CN1340378A - High-activity catalyst for preparing vinyl acetate by ethylene method - Google Patents
High-activity catalyst for preparing vinyl acetate by ethylene method Download PDFInfo
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- CN1340378A CN1340378A CN 00119796 CN00119796A CN1340378A CN 1340378 A CN1340378 A CN 1340378A CN 00119796 CN00119796 CN 00119796 CN 00119796 A CN00119796 A CN 00119796A CN 1340378 A CN1340378 A CN 1340378A
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- catalyst
- koac
- vinyl acetate
- preparing vinyl
- sio
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Abstract
A high-activity catalyst for preparing vinyl acetate by the ethylene method is composed of carrier (SiO2 or SiO2-Al2O3 mixture) and active component (Pd 0.5-4 wt.% and KOAc 4-22 wt.%) in the form of non-uniformly distributed egg shell, and the catalyst shape may be in sphere, bar, cylinder or Rhoshigring. It can prevent the too high initial activity of catalyst by containing cocatalyst KOAc.
Description
The present invention relates to ethene, acetic acid and oxygen or oxygen-containing gas is raw material, and gas-phase reaction prepares the method for vinylacetate.
With ethene, acetic acid and oxygen or oxygen-containing gas is raw material, to prepare vinylacetate be ripe technology to gas-phase reaction in fixed bed reactors, appropriate catalyst is that active constituent contains Pd and KOAc, and can contain Au, Ba, Au or Cu, and/or its corresponding salt compounds, these active constituents are carried on SiO usually
2Or SiO
2-Al
2O
3Mixture on, it is ripe that this class catalyst has been tending towards equally.In recent years, it is the main method that majority state increases vinylacetate output that original device is carried out reorganization and expansion, and one of its core technology is exactly the improvement to catalyst, and wherein comparatively general way is to adopt the high activity vinyl acetate catalyst.At present, improving activity of such catalysts mainly is to realize by the content that increases the active constituent palladium.But but there is some problem in the content that only increases palladium, as for certain process units, and system's transfer reaction heat limited in one's ability, and the raising of the content of active constituent palladium makes the catalyst initial activity too high, thus cause reaction heat to be difficult for shifting.
Patent US5,990,344 proposed a kind of in the technical scheme that is higher than 500 ℃ of palladiums on the sintering temperature carrier, in the hope of solving the too high problem of above-mentioned catalyst initial activity.Can make rising appreciably of palladium metal particle by this sintering step, suppress the too high purpose of catalyst initial activity thereby reach, but its obvious defects has been many this step of sintering.
The purpose of this invention is to provide a kind of new high activated catalyst that is used for ethylene process of preparing vinyl acetate, it solves the too high technical barrier of catalyst initial activity by the content that improves co-catalyst KOAc in the catalyst, thereby can overcome the defective of prior art easily and effectively.
Details are as follows for the high activated catalyst that is used for ethylene process of preparing vinyl acetate provided by the invention:
Catalyst carrier is SiO
2Perhaps be SiO
2-Al
2O
3Mixture, the active constituent of load contains Pd and KOAc.The weight percentage of Pd is 0.5～4.0%, and optimum content is 0.7～2.0%; The weight percentage of KOAc is 4.0～22.0%, and optimum content is 10.0～20.%.Active constituent is preferably the eggshell type non-uniform Distribution, and that catalyst shape can be is spherical, bar-shaped, cylindric, Raschig ring shape etc.Also can contain co-catalyst component A in the active constituent, A is selected from any a group in following three groups of materials:
The salt compounds of Au, Au or both mixtures, perhaps,
The salt compounds of Ba, Ba or both mixtures, perhaps,
The salt compounds of Cd, Cd or both mixtures.
The weight percentage of co-catalyst component A is 0.2～1.0% in the active constituent.
The inventor finds by a large amount of test, and to be controlled at weight percentage be can both obtain expected effect in 4.0～22.0% the scope to KOAc in the catalyst, and the weight percentage of KOAc was 10.0～20.% when catalyst performance was best.In operation, it should be noted that, owing to there is the co-catalyst KOAc of high level in the catalyst, should reduce the amount of adding KOAc in the reactor at the initial stage that catalyst comes into operation, and the KOAc of catalyst reactor amount can calculate by the amount of the KOAc in the analytical reactions liquid.In addition, a month planted agent in reaction keeps higher relatively acetic acid input amount.After one month, the input amount of acetic acid is reduced to normal level.
Catalyst can be known with those skilled in the art, be used to prepare the method that similar sphere or special-shaped particle and active constituent be the eggshell distribution and prepare, and following described preparation process is that the present invention recommends.
At first select a kind of carrier for use, its specific area is 50～250m
2/ g, pore volume generally can be SiO for being 0.5～1.5ml/g
2Perhaps SiO
2-Al
2O
3Mixture.
Use the solution impregnating carrier of Pd and co-catalyst A then, the introducing of Pd can be selected the compounds such as soluble-salt of Pd in the solution, as palladium bichloride, palladium, palladium nitrate or the acid of chlorine palladium; The introducing of A can be selected the salt of solubility.
