CN1297883A - Ethylene process of preparing vinyl acetate - Google Patents
Ethylene process of preparing vinyl acetate Download PDFInfo
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- CN1297883A CN1297883A CN 99124194 CN99124194A CN1297883A CN 1297883 A CN1297883 A CN 1297883A CN 99124194 CN99124194 CN 99124194 CN 99124194 A CN99124194 A CN 99124194A CN 1297883 A CN1297883 A CN 1297883A
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- vinyl acetate
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Abstract
The ethylene process of preparing vinyl acetate in a fixed bed reactor uses ethylene and acetic acid or oxygen containing gas as material and has reaction temperature of 100-210 deg.c and reactor inlet pressure of 0.5-2.0 MPa. The catalyst for the process includes SiO2 or SiO2-Al2O3 mixture as carrier and Pd and KOAc containing active components. The catalyst grains are 3-6 mm long rod and have cross section of vane wheel shape of 3.5-8.0 mm outer diameter with one central circular hole of 1.0-2.5 mm diameter and 3-7 vanes. The present invention has the advantages of proper gas passage in the catalyst bed layer and thus high time space yield, low pressure loss in bed layer and excellent selectivity.
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 vinyl acetate.
With ethene, acetic acid and oxygen or oxygen-containing gas is raw material, to prepare vinyl acetate be more sophisticated technology to gas-phase reaction in fixed-bed reactor, appropriate catalyst is that active constituent contains Pd and KOAc, and can contain Au, Ba or Cd, 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 activity of such catalysts component is tending towards already, what people were more after the seventies is that the distribution mode of its active constituent on carrier launched research, and the catalyzer that constantly has yolk type, protein type and eggshell type isoreactivity component to be non-uniform Distribution is released.The catalyzer of active constituent non-uniform Distribution is with respect to equally distributed catalyzer, and its apparent activity, selectivity and anti-poisoning capability all are significantly improved.
Above-mentioned traditional catalyzer, no matter whether active constituent is evenly or non-uniform Distribution, granules of catalyst is generally sphere, later result of study is found, catalyzer based on ball type carrier is too big in the pressure drop of high-speed reaction conditions lower bed layer, brought difficulty to technological operation, some aspheric special-shaped beaded catalysts then can adapt to the operational condition of high-speed preferably.Just released the multiple special-shaped bar-shaped catalyzer that gas-phase reaction prepares vinyl acetate that is used for as patent EP 0464633A1, cross-sectional shape has the figure of eight, " product " font and porous circle etc.Compare with the traditional spheroidal catalyzer, special-shaped, particularly have more gas passage in the beds that the catalyst loading of porous abnormal shape becomes, experimental data shows that the space-time yield of such catalyzer has comparatively significantly raising, and the bed pressure drop loss reduces to some extent.
Yet,, but have a whether problem of appropriateness with the size of gas passage volume in the beds of shape of catalyst institute direct correlation.Obviously the increase of gas passage volume, can obtain higher space-time yield and make the bed pressure drop loss reduce, but the aggravation of the excessive material air-teturning mixed phenomenon that then can induce reaction, reaction mass is overstand in beds, make heat of reaction be difficult in time removing on the contrary, this will cause the increase of side reaction.Simultaneously, the product over-drastic that more serious material back-mixing also makes first set reaction generate stops and causes deep oxidation, thereby causes the coking of catalyst surface, the active centre on blocking catalyst surface.All these finally all will cause selectivity of catalyst to descend, and can't make catalyzer keep good reaction activity in the long time.More or less there are the problems referred to above in the special-shaped catalyst of existing preparation vinyl acetate.
The purpose of this invention is to provide a kind of new be raw material with ethene, acetic acid and oxygen or oxygen-containing gas, gas-phase reaction prepares the method for vinyl acetate, the catalyzer that is adopted is special-shaped beaded catalyst, its suitable particle shape makes the gas passage that has suitable volumes in the catalyzer, and it has overcome the defective that prior art exists effectively.
