CN1154873A - Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same - Google Patents
Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same Download PDFInfo
- Publication number
- CN1154873A CN1154873A CN 96123308 CN96123308A CN1154873A CN 1154873 A CN1154873 A CN 1154873A CN 96123308 CN96123308 CN 96123308 CN 96123308 A CN96123308 A CN 96123308A CN 1154873 A CN1154873 A CN 1154873A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- ethylene
- radius
- particulate
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A catalyzer for oxychlorinating ethylene to 1, 2-dichloroethane, contains copper chloride as a main component, has a format of hollow cylindric particle, wherein at least three through holes are provided in the particle and are obtained by compressing molded, a lubricant is used on a wall face of a molding chamber and on a plunger of a mould for lubricating.
Description
The present invention relates to a kind of ethylene oxychlorination (oxichlorination) be become 1, the fixed bed beaded catalyst of 2-ethylene dichloride, described catalyzer are by the acquisition of special compressed moulding (in flakes) method.Specifically, the present invention relates to a kind of cupric chloride (CuCl that contains
2) conduct be stated from the catalyzer of the active ingredient on the aluminum oxide.
These catalyzer have very narrow void distribution.Because described granules of catalyst can provide high surface/volume rate, and because its pore character, these catalyzer are reduced in load (load) loss that takes place in the fixed-bed reactor significantly, and improve activity of such catalysts and selectivity widely.
The applicant application examining described a kind of catalyzer and had the support of the catalyst of geometry in particular in first to file, for example, have the cylindrical of through hole (through holes), cross section with circle or multi-petal shape, this catalyzer is made powder in flakes by using exterior lubricant, lubricant wherein is applied on the plunger of the surface of forming room and mould, rather than is distributed in the body of powder of wanting in blocks.
This application is not described and is used for ethylene oxychlorination is become 1 the catalyzer of 2-ethylene dichloride.
Synthesize 1 by oxychlorination of ethylene in fluidized-bed or fixed-bed reactor, the 2-ethylene dichloride is known.Under first kind of situation, in reactor, can obtain more uniform temperature and distribute (having avoided local superheating), because the granules of catalyst bonding has some unfavorable factor in fluidisation.Under second kind of situation, reaction parameter is controlled easily, but because between the granules of catalyst and the heat exchanger effectiveness between described particle and the reactant gases low, local temperature may take place to raise, form so-called " focus ".Consider selectivity of catalyst and its useful life longevity, the rising of this local temperature should be avoided.
Being used for for solution that first kind of heat exchange problem between the granules of catalyst of ethylene oxychlorination make great efforts is circle and the cylindrical particle that adopts annular particles or have certain aspect ratio.
Synthesizing 1 effectively with fixed-bed reactor, in the situation of 2-ethylene dichloride, the heat exchange coefficient problem is not unique technical problem that will solve.
In fact, for the beaded catalyst in the fixed bed that is used in ethylene oxychlorination, following feature also needs:
-low gas flow resistance (catalyst bed for same thickness has low load loss);
-Gao effective surface that is to say, has high surface/volume rate;
-good physical strength is with the packing of the fragmentation that prevents granules of catalyst and the bed that causes therefrom.
The catalyzer (being formed as ball, solid cylinder or the ring of various size) that is generally used in the fixed bed oxychlorination process addresses these problems unsatisfactorily.In addition, when using these known configurations, be very limited from the added diffusion of granule interior in the diffusion of the reactant gases of catalyst particles intragranular and reaction product.This means, in the heterogeneous system that is adopted, owing to carry out easilier and more selective at particulate outside surface oxi-chlorination, so can not use oxychlorination catalyst effectively with known form.Therefore, the desirable transformation efficiency that obtains of a large amount of catalyzer be used, and in the tube bank fixed bed, pipe must be used with enough height.Use the oxychlorination catalyst of known form, this can cause the further increase of load loss, and this is also because the space of catalyst particles intergranular is little.
