CN104437654A - Vinyl acetate catalyst and preparation method thereof - Google Patents
Vinyl acetate catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a vinyl acetate catalyst and a preparation method thereof, and a synthesis method of vinyl acetate, mainly aiming at solving the problem that an existing vinyl acetate catalyst is low in space time yield and selectivity. For the vinyl acetate catalyst provided by the invention, SiO2, Al2O3 or a mixture thereof is used as a carrier, and a loaded active ingredient comprises metal palladium, metal gold or alkali metal acetate, wherein the metal palladium and the metal gold are existent in a palladium-gold alloy form, the content of the palladium in the catalyst is 1-12g/L, the content of the gold is 0.1-10g/L, and the content of the alkali metal acetate is 10-100g/L; and a surface PdAu alloy layer of the catalyst is in bimodal distribution in an EDS-electronic probe radial scanning detection, and the bimodal space of the bimodal distribution is 10-200 microns. The problem is well solved, and the vinyl acetate catalyst can be applied to industrial production of vinyl acetate.
Description
Technical field
The catalyst that the present invention relates to synthesizing vinyl acetate with and preparation method thereof and vinyl acetate synthesis method.
Background technology
Vinyl acetate is important industrial chemicals, is widely used in aspects such as manufacturing polyvinyl alcohol, vinyl copolymer resin, binding agent, coating, textile processing, paper coating.The production process route of vinyl acetate mainly contains ethylene process and acetylene method two kinds, and wherein ethylene process is due to manufacturability, good economy performance and occupy leading status, adopts the vinyl acetate production ability of the method to account for 82% of total productive capacity.The U.S. completes the conversion all adopting ethylene process route in nineteen eighty-three.At present, the method that most countries increases vinyl acetate output original device is carried out to the update of reorganization and expansion and catalyst, the development trend of ethylene process route, has been summed up several aspect: (1) process units scale trend maximizes.If USI company of U.S. the seventies initial stage process units scale is 13.6-15.9 ten thousand tons/year, nineteen ninety unit scale reach 360,000 tons/year, also have the expansion energy of the above Hoechst company VAC device; (2) although ethylene process VAC flow process comparative maturity, but still in improvement, to reduce unit consumption and energy consumption; Current state-of-the-art ethylene process technique is the Leap technique of Amoco company and the Vantage technique of Celanese company.The investment of acetylene method process unit is higher, and environmental protection difficulty is comparatively large, but high along with crude oil price, will keep suitable competitive advantage over a period to come, and the research and development of direct promotion C1 chemical method.
The main method of the world today producing vinyl acetate is for raw material with ethene, oxygen and acetic acid, catalyst is made with palladium-Jin-potassium acetate/silica, produced by gas phase catalytic reaction, generate vinyl acetate, water and accessory substance carbon dioxide, also generate the ethyl acetate of trace, acetaldehyde and other acetoxylation product.The temperature of the reactor shell-side of this reaction can be about 100 to about 180 DEG C, and reaction pressure is about 0.5-1.0MPa, and gas volume air speed is about 500 to about 3000hr
-1.
The patent (CN1226188A, the palladium-gold catalyst for the preparation of vinyl acetate) of Hanchester rayon Co., Ltd provides a kind of and prepares the preparation method that load has the catalyst of major catalyst noble metal, promoter metal and alkali metal or alkaline earth metal compound.Its concrete manufacture process is as follows: the mixed liquor of the noble metal configured and co-catalyst, in the dipping tank rotated, adds, passes into heated air drying by (1); (2) solution getting the alkaline matters such as a certain amount of sodium metasilicate makes an addition in dried catalyst, and the palladium of the chlorination state of original water soluble and gold are changed into water insoluble hydroxide state palladium and gold; (3) in nitrogen atmosphere, reduce the palladium of hydroxide state and Au catalyst, be namely reduced into palladium and the Au catalyst of metallic state; (4) be washed till without chlorion, dry; (5) soak potassium acetate, after drying, namely obtain described catalyst.The space time yield of the catalyst that the method obtains and selective all lower.
Summary of the invention
One of technical problem to be solved by this invention is vinyl acetate catalyst space time yield and selective low problem in prior art, a kind of vinyl acetate catalyst is provided, in industrial production, uses this vinyl acetate catalyst to have space time yield and selective high feature.
Technical problem two to be solved by this invention, is to provide the preparation method of one of a kind of and above-mentioned technical problem described catalyst.