Details are as follows for the method for preparing vinyl acetate provided by the invention:
It is a raw material with ethene, acetic acid and oxygen or oxygen-containing gas, temperature of reaction is 100～210 ℃, reactor inlet pressure is 0.5～2.0MPa, and the molar percentage of charge raw material is: ethene: acetic acid: oxygen=(75～8 5): (10～20): (3～7), WWH is (1600～3000) hr
-1, the fixed bed that the reaction raw materials gas mixture constitutes by following catalyzer is reacted and is made vinyl acetate.Support of the catalyst is SiO
2Perhaps be SiO
2-Al
2O
3Mixture, the active constituent of load contains Pd and KOAc, active constituent is the eggshell type non-uniform Distribution, it is characterized in that granules of catalyst is bar-shaped, and the cross section is the impeller shape, there is hole, a garden at the impeller center, leaf is half garden shape, and number of sheets order is 3～7, and particle length L is 3～6mm, garden, center bore dia D1 is 1.0～2.5mm, and impeller outer garden diameter D2 is 3.5～8.0.
Preferred 3～5 of the number of above-mentioned leaf, the preferred 4～5mm of particle length L, the preferred 1.5～2.0mm of garden, center bore dia D1, the preferred 4.0～6.0mm of impeller outer garden diameter D2.
Also can contain promotor 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 content of Pd is 0.5～3.0% (w.t.) in the above-mentioned active constituent, and optimum content is 0.7～1.2% (w.t.); The content of KOAc is 1.0～10.0% (w.t.); The content of promotor component A is 0.2～0.6% (w.t.).
Catalyzer can be known with those skilled in the art, be used to prepare the method that similar special-shaped particle and active constituent be the eggshell distribution and prepare, and following described preparation process is that the present invention recommends.
The preparation of carrier is the fs of Preparation of Catalyst, with SiO
2Perhaps SiO
2-Al
2O
3Mixture add binding agent and make microballoon, add organic filler and lubricant then, the binding agent of recommending to use is the carbonate of C2～C26 of Li, Mg, Al, Zn, Fe or Mn, passes through extrusion molding.The roasting 0.5～5 hour under 500～900 ℃ temperature and in oxygen-containing atmosphere subsequently of carrier granule blank, the carrier specific surface area that makes is 50～250m
2/ g, pore volume is for being 0.5～1.5ml/g.
Use the solution impregnating carrier of Pd and Au (is promotor as selecting Au) then, the introducing of Pd can be selected the compounds such as soluble salt of Pd in the solution, as Palladous chloride, Palladous nitrate or the acid of chlorine palladium; The introducing of Au can be selected the gold trichloride or the tetra chlorauric acid salt of solubility.
With above-mentioned soaked carrier particle drying to moisture percentage is 90～99%, carries out the alkali lye dip treating then, and available alkali is alkali-metal oxyhydroxide or alkali-metal silicate.Precious 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 oxyhydroxide, and 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 catalyzer 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 reductive 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 hour.
Process afterwards is washing and dry, and then the promotor Potassium ethanoate is carried on the carrier, adopts pickling process usually, carries out at last getting finished catalyst after the drying.
Compared with prior art, vinyl acetate between to for plastic preparation method provided by the invention is because the catalyzer that adopts has suitable particle shape, so there is the gas passage of suitable volumes in the beds that loads, it not only has higher space-time yield and lower bed pressure drop loss, and selectivity is also very good.
Figure of description has been showed the profile synoptic diagram of the catalyst embodiments that method provided by the invention adopted.
By accompanying drawing as seen, the cross section of granules of catalyst is the impeller shape, and particle length is L, and it is the hole, garden of D1 that catalyst center has a diameter, and impeller outer garden diameter is D2, and the number of sheets order of the present embodiment is 4.
Below will further describe details of the present invention by embodiment.Because major technique of the present invention is characterised in that the improvement of catalyzer, other process of reaction then is that the those skilled in the art in present technique field are known.Therefore, embodiment will pay attention to the description of catalyzer, and by positively effect of the present invention is showed in the evaluation of catalyzer.
