterbatch, the specified palladium loading of this batch masterbatch is 0.58%, the Au/Pd ratio is 0.5, and KOAc loading 5.3% estimates that initial chloride content is about 200ppm.Chloride adds the KOAc dipping solution with the form of KCl.
On the basis of The above results, study, to determine whether that other impurity can cause above-mentioned influence in addition.Will be to original catalyst and clean again after comparison shows that of carrying out of the icp analysis data done of modification; The sodium content difference of the two is bigger, and does not find that the content of other impurity has marked difference.
Example III
For of the influence of check sodium to catalyst activity, carried out a series of experiments (test), in these experiments, sodium content is different, and potassium content remains unchanged.In another group serial experiment (test), sodium is constant with the ratio variation and the maintenance alkali metal total mole number of potassium.These two groups of serial experiments the results are shown in Table H.These results show that the increase of sodium content in fact makes catalyst activity reduce really.
In the test 2 of table H, the catalyst after the cleaning again of a kind of impregnated sodium that contains the quantity close with original not cleaning catalyst (test 4 of following table H) shows quite high activity.This provides an enlightenment: may also have other objectionable impurities to be eliminated in the cleaning process again.
Table H
Sodium is to the affecting the selective K content constant of tested number %K %Na STY % of catalyst performance and Na content changes, (a) 1 2.24 0.117 642 93.1 2 2.22 0.457 609 93.5 3 2.18 0.912 540 94.1 4 2.31 0.453 563 93.4Na/K change and the alkali metal molal quantity is constant, (b) 1 2.21 0.435 616 93.6 2 1.77 0.705 584 94.0 3 0.77 1.300 501 94.2, (a) with KOAc and NaOAc solution the catalyst through again post cleaning is flooded again. (b) be prepared into by in the sub-sample of catalyst I masterbatch, suitably adding KOAc and NaOAc.
Example IV
Do one group of experiment (following test IV-1 to IV-4) to further specify the influence shown in the top routine I.An other purpose of this group experiment is to think explanation: benefit of the present invention also can utilize interrupted cleaning procedure to obtain, and this program is more suitable in extensive Catalyst Production than the post cleaning procedure that has adopted among the top routine I.
Comparative test IV-1: adopt the Preparation of Catalyst program, I prepares catalyst with the 80g carrier.With NaOH as precipitating reagent.After reduction step, liquid is discharged from the catalyst microballon, get microballon express developed with the volume water roughly suitable then with catalyst volume.Catalyst is divided into quarter, is designated as sample A, B, C and D.Sample B, C and D wait until in the later example and use.Adopt interrupted cleaning procedure to clean sample A, this program comprises with the 23ml deionized water there be not catalyst, and makes it to stop 36 minutes.Outwell above-mentioned water and do not have catalyst with the 23ml fresh water in addition.In this way, clean carrying out 5 times altogether in 3 hours altogether.After last the cleaning, water washes microballon once again, then 60 ℃ of down dry a whole nights.Potassium content in the analysis of catalyst (0.30%), the solution impregnation catalyst that in 11.7ml water, forms with the 0.955g potassium acetate then.After 60 ℃ of down dry a whole nights, catalyst is made an appraisal, the results are shown in Table I.
Test IV-2: adopt with top test IV-1 in specified identical program, with the interrupted sample B that cleans among the top IV-2 of test of the potassium acetate solution of 23ml 5%, in 3 hours, carry out 5 such cleanings altogether.After water has washed microballon, catalyst 60 ℃ of down dry a whole nights, is analyzed its potassium content (1.42%) then.The solution impregnation catalyst that in 11.7ml water, forms with the 0.359g potassium acetate then.Make catalyst after 60% ℃ of down dry a whole night, evaluate catalysts, gained the results are shown in Table I.
Comparative test IV-3: by and the identical mode of top test IV-1, water cleans from the sample among top test IV-1 C5 time, difference is lasting 96 minutes of each cleaning, scavenging period is altogether 8 hours.The analysis showed that the potassium content after the cleaning is 0.33%.With 0.934g potassium acetate formed solution impregnation sample in 11.7ml water, then 60 ℃ of down dry a whole nights.Test result sees Table I.