The catalyzer different with the traditional catalyst particle shape is described in the U.S. Pat 4 441 990, and it relates to a kind of tubular particle of extruding with trilateral or dimetric many lobes cross section.This catalyzer is stoping broken and pressure provides advantage aspect falling, but compares with traditional catalyst, and its result is certain not to have too big difference.
Extruding is a kind of industrial method that is commonly used to form catalyzer.
This method is very simple technically; But its shortcoming is to be suitable for being used for forming the complicated shape that can address the above problem satisfactorily anything but.
Catalyzer of the present invention obtains by compressed moulding, and this method is known as compressing tablet, and wherein lubricant is not to be dispersed in (main body is lubricated) in the powder mass of wanting moulding, but is applied on the wall of forming room on the plunger with model (external lubrication).
Compare with the catalyzer that lubricates preparation with main body, the catalyzer of producing with this method has higher porosity and narrower pore size distribution.Pore volume above 40% has the radius corresponding to the peak value of void distribution curve.Porosity is generally 0.20-0.5cm
2/ g (using the mercury determination of adsorption method).Its surface-area is generally 80-180m
2/ g (BET method).
This catalyzer also has the constant particle size parameters.Can not obtain the constant of these parameters in the forming method that the main consuming body lubricates, this is because the sintering of significant can make part or all of granules of catalyst distortion.
Because this distortion, the lubricated forming method of the main consuming body can not be used for producing the particulate industrial practice with complex geometric shapes.
Preferred oxychlorination catalyst is to load on the alumina particle with desirable geometrical shape by the halogenide (preferred Repone K and magnesium chloride) with cupric chloride and basic metal or alkaline-earth metal to prepare.
Alumina supporter is to utilize method of the present invention, will disperse the aluminum oxide moulding of (bohemite) form, and particle is obtained at 400-700 ℃ roasting temperature.At last, particle is flooded with cupric chloride and potassium chloride solution.Below be the representative compositions based on the catalyzer of weight: Al
2O
3=80%; CuCl
2=15%; KCl=5%.
The porosity of used dispersive aluminum oxide can change in wide scope, as 0.5-1.9cm
3/ g.With the catalyzer that the aluminum oxide of discrete form obtains, the radius that surpasses 40% pore volume is between 60-70A.Its surface-area is at 80-380m
2Between/the g.
The lubricant that can be used for preparing catalyzer of the present invention comprise be suitable for reducing the powder of wanting compressing tablet with and some part of the tabletting machine that contacts of described powder between the solid and the liquid of frictional coefficient.
Examples of suitable lubricants is stearic acid and palmitinic acid; The basic metal that these are sour and the salt of alkaline-earth metal are as stearic magnesium, potassium or aluminium salt; Carbon black, talcum, list-or triglyceride, as glyceryl monostearate and XU 61518.10, paraffin oil, and PFPE.
Liquid lubricant can use with the form of solution or the dispersion liquid in dispersion agent.
The consumption of liquid lubricant is generally each particle 0.025-25mg.
Solid lubricant can apply by dusting on forming room and plunger (dusting), that is to say, covers the very thin lubricant powder with the continuous air flow transmission of one deck thereon.
Forming room and plunger can be made with self-lubricating material, or apply with self-lubricating material, and this examples of material has tetrafluoroethylene or stupalith.This just can be avoided or reduce lubricant.
Catalyzer of the present invention has at least three through holes, and its axis preferably is parallel to each other substantially, and parallel with the particulate axis, and equidistant substantially each other.
Preferably, through hole has circular cross section, and with respect to the particulate cross section, its axis forms the angle that is essentially equilateral triangle; The point orientation that described angle contacts with external garden towards cross section.In preferred embodiment of the present invention, cylindrical-circular lobe that particle has, these lobes are identical, and coaxial with through hole.