In the evaluating data of catalyzer:
Embodiment 1～5:
One, Preparation of catalysts:
At first at SiO
2The middle binding agent Magnesium Stearate that adds is made microballoon, adds organic filler and lubricant then, passes through extrusion molding.The roasting 3 hours under 750 ℃ temperature and in oxygen-containing atmosphere subsequently of carrier granule blank, the carrier specific surface area that makes is 160～200m
2/ g, pore volume is for being 0.7～0.9ml/g.
With containing the Na that is equivalent to 3.69 gram palladiums
2PdCl
4With the HAuCl that is equivalent to 1.71 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 percentage is 98%, then carrier is placed 540ml to contain 275 gram Na
2SiO
3.9H
2In the solution of O, left standstill under the room temperature 12 hours, the pH value of measuring solution then should be 7.9.Left standstill 4 hours after adding the hydrazine hydrate that 25ml concentration is 85% (w.t.), 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 elutant, do not contain Cl
-1End.Then in 100 ℃ dry 4 hours down, be cooled to the aqueous solution incipient impregnation that indoor Wen Houyong contains 33 gram potassium acetates, take out the back and under 100 ℃, be dried to moisture percentage less than 2%, finally obtain finished catalyst.The shape and size middle period number of catalyzer, particle length L, garden, center bore dia D1, impeller outer garden diameter D2 etc. see Table 1.
Two, reaction process:
In 900 milliliters of fixed-bed reactor, pack into behind the 900ml catalyzer, use ethene pressure testing leak test earlier, after affirmation does not have leakage, the ethene flow is transferred to 63.9mol/h, heat up simultaneously, when temperature in the beds reaches 120 ℃, can drop into acetic acid, the acetic acid flow is 9.31mol/h, after half an hour, progressively drops into oxygen, throw sufficient oxygen amount after 2 hours, flow reaches 4.34mol/h, promptly controls raw material ratio to be: ethene/acetic acid/oxygen=82.4/12.0/5.6 (molar percentage), WWH is: 1930hr
-1Control bed hot(test)-spot temperature is 142 ℃ in the reaction process, reactor inlet pressure 0.8MPa.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 reaction product vinyl acetate and unreacted acetic acid amount wherein, and side reaction product carbonic acid gas in the tail gas, uncooled vinyl acetate and unreacted oxygen.
The evaluation result of catalyzer sees Table 2.
Table 1.
| Number of sheets order (individual) | ?????L ???(mm) | ????D1 ???(mm) | ????D2 ???(mm) | |
| Embodiment 1 | ????3 | ????6.0 | ????2.0 | ????4.2 |
| Embodiment 2 | ????4 | ????4.8 | ????1.9 | ????5.4 |
| Embodiment 3 | ????5 | ????3.5 | ????1.8 | ????4.5 |
| Embodiment 4 | ????6 | ????5.5 | ????1.7 | ????4.8 |
| Embodiment 5 | ????7 | ????4.0 | ????1.6 | ????5.0 |
Table 2.
| (MPa) falls in pressure | Space-time yield (g/lhr) | Selectivity (%) | |
| Embodiment 1 | ????78 | ????525 | ????96.1 |
| Embodiment 2 | ????75 | ????540 | ????96.5 |
| Embodiment 3 | ????81 | ????533 | ????96.9 |
| Embodiment 4 | ????67 | ????512 | ????9?5.3 |
| Embodiment 5 | ????69 | ????504 | ????95.4 |
Claims (6)
- It is 1, a kind of that to be used for ethene, acetic acid and oxygen or oxygen-containing gas be raw material, gas-phase reaction prepares the method for vinyl acetate, temperature of reaction is 100～210 ℃, reactor inlet pressure is 0.5～2.0MPa, the molar percentage of charge raw material is: ethene: acetic acid: oxygen=(75～85): (10～20): (3～7), WWH is (1600～3000) hr -1, the fixed bed that the reaction raw materials gas mixture constitutes by following catalyzer is reacted and is made vinyl acetate, and support of the catalyst is SiO 2Perhaps be SiO 2-Al 2O 3Mixture, the active constituent of load contains Pd and KOAc, active constituent is the eggshell type non-uniform Distribution, it is characterized in that granules of catalyst is bar-shaped, and its cross section is the impeller shape, there is hole, a garden at the impeller center, leaf is half garden shape, and number of sheets order is 3～7, and particle length L is 3～6mm, garden, center bore dia D1 is 1.0～2.5mm, and impeller outer garden diameter D2 is 3.5～8.0.