Test IV-4: the program of test IV-3 above adopting, the potassium acetate solution with 5% cleans the sample D from top test IV-1, cleans altogether 5 times.The analysis showed that the potassium content after the cleaning is 1.69%.With 0.216g potassium acetate formed solution impregnation sample in 11.7ml water, then 60 ℃ of down dry a whole nights.Test result sees Table I.
Table I
Intermittently clean with potassium acetate Effect on Performance
Test %K %Na STY
IV-1* 2.2 0.47 512
IV-2 2.4 0.22 531
IV-3* 2.1 0.47 535
IV-4 2.2 0.19 573* comparative examples
Example V
Carrying out one group further tests to determine to significantly improve the optimal cost benefit amount of active required potassium acetate.In these experiments, the catalyst that portion is heavy dose of is at 6 equal portions shown in the preceding Fig. 2 of being divided into of cleaning step (being the step (d) of technology of the present invention).Adopt interrupted cleaning procedure, intermittently clean all catalyst, clean altogether 5 times.The variation of the composition of cleaning solution as shown in Figure 2.Such as, can intermittently clean first part of catalyst 5 times for water; Water cleans second part and cleans 2 times with 5% potassium acetate solution then for 3 times again, or the like.Make the catalyst drying, use atomic absorption spectrometry potassium and sodium content then.Every part of catalyst is subdivided into ＂ A ＂ and ＂ B ＂ two parts again.Handle each part with the potassium acetate of capacity then, make potassium content in the catalyst of generation about 2.9%.Those catalyst members that are labeled as ＂ B ＂ have also absorbed the sodium acetate of capacity, make their final sodium contents be returned to the catalyst that cleans through water in contained roughly the same level (level in the catalyst that the V-1 water cleans is tested in following interview).
So just obtained two groups of catalyst: one group (＂ A ＂ series) has shown that potassium acetate cleans the influence to catalyst performance; Second group (＂ B ＂ series) has shown the contribution of suitable removing sodium to this influence.These results are summarized among the table J.
Comparative test V-1: adopt the Preparation of Catalyst program, prepare catalyst with 100g carrier I and sodium metasilicate.After the reduction step, outwell solution, water flushing catalyst 4 times.Venting precipitating reagent and reductant solution are divided into 6 equal portions with still moist catalyst, are labeled as A, B, C, D, E and F respectively.Sample B to F waits until in the following example and uses.Intermittently cleaning sample A5 time with 20ml water in 8 hours altogether at every turn.After 60 ℃ of down dry a whole nights,, dry down at 60 ℃ then with the solution impregnation catalyst that the 1.098g potassium acetate forms in 9.6ml water.The catalyst (its potassium, sodium content calculated value see Table J) that is generated is carried out the evaluation of the activity of relevant vinylacetate.The results are shown in Table J.
Test V-2: by the mode interrupted sample B that clean from top test V-1 identical with top test V-1, difference is that first three time water cleans, and back secondary cleans with 5% potassium acetate solution.After 60 ℃ of down dry a whole nights, catalyst is halved.The solution impregnation first that in 4.6ml water, forms with the 0.26g potassium acetate.After 60 ℃ of following dryings, catalyst has the listed composition that calculates among the table J (test V-2A), and what provide the results are shown in the same table.Second the moiety sample of solution impregnation that in 4.6ml water, forms with 0.26g potassium acetate and 0.090g sodium acetate.Composition that calculates and test result see Table J (test V-2B).
Test V-3: by the interrupted sample C that cleans from top test V-1 of the mode identical with top test V-1, difference is preceding twice water for cleaning, the back potassium acetate solution that cleans with 5% for three times.After 60 ℃ of down dry a whole nights, catalyst is halved.The solution impregnation first that in 4.6ml water, forms with the 0.20g potassium acetate.After the drying, this catalyst has the composition that calculates shown in the table J (test V-3A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.20g potassium acetate and 0.097g sodium acetate.Composition that calculates and test result see Table J (test V-3B).