Utilize the particulate special geometry,, can promote the high-level disturbance of reactant gases on described particle under the operational condition of the fixed-bed reactor that are generally used for ethylene oxychlorination by means of these features.Because described particle has in a large number cross section freely, less to the resistance of gas flow, corresponding load loss is also few.In addition, low equivalent diameter (equivalent diameter is the value of 6 * volume/total area) means to have bigger surface-area, that is to say to have the ratio of high surface-area to volume.This just makes reactant gases have preferably with catalyst surface and contacts, and helps the conversion of reactant and has limited the internal divergence phenomenon, has correspondingly improved the selectivity of oxi-chlorination.The catalyzer that uses catalyzer of the present invention and use to have known form is compared, and it is high by 1 that per unit volume uses more a spot of catalyzer to obtain, the productive rate of 2-ethylene dichloride.
Granules of catalyst also can have and is essentially the triangular cross section that has the angle, garden.
The ratio of the diameter in through-hole spacing (being the distance between their respective axis) and described hole is preferably between 1.15-1.5, further preferably between 1.3-1.4.
The ratio of particulate height and through-hole spacing is preferably between 1.5-2.5, further preferably between 1.7-2.3.
Have at catalyzer under the situation of circular cross section, the ratio of the radius-of-curvature of each lobe and the spacing of through hole is preferably between 0.6-0.9, further preferably between 0.7-0.8.The ratio of the radius-of-curvature of lobe and the radius of through hole is preferably between 1.3-2.7, further preferably between 1.8-2.10.The ratio of the radius in the external garden of cross section and the radius-of-curvature of circular lobe is preferably between 1.6-2, further preferably between 1.7-1.85.Each many lobes type particulate surface area/volume ratio value preferably is higher than 2.0, further preferably is higher than 2.2.
Have at catalyzer under the situation of triangular cross section, the radius-of-curvature at each angle, garden and the ratio of through-hole spacing are preferably between 0.6-0.9, further preferably between 0.7-0.8.The ratio of the rate radius at the radius in the external garden of cross section and each angle, garden is preferably between 1.6-2, further preferably between 1.7-1.85.The particulate surface area/volume ratio rate of each many triangle sections pattern is preferably greater than 2.0, further is preferably greater than 2.2.
Provide embodiment in mode below to non restrictive description of the present invention.Embodiment 1
With surface-area is 270m
2/ g, pore volume are 0.5cm
3The dispersed alumina compressing tablet of the powder type of/g, to form three lobe right cylinders, each has three through holes.The high 5mm of cylinder, through-hole diameter are 1.7mm, and the overall dimension of cross section is 5.7mm; The average total surface area of each particulate is 202mm
2
On the wall of forming room that is used for forming through hole and plunger, cover the thin hard ester acid of one deck with continuous air flow.
Three lobe particles were 550 ℃ of following roastings 3 hours, and with the aqueous solution dipping of cupric chloride and Repone K, the cupric chloride that contains in the aqueous solution and the amount of Repone K can provide following catalyst composition (weight): CuCl then
2=15%; K=5%; Al
2O
3=80%.
Behind the dipping, particle is following dry 3 hours at 150 ℃.
The surface-area of resulting granules of catalyst is 92m
2/ g (BET), porosity is 0.28cm
3/ g (mercury porosimeter).The distribution of pore volume is the radius that has 60-70A above 40% hole.Its axial rupture stress (breaking strain) is the 68kg/ particle.
For determining its activity, productive rate, selectivity and the pressure-losses, it is 26.6mm that catalyzer is installed to an internal diameter, and in the nickel pipe reactor of high 1300mm, reactor is placed in the thermostatically controlled silicone oil bath.
Shape of the load from top to bottom is as follows:
-the first layer, thick 400mm is mixed by the catalyzer and the graphite of the right cylinder form of extruding, and cylinder is 5 * 5mm, and the volume ratio of catalyzer/thinner is 1: 1;
-the second layer, thick 400mm is made up of granules of catalyst.