Technical problem three to be solved by this invention, is to provide a kind of synthetic method adopting the vinyl acetate of the described catalyst of one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, technical scheme of the present invention is as follows: vinyl acetate catalyst, with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic gold and alkali metal acetate, wherein Metal Palladium and metallic gold exist with the form of Polarium, in described catalyst, the content of palladium is 1 ~ 12g/L, the content of gold is 0.1 ~ 10g/L, the content of alkali metal acetate is 10 ~ 100g/L, the PdAu alloy-layer of described catalyst coating in the radial scan of EDS-electron probe detects by interior and table in bimodal distribution; The Peak Separation of described bimodal distribution is 10 ~ 200 μm.
In technique scheme, described alkali metal acetate is preferably potassium acetate; The Peak Separation of described bimodal distribution more preferably 80 ~ 120 μm.The bimodal ratio by peak intensity that is interior and that show of described bimodal distribution is preferably 1:(0.05 ~ 20), be more preferably 1:(0.125 ~ 8), more more preferably 1:(0. 5 ~ 1.5).
The preferred version that in technique scheme, effect is best is: the Peak Separation of described bimodal distribution 80 ~ 120 μm, and the bimodal ratio by peak intensity that is interior and that show of described bimodal distribution is 1:(0. 5 ~ 1.5).
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the described catalyst of one of above-mentioned technical problem, comprises the following steps:
A the solution be dissolved with containing palladium compound and gold-containing compound mixes with carrier by (), obtained catalyst precarsor I;
B () obtains catalyst precarsor II with the alkaline solution treatment catalyged precursor I of pH=m, obtain catalyst precarsor III by reducing agent reducing catalyst precursor II;
C the solution be dissolved with containing palladium compound and gold-containing compound mixes with catalyst precarsor III by (), obtained catalyst precarsor IV;
D () obtains catalyst precarsor V with the alkaline solution treatment catalyged precursor IV of pH=n, obtain catalyst precarsor VI with reducing agent reducing catalyst precursor V;
E (), with alkali metal acetate solution impregnation catalyst precursor VI, obtains described catalyst after dry;
Wherein m and n is 8.5 ~ 10.5, and the absolute value of the difference of m and n is 0.3 ~ 2.0.
In technique scheme, the described palladium compound that contains is preferably the acid of chlorine palladium or chloropalladate, and gold-containing compound is preferably gold chloride or chloroaurate; Described aqueous slkali is preferably alkali-metal silicate or hydroxide; Reducing agent is preferably hydrazine hydrate or hydrogen; Described step (a) is preferably 1:(0.1 ~ 10 containing the total amount of palladium compound and gold-containing compound and step (c) containing the ratio of the total amount of palladium compound and gold-containing compound); Be more preferably 1:(0.25 ~ 4).
For solve the problems of the technologies described above three, technical solution of the present invention is as follows: under catalyst according to any one of one of above-mentioned technical problem technical scheme exists, oxygen is consisted of: ethene: nitrogen: acetic acid=1:(5 ~ 7 with molar ratio computing unstripped gas): (4 ~ 8): (1 ~ 2), reaction pressure is 0.5 ~ 0.9MPa, reaction temperature is 130 ~ 200 DEG C, and feed gas volume air speed is 1600 ~ 3000hr
-1.
The result that catalyst often causes over oxidation in commercial Application because noble metal alloy layer is blocked up, thus cause the active selectable of catalyst to reduce, adopt the vinyl acetate catalyst of the inventive method, step impregnation is adopted because of during preparation, alloy-layer is made to be bimodal distribution, thus minimizing over oxidation, improve its space time yield and selective.Experimental result shows, reaction pressure is 0.7MPa, reaction temperature 140 DEG C, reacting gas is with molar ratio computing oxygen: ethene: nitrogen: during acetic acid=1:6.8:7.2:1.7, the space time yield of catalyst of the present invention brings up to 585 g/Lhr by the 485g/Lhr of prior art catalyst, catalyst choice brings up to 98.2% by 93.4% of prior art, achieves good technique effect.
Detailed description of the invention
[embodiment 1]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
For the ease of comparing, the preparation condition of catalyst is listed in table 1.
(2) catalyst characterization
Use the radial scan of EDS-electron probe to detect PdAu alloy-layer radial distribution situation on a catalyst, use inductively coupled plasma spectrum generator (ICP) to measure the content of each element in catalyst, income analysis characterization data lists in table 2.
(3) evaluating catalyst
Use fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 400ml;
Reaction raw materials composition (with molar ratio computing): oxygen: ethene: nitrogen: acetic acid=1:6.8:7.2:1.7;
Reaction raw materials volume space velocity: 2000hr
-1;
Reaction pressure: 0.7MPa;
Reaction temperature: 140 DEG C;
Reaction time: 500hr;
With the content of each component in gas chromatography analytical reactions product, calculate the space time yield of this catalyst and selective, table 2 lists catalyst characterization and evaluating data.