Test V-4: by the interrupted sample D that cleans from top test V-1 of the mode identical with top test V-1, difference is water for cleaning for the first time, the back potassium acetate solution that cleans with 5% for four times.After 60 ℃ of down dry a whole nights, catalyst is halved.The solution impregnation first that in 4.6ml water, forms with the 0.155g potassium acetate.After the drying, this catalyst has the listed composition that calculates among the table J (test V-4A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.155g potassium acetate and 0.094g sodium acetate.Dried composition that calculates and test result see Table J (test V-4B).
Test V-5: by the interrupted sample E that cleans from top test V-1 of the mode identical with top test V-1, difference is first three time water for cleaning, and twice cleaning in back is with 10% potassium acetate solution.After 60 ℃ of down dry a whole nights, catalyst is halved.The solution impregnation first that in 4.6ml water, forms with the 0.032g potassium acetate.After the drying, this catalyst has the composition that calculates shown in the table J (test V-5A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.032g potassium acetate and 0.098g sodium acetate.Dried composition that calculates and test result see Table J (test V-5B).
Test V-6: by the mode interrupted sample F of cleaning from top test V-1 identical with top test V-1, difference is preceding twice water for cleaning, then the potassium acetate solution that cleans with 10% for three times.After 60 ℃ of down dry a whole nights, catalyst is halved.First is no longer directly carried out drying and portioning with the further dipping of potassium acetate.The results are shown in the same table of catalyst with composition that calculates listed among the table J (test V-6A).With 0.12g sodium acetate second moiety sample of formed solution impregnation in 4.6ml water.Dried composition that calculates and test result see Table J (test V-6B).
Table J
Interrupted development test %K (a) %Na (a) STY % selecting property washing lotion and the order of cleaning
Reducing sodium-＂ series A ＂ V-1* 2.83 0.518 527 93.7 5 * H2OV-2A 2.87 0.268 603 93.3 3 * H2O adds 2 * 5%KOAcV-3A, 2.88 0.249 615 93.2 2 * H2O and adds 3 * 5%KOAcV-4A, 2.90 0.258 630 93.2 1 * H2O and add 4 * 5%KOAcV-5A, 2.94 0.247 604 93.3 3 * H2O and add 2 * 10%KOAcV-6A, 2.95 0.181 571 93.5 2 * H2O and add 3 * 10%KOAc
Reduce Na and then add ＂ series B ＂ V-1* 2.83 0.518 527 93.7 5 * H2OV-2B* 2.84 0.554 516 93.6 3 * H2O and add 2 * 5%KOAcV-3B*, 2.85 0.558 519 93.9 2 * H2O and add 3 * 5%KOAcV-4B*, 2.86 0.561 534 93.5 1 * H2O and add 4 * 5%KOAcV-5B*, 2.90 0.567 502 93.8 3 * H2O and add 2 * 10%KOAcV-6B*, 2.90 0.574 488 94.1 2 * H2O and add 3 * 10%KOAc (a) estimated value. Amount according to AA analysis result before the KOAc/NaOAc dipping and the acetate that added is calculated.* comparative example
As seen, take test V-1 to compare with test V-2A to V-6A from table J, ＂ A series ＂ activity of such catalysts significantly improves, and these raisings conform to the reduction of these catalyst sodium contents substantially.＂ B series ＂ catalyst data shows, sodium is added the level (taking test V-1 and test V-2B to V-6B relatively) that ＂ A series ＂ catalyst can be reduced to catalyst activity the catalyst initial, that water cleaned again.These results have supported this viewpoint once more, i.e. the removal of sodium makes viewed active the raising.