With above-mentioned soaked carrier particle drying to moisture percentage is 90～99%, carries out the alkali lye impregnation process then, and available alkali is alkali-metal hydroxide or alkali-metal silicate.Noble metal runs off in the alkali steeping process in order to avoid, and the volume of alkali lye should be equivalent to the total pore volume of carrier, promptly carries out isopyknic dipping.Required alkali number can calculate from Pd and Au are changed into the required amount of hydroxide.Experiment finds that the appropriate excessive of alkali is favourable, and it is excessive 30%～80% to it is generally acknowledged, suitable.The time that alkali steeping is handled is 5～20 hours.Then catalyst is reduced processings, can at room temperature flood usually or at high temperature place reducing gas to realize with hydrazine hydrate solution.The amount of reducing agent depends on the amount of Pd and Au, and reducing equivalent should be 1～1.5 times of oxidation equivalent.Recovery time was generally 2～10 hours.
Process afterwards is washing and dry, and then the co-catalyst potassium acetate is carried on the carrier, adopts infusion process usually, carries out at last getting finished catalyst after the drying.
The invention has the advantages that by improvement catalyst activity component, solved the too high technical barrier of high activity vinyl acetate catalyst initial activity, compared with existing method, the present invention is more simple, need not increase agglomerating plant, thereby reduce production cost.With
Under will further describe details of the present invention by embodiment.In the evaluating data of catalyst:
Embodiment 1～8: one, Preparation of catalysts:
Embodiment 1:
Pure SiO
2Ball type carrier, diameter 5～7mm, specific area is 120～200m
2/ g, pore volume is for being 0.7～0.9ml/g.With containing the Na that is equivalent to 6.6 gram palladiums
2PdCl
4With the HAuCl that is equivalent to 2.8 gram gold
4Obtained aqueous solution 450ml gets 1.1 then and goes up and state carrier and flood a moment therein, and carrier takes out and to be dried to moisture content is 98%, then carrier is placed 540ml to contain 47.4 gram Na
2SiO
39H
2In the solution of O, left standstill under the room temperature 12 hours.The pH value of measuring solution then is 8.2.Left standstill 4 hours after adding the hydrazine hydrate that 30ml concentration is 85% (wt.), the palladium of load on the carrier and the compound of gold are reduced into simple substance palladium and gold fully.Use deionized water rinsing then, in eluate, do not contain Cl
-1Till.Then in 100 ℃ dry 4 hours down, be cooled to indoor temperature after, the aqueous solution incipient impregnation with containing 60 gram potassium acetates takes out and is dried to moisture content less than 2% under 100 ℃, finally obtains active constituent and is the finished catalyst that eggshell type distributes.
The catalyst preparation process of embodiment 2～8 and comparative example is identical, and composition separately sees Table 1..Two, the evaluation of catalyst:
The catalyst of filling 2790 gram the foregoing descriptions 1～8 and comparative example is used earlier the ethene leak test in fixed bed reactors, after the affirmation nothing is leaked, the ethene flow is transferred to 567.41mol/h, heat up simultaneously, when temperature in the beds reaches 120 ℃, drop into acetic acid, the acetic acid amount is 69.20mol/h, after several hours, progressively drop into oxygen, initial throwing oxygen amount 13.84mol/h, the final oxygen amount 41.52mol/h that throws, the acetic acid input amount was increased to 83.04mol/h at the 5th day that reacts.
Control bed hot(test)-spot temperature is 142～150 ℃ in the course of reaction, reactor inlet pressure 0.8Mpa (gauge pressure), and the entire reaction time is 1000 hours.Ethene, acetic acid and oxygen are chargings after mixing in preheater.Regulate the acetic acid pump to control its flow, ethene and oxygen flow all adopt the control of mass velocity controller, reaction gas discharges after condenser condenses, extract reaction solution analysis product vinyl acetate and unreacted acetate amount wherein, and side reaction product carbon dioxide in the tail gas, uncooled vinyl acetate and unreacted oxygen.
The evaluation result of catalyst sees Table 2..Table 1.
Table 2.