- 2, the method for preparing vinyl acetate according to claim 1, the content that it is characterized in that Pd in the described catalyzer are 0.5～3.0% (w.t.), and the content of KOAc is 1.0～10.0% (w.t.).
- 3, the method for preparing vinyl acetate according to claim 2, the content that it is characterized in that Pd in the described catalyzer are 0.7～1.2% (w.t.).
- 4, the method for preparing vinyl acetate according to claim 1 is characterized in that the active constituent of catalyst cupport also contains component A, and A is 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.
- 5, the method for preparing vinyl acetate according to claim 4, the content that it is characterized in that component A in the described catalyzer are 0.2～0.6% (w.t.).
- 6, according to claim 1,2,3, the 4 or 5 described methods that prepare vinyl acetate, it is characterized in that number of sheets order is 3～5 on the described granules of catalyst cross section, particle length L is 4～5mm, and garden, center bore dia D1 is 1.5～2.0mm, and impeller outer garden diameter D2 is 4.0～6.0mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99124194A CN1115323C (en) | 1999-12-02 | 1999-12-02 | Ethylene process of preparing vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99124194A CN1115323C (en) | 1999-12-02 | 1999-12-02 | Ethylene process of preparing vinyl acetate |
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| Publication Number | Publication Date |
|---|---|
| CN1297883A true CN1297883A (en) | 2001-06-06 |
| CN1115323C CN1115323C (en) | 2003-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99124194A Expired - Lifetime CN1115323C (en) | 1999-12-02 | 1999-12-02 | Ethylene process of preparing vinyl acetate |
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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 |
| 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 |
| CN103058863A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of allyl acetate |
| CN103121953A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing vinyl acetate from ethylene by gas-phase oxidation |
| CN103958453A (en) * | 2011-08-30 | 2014-07-30 | 瓦克化学股份公司 | Method for the acetoxylation of olefins in gas phase |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69101032T2 (en) * | 1990-07-03 | 1994-08-11 | Kuraray Co | Catalyst and process for the production of unsaturated esters. |
-
1999
- 1999-12-02 CN CN99124194A patent/CN1115323C/en not_active Expired - Lifetime
Cited By (7)
| 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 |
| CN103958453A (en) * | 2011-08-30 | 2014-07-30 | 瓦克化学股份公司 | Method for the acetoxylation of olefins in gas phase |
| CN103058863A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of allyl acetate |
| CN103058863B (en) * | 2011-10-24 | 2015-01-07 | 中国石油化工股份有限公司 | Preparation method of allyl acetate |
| CN103121953A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing vinyl acetate from ethylene by gas-phase oxidation |
| CN103121953B (en) * | 2011-11-18 | 2015-07-08 | 中国石油化工股份有限公司 | Method for preparing vinyl acetate from ethylene by gas-phase oxidation |
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| Publication number | Publication date |
|---|---|
| CN1115323C (en) | 2003-07-23 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: SHANGHAI PETROCHEMIAL CO LTD, CHINA PETROCHEMICAL CORP Effective date: 20050930 |
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Effective date of registration: 20050930 Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee after: Sinopec Corp. Address before: Shanghai City, Jinshan District Jinyi road 200540 Patentee before: Shanghai Petrochemical Co., Ltd., SINOPEC |
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Granted publication date: 20030723 |
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