Example VI
Come from the effluent of post cleaning procedure and interrupted cleaning procedure terminal several times in the catalyst preparation process with ion chromatography analysis.These tests comprise adopts water and potassium acetate solution as washing lotion simultaneously, and the purpose of these experiments is in order to detect any impurity that the icp analysis method may not measured.It seems that sulfate be major impurity, however according to estimates its content in original catalyst less than 100ppm.Detect the phosphate and the chloride of lower content simultaneously.For determining whether that sulfate can have adverse effect to activity, the potassium sulfate of 500-1000ppm is added in two catalyst samples.As show shown in the K, it does not make significant difference to activity.
Table K
The ppm value that influences the potassium sulfate that sulfate STY % selectivity 0 550 93.8500 552 93.91000 577 93.8 (a) add with the potassium acetate co-catalyst of the sulfate that is added.
Following routine VII to XII shows most preferred embodiment of the present invention represented among Fig. 3.
Example VII
Adopt the Preparation of Catalyst program, with NaOH do precipitating reagent Preparation of Catalyst to 50g carrier I.After the reduction step, liquid is discharged from catalyst, clean microballon for 4 times to remove kish with moisture.Wet catalyst is divided into three equal parts, is labeled as sample A, B and C.Sample B and C wait until in the following example and use.Interrupted cleaning procedure above adopting among the test IV-4, the potassium acetate solution with 23ml 5% cleans sample A5 time at every turn, and scavenging period is 8 hours altogether.The each cleaning continues 96 minutes.Water does not clean, and directly makes the catalyst drying under 60 ℃, and estimates its vinylacetate activity under the condition that does not further add potassium acetate.Analysis and test result see Table L.
Example VIII
Clean sample B by the preparation of this example by mode described in the top routine VII, difference is the preceding potassium acetate that cleans with 5% for 4 times, and each the cleaning continues 1 hour, the last cleaning lasting 4 hours.Non-flushing washing directly makes the catalyst drying under 60 ℃.Analysis and test result see Table L.
Example IX
Clean sample C by the preparation of this example by mode described in the top routine VII, difference is that used is 7% potassium acetate solution.Non-flushing washing directly makes the catalyst drying under 60 ℃.Analysis and test result see Table L.
Comparative example X
Adopting the Preparation of Catalyst program to prepare total amount in a pilot plant is 20 liters catalyst, and cleans by interrupted cleaning procedure water.Analysis and test result see Table L.
Example XI
Prepare 20 liters of catalyst samples with technology described in the above-mentioned routine VII.Analysis and test result see Table L.
Example XII
In a commercialization manufacturer, prepare 520 liters of catalyst samples with technology described in the top routine VII.Analysis and test result see Table L.
Table L
Performance test %Pd %Au %K %Na STYIV-3* 0.54 0.19 2.2 0.47 535VII with the prepared catalyst of five step preparation procedures--0.20 2.5 0.10 643VIII, 0.57 0.22 2.5 0.11 645IX, 0.56 0.22 2.9 0.10 592X*, 0.53 0.20 2.3 0.73 587XI, 0.56 0.26 2.9 0.12 695XII, 0.56 0.25 3.0 0.18 666* comparative example (seven steps preparation sample).
Tables of data is understood and to be utilized the obtained progress of the present invention among the table L.
Example XIII
With the catalyst sample of potassium acetate solution dipping from top routine XII, solution concentration makes the potassium loading improve about 0.8% probably.The catalyst that is generated contains 0.56%Pd, 0.25%Au, 3.7%K and 0.17%Na, and its STY value is 550.
The purpose of following routine XIV to XXIV is to show the use of various cation exchange solution in embodiment of the invention C.
Comparative example XIV
According to the Preparation of Catalyst program, also prepare catalyst as precipitating reagent with NaOH with the 90g carrier.After reduction step, drain catalyst, and water washes catalyst 4 times altogether.Wet catalyst is divided into 6 equal portions, is labeled as sample A, B, C, D, E and F respectively.Sample B to F waits until in the following Example and uses.Interrupted cleaning procedure described in the routine IV-3 above adopting is with the water cleaning sample A of 5 parts of 20ml.The evaluating catalyst that is generated be the results are shown in Table M.