| The composition of catalyst activity component | Carrier | |
| Comparative example | ?Pd(1.47％wt)Au(0.62％wt)KOAc(6.75％wt) | ????SiO 2 |
| Embodiment 1 | ?Pd(1.47％wt)Au(0.62％wt)KOAc(10.48％wt) | ????SiO 2 |
| Embodiment 2 | ?Pd(1.47％wt)Au(0.62％wt)KOAc(13.33％wt) | ????SiO 2 |
| Embodiment 3 | ?Pd(1.47％wt)Au(0.62％wt)KOAc(16.78％wt) | ????SiO 2 |
| Embodiment 4 | ?Pd(1.47％wt)Au(0.62％wt)KOAc(20％wt) | ????SiO 2 |
| Embodiment 5 | ?Pd(1.80％wt)Au(0.76％wt)KOAc(10.48％wt) | ????SiO 2 |
| Embodiment 6 | ?Pd(1.80％wt)Au(0.76％wt)KOAc(13.33％wt) | ????SiO 2 |
| Embodiment 7 | ?Pd(1.80％wt)Au(0.76％wt)KOAc(16.78％wt) | ????SiO 2 |
| Embodiment 8 | ?Pd(1.80％wt)Au(0.76％wt)KOAc(20％wt) | ????SiO 2 |
| Initial stage space-time yield (g/lh) in 480 hours | Initial stage selectivity (%) in 480 hours | Space-time yield after 480 hours (g/lh) | Selectivity after 480 hours (%) | |
| Comparative example | ????1083 | ????92.5 | ????1025 | ????92.7 |
| Embodiment 1 | ????957 | ????93.3 | ????1087 | ????93.1 |
| Embodiment 2 | ????846 | ????93.6 | ????1060 | ????93.5 |
| Embodiment 3 | ????730 | ????94.4 | ????983 | ????94.1 |
| Embodiment 4 | ????683 | ????94.8 | ????795 | ????94.5 |
| Embodiment 5 | ????950 | ????92.2 | ????1012 | ????92.5 |
| Embodiment 6 | ????912 | ????93.2 | ????1096 | ????92.8 |
| Embodiment 7 | ????926 | ????94.3 | ????1203 | ????93.2 |
| Embodiment 8 | ????857 | ????94.5 | ????1005 | ????93.6 |
Claims (4)
1, a kind of high activated catalyst that is used for ethylene process of preparing vinyl acetate, catalyst carrier is SiO
2Perhaps be SiO
2-Al
2O
3Mixture, the active constituent of load contains Pd and KOAc, the weight percentage of Pd is 0.5～4.0%, the weight percentage of KOAc is 4.0～22.0%.
2, the high activated catalyst that is used for ethylene process of preparing vinyl acetate according to claim 1 is characterized in that also containing in the described catalyst activity component co-catalyst component A, and A is selected from any a group in following three groups of materials:
The salt compounds of Au, Au or both mixtures, perhaps,
The salt compounds of Ba, Ba or both mixtures, perhaps,
The salt compounds of Cd, Cd or both mixtures,
The weight percentage of component A is 0.2～1.0%.
3, the high activated catalyst that is used for ethylene process of preparing vinyl acetate according to claim 1 and 2, the weight percentage that it is characterized in that Pd in the described catalyst activity component is 0.7～1.8%; The weight percentage of KOAc is 10.0～20.0%.
4, the high activated catalyst that is used for ethylene process of preparing vinyl acetate according to claim 1 and 2 is characterized in that described catalyst activity component is the eggshell type non-uniform Distribution, and catalyst shape is spherical, bar-shaped, cylindric, Raschig ring shape etc.,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00119796 CN1112241C (en) | 2000-08-30 | 2000-08-30 | High-activity catalyst for preparing vinyl acetate by ethylene method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00119796 CN1112241C (en) | 2000-08-30 | 2000-08-30 | High-activity catalyst for preparing vinyl acetate by ethylene method |
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|---|---|
| CN1340378A true CN1340378A (en) | 2002-03-20 |
| CN1112241C CN1112241C (en) | 2003-06-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7030056B2 (en) | 2002-03-27 | 2006-04-18 | Shell Oil Company | Process for preparing a catalyst, the catalyst and a use of the catalyst |
| CN1314490C (en) * | 2003-04-23 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
| US7425647B2 (en) | 2001-03-30 | 2008-09-16 | Shell Oil Company | Process for preparing a group V111-metal containing catalyst, use thereof for preparing an alkenyl carboxylate |
| CN101927196B (en) * | 2009-06-26 | 2012-03-07 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof |
| CN106582821A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
-
2000
- 2000-08-30 CN CN 00119796 patent/CN1112241C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7425647B2 (en) | 2001-03-30 | 2008-09-16 | Shell Oil Company | Process for preparing a group V111-metal containing catalyst, use thereof for preparing an alkenyl carboxylate |
| US7030056B2 (en) | 2002-03-27 | 2006-04-18 | Shell Oil Company | Process for preparing a catalyst, the catalyst and a use of the catalyst |
| CN1314490C (en) * | 2003-04-23 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyzer in use for synthesizing vinyl acetate, and preparation method |
| CN101927196B (en) * | 2009-06-26 | 2012-03-07 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof |
| CN106582821A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
| CN106582821B (en) * | 2015-10-19 | 2019-12-10 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1112241C (en) | 2003-06-25 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: SHANGHAI PETROCHEMIAL CO LTD, CHINA PETROCHEMICAL CORP Effective date: 20051014 |
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Effective date of registration: 20051014 Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee after: Sinopec Corp. Address before: 200540 Shanghai city Jinshan District Jin Road No. 48 Patentee before: Shanghai Petrochemical Co., Ltd., SINOPEC |
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Granted publication date: 20030625 |