[embodiment 2]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 3]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=10.5, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=8.5, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 4]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 0.25g/L, and the content of gold is 0.057g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 2.50g/L, and the content of gold is 0.57g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 5]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 2.50g/L, and the content of gold is 0.57g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 0.25g/L, and the content of gold is 0.057g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 6]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=9.3, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 7]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.3, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 8]
(1) catalyst preparing
Step (a): get the solution 1200ml containing potassium chloropalladate and potassium chloroaurate, wherein in solution, the content of palladium is 1.375g/L, the content of gold is 0.3125g/L, and the preparing spherical SiO 2 carrier of dipping volume to be 1100ml diameter be 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=8.5, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing potassium chloropalladate and potassium chloroaurate, wherein in solution, the content of palladium is 1.375g/L, the content of gold is 0.3125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.5, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 9]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 0.55g/L, and the content of gold is 0.125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 2.20g/L, and the content of gold is 0.50g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 10]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 2.20g/L, and the content of gold is 0.50g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 0.55g/L, and the content of gold is 0.125g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 11]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 0.46g/L, and the content of gold is 0.0525g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=9.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 0.46g/L, and the content of gold is 0.0525g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[embodiment 11]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 5.5g/L, and the content of gold is 5.21g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium hydrate aqueous solution getting pH=9.0, wherein in solution, the concentration of NaOH is 2.75g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrazine hydrate solution by catalyst precarsor II, wherein the content of hydrazine hydrate is 450g/L, recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 5.5g/L, and the content of gold is 5.21g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=10.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrazine hydrate solution by catalyst precarsor V, wherein the content of hydrazine hydrate is 450g/L, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
[comparative example 1]
The aqueous solution 1200ml got containing the acid of chlorine palladium and gold chloride is maceration extract, and wherein in solution, palladium content is 2.75g/L, and gold content is 0.625 g/L, and dipping 1100ml diameter is that the preparing spherical SiO 2 carrier of 4 ~ 6mm obtains catalyst precarsor; 27.5g sodium metasilicate is made into the 100 ml aqueous solution, wherein the pH value of solution is 9.5, is added in above-mentioned catalyst precarsor, mixes, and leaves standstill 24hr, then at 80 DEG C of dry 8hr.Reduced in hydrogen atmosphere by dried product, hydrogen flow rate is 0.2 ml/min, and pressure is 0.5MPa, and reduction temperature is 200 DEG C, and dipping liquor kalii acetici makes the content of potassium acetate be 30g/L, dry obtained finished catalyst.The method of evaluating performance of catalyst physical property sign and catalyst is with embodiment 1.For the ease of comparing the physical data of the preparation condition of catalyst, catalyst, catalysts towards ethylene is selective lists in table 1 and table 2.
[comparative example 2]
(1) catalyst preparing
Step (a): get containing the acid of chlorine palladium and the solution 1200ml of gold chloride, wherein in solution, the content of palladium is 1.375g/L, and the content of gold is 0.3125g/L, to flood volume be 1100ml diameter is the preparing spherical SiO 2 carrier of 6mm, obtains catalyst precarsor I;
Step (b): the 100ml sodium silicate aqueous solution getting pH=8.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor I, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor II, then reduced in hydrogen atmosphere by catalyst precarsor II, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor III;
Step (c): get the solution 1200ml containing the acid of chlorine palladium and gold chloride, wherein in solution, the content of palladium is 0.46g/L, and the content of gold is 0.0525g/L, and impregnated catalyst precursor II I, obtains catalyst precarsor IV;
Step (d): the 100ml sodium silicate aqueous solution getting pH=11.0, wherein the concentration of solution mesosilicic acid sodium is with SiO
2count 1.35g/L, add in catalyst precarsor IV, mix, leave standstill 24hr, then at 80 DEG C of dry 8hr, obtained catalyst precarsor V, then reduced in hydrogen atmosphere by catalyst precarsor V, hydrogen flow rate is 0.2 ml/min, pressure is 0.5MPa, reduction temperature is 200 DEG C, and the recovery time is 3 hours, obtains catalyst precarsor VI;
Step (e): be washed to without chlorion, the dipping potassium acetate aqueous solution, makes potassium acetate content be 30g/L, dry obtained finished catalyst.
Other steps are all identical in embodiment 1, for the ease of comparing the physical data of the preparation condition of catalyst, catalyst, the space time yield of catalyst and selectively listing in table 1 and table 2.
The present inventor finds that the catalyst adopting different pH value step impregnation to obtain prepares the effective of catalyst than single pH dipping, porpezite mass ratio in step (a) and the middle solution of step (c) is further adopted to be 1:1, when the difference of step (b) and step (d) aqueous slkali pH value is 1.0, the alloy-layer forming bimodal distribution has better reactivity and selective.
table 1 (continued). catalyst preparation conditions
table 1 (Continued). catalyst preparation conditions
table 2 catalyst physical property and evaluating data
Note: EDS-electron probe scanning catalyst coating PdAu alloy-layer institute is bimodal distribution by interior and show to be labeled as peak 1, peak 2 respectively.