Example XV
According to program described in the top routine XIV, clean from this routine sample B with the ammonium carbonate solution of every part of 20ml 2%.The evaluation result that the catalyst of making is done sees Table M.
Example XVI
According to program described in the top routine XIV, clean from this routine sample C with the lithium acetate aqueous solution of every part of 20ml 2%.The evaluation result that catalyst is done sees Table J.AA analyzes discovery, and the lithium content of the catalyst of making is 0.18%.
Comparative example XVII
According to program described in the top routine XIV, clean from this routine sample D with the aqueous sodium acetate solution of every part of 20ml 2%.The evaluation result that catalyst is done sees Table M.
Example XVIII
According to program described in the top routine XIV, clean from this routine sample E with the potassium nitrate aqueous solution of every part of 20ml 2%.The evaluation result that catalyst is done sees Table M.
Example XIX
According to program described in the top routine XIV, clean from this routine sample F with the wet chemical of every part of 20ml 2%.The evaluation result that catalyst is done sees Table M.
Table M
Various cation exchange solution influence example salt %Pd %Au %K %Na STYXV to catalyst activity *None 0.58 0.22 2.23 0.37 474 *XVI (NH 4) 2CO 30.58 0.22 2.20 0.13 527XVII LiOAc, 0.58 0.23 2.22 0.19 486XVIII *NaOAc 0.57 0.22 2.26 0.79 447XIX KNO 30.59 0.23 2.26 0.13 492XX K 2CO 30.59 0.23 3.06 0.14 523* comparative example.* STY is respectively the mean value of 453,498 and 470 three times tests.
Comparative example XX
Prepare catalyst by top routine XV program.After reduction step, wet catalyst is divided into 6 equal portions, be labeled as sample A, B, C, D, E and F respectively.Sample B to F waits until in the following example and uses.By the water cleaning sample A of mode described in the top routine XV with 5 parts of 20ml.To the N that the results are shown in Table that catalyst judged.
Example XXI
According to mode described in the top routine XV, clean sample B from routine XXI with the ammonium acetate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyst judged.
Example XXII
According to mode described in the top routine XV, clean sample C from routine XXI with the potassium acetate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyst judged.
Example XXIII
According to mode described in the top routine XV, clean sample D from routine XXI with the potassium sulfate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyst judged.Potassium sulfate solution is not very suitable cation exchange solution, and is obviously quite slow because it is converted into effective form (potassium acetate).
Example XXIV
According to mode described in the top routine XV, clean sample F from routine XXI with the magnesium acetate aqueous solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyst judged.
Table N
Various cation exchange solution are to the influence of catalyst activity.Example salt %Pd %Au %K %Na STYXXI *None 0.560 0.196 2.27 0.52 523XXII NH 4OAc 0.576 0.187 2.49 0.11 594XXIII KOAc 0.613 0.209 2.13 0.13 561XXIV K 2SO 40.618 0.216 2.13 0.12 493 *XXV Mg (OAc) 0.573 0.225 2.39 0.17 575* comparative example.* can't show the influence of this cation exchange solution because the reaction time is not enough.
The composition of catalyst of the present invention
All can be used for the reaction of a kind of olefine of catalysis, a kind of alkanoic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate with the prepared catalyst of the present invention of technology in any the foregoing description (being embodiment A, B or C), described catalyst is made of carrier granular, these particles energy exchange cations, through palladium, gold and a kind of potassium promoter that dipping contains precipitation and reduced, existing any type of sodium preferably is no more than 0.3Wt% (total catalyst weight is 100Wt%) in the catalyst.
Wish to be higher than the 0.25Wt% of total catalyst weight with the palladium content of the prepared catalyst of the present invention of any the foregoing description technology, the 0.5Wt% that is higher than total catalyst weight is better, preferably can be higher than the 0.5-1.7Wt% of total catalyst weight.Better when the weight ratio of gold and palladium is 0.2-1.5 in the catalyst, 0.4-1.2 is best.
The catalyst that the catalyst of being produced with any the foregoing description technology of the present invention preferably floods through layer, wherein the particle diameter of catalyst carrier is extremely about 7mm of about 3mm, porosity is 0.2-1.5ml/g.Palladium and gold preferably are distributed in the thick layer of catalyst carrier particle most external 1.0mm.Catalyst preferably contains about potassium of 1.4 to about 3.8Wt%, and it is better to contain 2 to 3.6Wt% potassium, and these potassium come from potassium promoter.
The catalyst of being produced with any the foregoing description technology of the present invention all makes sodium content reduce.Relatively good when the sodium content of catalyst is no more than the 0.3Wt% of catalyst weight, it is better that the sodium content of catalyst is no more than 0.2Wt%, and preferably the sodium content of catalyst is no more than about the 0.1Wt% of catalyst weight.The amount of sodium will depend on many factors in the catalyst of the present invention, as used starting material, wash number, total scavenging period, the amount of cleaning solution and the cation concn in the cation exchange solution.
The catalyst of being produced with any the foregoing description technology of the present invention can be made with above-mentioned technology of the present invention and with technology described in two U.S. Patent applications of submitting simultaneously with the application above-mentioned equally.
Be used to make the technology of the present invention of alkenyl alkanoate.
The technology of the present invention that is used to make alkenyl alkanoate is included under the condition of the catalyst of the present invention that has above-described catalytic amount a kind of olefine, a kind of alkanoic acid and a kind of oxygen-containing gas is reacted.This technology is being carried out better (be preferably under 140 ℃ to 200 ℃ and carry out) under 100 ℃ to 250 ℃ the temperature; Simultaneously, pressure 15psi (pound/square inch) between the 300psi better, best between 90psi to 150psi.This technology is preferably in the gas phase carries out continuously.
The technology of the present invention that is used to make alkenyl alkanoate is characterised in that catalyst has bigger activity.In general, these activity of such catalysts (alkenyl alkanoate that generates with unit interval unit catalyst is a unit) than contained sodium from more than 0.3% to 1% (weight) and the identical activity of such catalysts of others is big by 5% to 25%.Though selection of catalysts (producing the trend of alkenyl alkanoate rather than carbon dioxide and so on byproduct) can reduce slightly when sodium content reduced, this shortcoming is compensated by catalyst activity increases already, when particularly sodium content was in the content range (as sodium content up to about 1.0Wt%) of sodium in the commodity alkenyl alkanoate, situation was all the more so.
The best alkanoic acid starting material that technology of the present invention adopted that is used for making alkenyl alkanoate contains 2 to 4 carbon atoms (can be acetate, propionic acid and butyric acid such as these acid).Best olefine starting material contains 2 to 4 carbon atoms (can be ethene, propylene and n-butene such as these hydrocarbon).The best product of this technology is vinylacetate, vinyl propionic ester, vinyl butyrate and allyl acetic acid ester.
An aspect that is used to make the technology of the present invention of olefine alkanoate comprises and adopts the model shown in the previous table G to come pre-oxygen determination with respect to the conversion ratio of vinylacetate, activity of such catalysts, the catalyst output with respect to the output of the selectivity of vinylacetate, ethyl acetate byproduct and/or heavy byproduct.
The alkenyl alkanoate that technology of the present invention is produced be known compound with known application (such as, vinylacetate can be used for producing polyvinylacetate).

Claims (6)

1. technology of making a kind of catalyst, described catalyst can be used for reaction between a kind of olefine of catalysis, a kind of alkanoic acid and a kind of oxygen-containing gas to generate a kind of alkanoic acid alkenyl ester, described catalyst comprise can exchange cation carrier granular, these carrier granulars flood with palladium, gold and potassium promoter, this co-catalyst is selected from alkanoic acid potassium and can changes into any compound of alkanoic acid potassium in described course of reaction, and described technology comprises the following steps:
(a) aqueous solution with water miscible palladium and gold compound comes impregnated support particles;
(b) with a kind of precipitating reagent water-fast palladium and gold compound are deposited on the carrier granular from above-mentioned solution;
(c) with a kind of reducing agent the water-fast palladium that is precipitated and gold compound are converted into palladium and gold on the carrier granular;
(d) water cleans carrier granular;
(e) make carrier granular drying after the cleaning;
(f) with the further impregnated support particles of a kind of potassium promoter; And
(g) make as with the impregnated carrier drying of upper type to prepare dry catalyst, this catalyst contains sodium because of there being sodium to exist in one or more used in the step (a) to (f) materials;
(h) water or contain a kind of aqueous solution cleaning-drying of potassium promoter after catalyst so that the sodium content in the catalyst in the no more than 0.3Wt% of the weight of catalyst, and then improves activity of such catalysts, and
(i) make the catalyst drying.