Claims (10)
1. vinyl acetate catalyst, with SiO
2, Al
2o
3or its mixture is carrier, load active component comprises Metal Palladium, metallic gold and alkali metal acetate, wherein Metal Palladium and metallic gold exist with the form of Polarium, in catalyst, the content of palladium is 1 ~ 12g/L, the content of gold is 0.1 ~ 10g/L, the content of alkali metal acetate is 10 ~ 100g/L, it is characterized in that the PdAu alloy-layer of this catalyst coating in the radial scan of EDS-electron probe detects by interior and table in bimodal distribution; The Peak Separation of described bimodal distribution is 10 ~ 200 μm.
2. vinyl acetate catalyst according to claim 1, is characterized in that alkali metal acetate is potassium acetate.
3. vinyl acetate catalyst according to claim 2, is characterized in that the Peak Separation 80 ~ 120 μm of described bimodal distribution.
4. vinyl acetate catalyst according to claim 1, the bimodal ratio by the peak intensity of interior and table that it is characterized in that described bimodal distribution is 1:(0.05 ~ 20).
5. vinyl acetate catalyst according to claim 4, the bimodal ratio by the peak intensity of interior and table that it is characterized in that described bimodal distribution is 1:(0.125 ~ 8).
6. the preparation method of catalyst described in claim 1, comprises the following steps:
A the solution be dissolved with containing palladium compound and gold-containing compound mixes with carrier by (), obtained catalyst precarsor I;
B () obtains catalyst precarsor II with the alkaline solution treatment catalyged precursor I of pH=m, obtain catalyst precarsor III by reducing agent reducing catalyst precursor II;
C the solution be dissolved with containing palladium compound and gold-containing compound mixes with catalyst precarsor III by (), obtained catalyst precarsor IV;
D () obtains catalyst precarsor V with the alkaline solution treatment catalyged precursor IV of pH=n, obtain catalyst precarsor VI with reducing agent reducing catalyst precursor V;
E (), with alkali metal acetate solution impregnation catalyst precursor VI, obtains described catalyst after dry;
Wherein m and n is 8.5 ~ 10.5, and the absolute value of the difference of m and n is 0.3 ~ 2.0.
7. preparation method according to claim 6, it is characterized in that described is the acid of chlorine palladium or chloropalladate containing palladium compound, gold-containing compound is gold chloride or chloroaurate.
8. preparation method according to claim 6, it is characterized in that described aqueous slkali is alkali-metal silicate or hydroxide, reducing agent is hydrazine hydrate or hydrogen.
9. preparation method according to claim 6, is characterized in that described step (a) is 1:(0.1 ~ 10 containing the total amount of palladium compound and gold-containing compound and step (c) containing the ratio of the total amount of palladium compound and gold-containing compound).
10. the synthetic method of a vinyl acetate, under catalyst exists as described in the appended claim 1, oxygen is consisted of: ethene: nitrogen: acetic acid=1:(5 ~ 7 with molar ratio computing unstripped gas): (4 ~ 8): (1 ~ 2), reaction pressure is 0.5 ~ 0.9MPa, reaction temperature is 130 ~ 200 DEG C, and feed gas volume air speed is 1600 ~ 3000hr
-1.
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| CN107282136A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method and vinyl acetate synthesis method of vinyl acetate catalyst |
| CN107614476A (en) * | 2015-06-29 | 2018-01-19 | 昭和电工株式会社 | The manufacture method of allyl acetate |
| CN107866277A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The preparation method of vinyl acetate catalyst |
| CN112642491A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method |
| CN114177938A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
| CN114425444A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
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| CN107614476A (en) * | 2015-06-29 | 2018-01-19 | 昭和电工株式会社 | The manufacture method of allyl acetate |
| CN107282136A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The preparation method and vinyl acetate synthesis method of vinyl acetate catalyst |
| CN107866277A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The preparation method of vinyl acetate catalyst |
| CN107866277B (en) * | 2016-09-26 | 2020-06-09 | 中国石油化工股份有限公司 | Preparation method of vinyl acetate catalyst |
| CN112642491A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method |
| CN112642491B (en) * | 2019-10-10 | 2023-01-24 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method |
| CN114177938A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
| CN114425444A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
| CN114425454A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and vinyl acetate synthesis method |
| CN114425444B (en) * | 2020-10-14 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
| CN114425454B (en) * | 2020-10-14 | 2024-02-02 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and vinyl acetate synthesis method |
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