2. in accordance with the method for claim 1, wherein step (i) is carried out step (i) and step (k) afterwards, and step (j) is the potassium promoter impregnation steps second time, and step (k) is for dry for the third time.
3. in accordance with the method for claim 1, wherein in initial potassium promoter impregnation steps [step (f)], use enough potassium acetates, thereby guarantee that step (i) products obtained therefrom contains the potassium promoter of the amount of meeting the requirements.
4. in accordance with the method for claim 1, wherein in step (h), use the aqueous solution that contains potassium promoter, thereby the resulting catalyst of the step of making (i) contains the potassium promoter of the amount of meeting the requirements.
5. in accordance with the method for claim 1, wherein the sodium content of the resulting catalyst of this method in the no more than 0.2Wt% of catalyst weight.
6. in accordance with the method for claim 1, wherein the sodium content of the resulting catalyst of this method in the no more than 0.1Wt% of catalyst weight.
CN92103424A 1991-05-06 1992-03-30 Production of alkenyl alkanoate catalysts Expired - Fee Related CN1036377C (en)

Priority Applications (9)

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US07/793,129 US5179057A (en) 1991-05-06 1991-11-18 Catalysts for alkenyl alkanoate production
MX9201440A MX9201440A (en) 1991-11-18 1992-03-30 PRODUCTION OF ALKENYL ALCANOATE CATALYSTS.
CN92103424A CN1036377C (en) 1991-11-18 1992-03-30 Production of alkenyl alkanoate catalysts
AU13900/92A AU643132B2 (en) 1991-11-18 1992-03-30 Alkenyl alkanoate catalyst process
NZ242166A NZ242166A (en) 1991-11-18 1992-03-30 Alkenyl alkanoate catalyst with reduced sodium content and preparation thereof
HU9201054A HU212447B (en) 1991-11-18 1992-03-30 Process for producing catalysts usable for the production of alkenyl alkanoates
US07/952,280 US5342987A (en) 1991-05-06 1992-09-28 Alkenyl alkanoate production
CA002081937A CA2081937C (en) 1991-05-06 1992-11-02 Catalysts for alkenyl alkanoate production
CA002081942A CA2081942C (en) 1991-11-18 1992-11-02 Production of alkenyl alkanoate catalysts

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US07/793,129 US5179057A (en) 1991-05-06 1991-11-18 Catalysts for alkenyl alkanoate production
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US5693586A (en) * 1996-06-28 1997-12-02 Hoechst Celanese Corporation Palladium-gold catalyst for vinyl acetate production
TW202204892A (en) * 2020-06-29 2022-02-01 美商瑟蘭斯國際股份有限公司 In-situ analysis of metal ions in vinyl acetate production

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Publication number Priority date Publication date Assignee Title
US3923688A (en) * 1972-03-02 1975-12-02 Ppg Industries Inc Thermally stable and crush resistant microporous glass catalyst supports and methods of making
US4048096A (en) * 1976-04-12 1977-09-13 E. I. Du Pont De Nemours And Company Surface impregnated catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923688A (en) * 1972-03-02 1975-12-02 Ppg Industries Inc Thermally stable and crush resistant microporous glass catalyst supports and methods of making
US4048096A (en) * 1976-04-12 1977-09-13 E. I. Du Pont De Nemours And Company Surface impregnated catalyst

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