Gas stream is introduced from the top down, and its flow is:
Ethene 21.6Nl/h
HCl 40Nl/h
Air 57Nl/h
It is such value of 99% that the temperature that thermostatic control is bathed remains on the transformation efficiency that can make HCl.
The pressure of reactor exit is 1 normal atmosphere, and the pressure compensation at Reactor inlet place is owing to fall by the caused pressure of reactor.
Cooling (chilling) reaction product.Use has can separate 1, and the Hewlett-Packard chromatographic instrument of the capillary column of 2-ethylene dichloride, chloral, ethyl chloride and other chlorinated secondary product carries out gas chromatographic analysis to liquid ingredient.Use has the separating ethene of being suitable for, CO, CO
2, O
2And N
2The Carlo ErbaFractovap gas chromatograph analytical gas component of pillar.
Bathing under 200 ℃ the temperature that provides by thermostatic control, be converted into 1, the selectivity of 2-ethylene dichloride is 99%; Ethyl chloride is 0.15% (mole), and chloral is 0.15% (mole).
The pressure-losses is 3.5mmH
2O.Comparing embodiment
Repeat the Preparation of catalysts method of embodiment 1, still, the cylindrical alumina particle of three lobes is to use the stearic acid acquisition that is dispersed in 3% in the alumina powder of wanting compressing tablet (weight).
The surface-area of resulting catalyzer is 107m
2/ g, porosity is 0.31cm
3/ g has quite wide pore volume distribution (radius distribution of 70% pore volume is in 50-200A).
The catalytic selectivity of measuring under the condition of embodiment 1 is 98% (mole); The ethyl chloride that forms is 0.2% mole, and the muriate of formation is 0.15% (mole).
Claims (12)
1. one kind contains cupric chloride and ethylene oxychlorination can be become 1 as hollow cylindrical particle form active ingredient, that have at least three through holes, the catalyzer of 2-ethylene dichloride is characterized in that at least 40% pore volume has the radius corresponding to the peak value of void distribution curve.
2. according to the catalyzer of claim 1, its surface-area is at 80-380m
3Between/the g.
3. according to the catalyzer of claim 1 or 2, the pore volume above 40% has the radius of 60-70A.
4. according to claim 1,2 or 3 catalyzer, wherein through hole is parallel to each other basically, and substantially parallel with the particulate axis.
5. according to the catalyzer of claim 4, wherein through hole has circular cross section, and it is the angle of equilateral triangle basically that its axis has formed on the particulate cross section.
6. according to the catalyzer of claim 4 or 5, wherein the particulate surface-area to the ratio of volume greater than 2.
7. 4 or 5 catalyzer as requested, the ratio of the radius-of-curvature of lobe and the radius of through hole is between 1.3-2.7.
8. according to the catalyzer of claim 4 or 5, particulate high with the ratio of the pitch of holes of the distance qualification between respective axis between 1.5-2.5.
9. according to the catalyzer of claim 5, wherein its axial rupture stress is higher than the 65kg/ particle.
10. according to the catalyzer of aforementioned claim, be to obtain with following method, this method comprises: make with lubricator on the wall of forming room and on the plunger of mould, with the aluminum oxide compressed moulding, after 400-700 ℃ of following roasting, with the muriatic aqueous solution dipping of cupric chloride and basic metal or alkaline-earth metal.
11. one kind prepares and contains cupric chloride and ethylene oxychlorination can be become 1 as hollow cylindrical particle form active ingredient, that have at least three through holes, the method of the catalyzer of 2-ethylene dichloride, the particle that it is characterized in that granules of catalyst and support of the catalyst prepares by compressed moulding, wherein, on forming room's wall and mould plunger, make with lubricator for lubricated.
12. one kind becomes 1 with ethylene oxychlorination in fixed bed, the method for 2-ethylene dichloride, the catalyzer that wherein fills catalyzer that claim 1-10 limited in the fixed bed or obtain by the method for claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96123308 CN1154873A (en) | 1995-11-21 | 1996-11-21 | Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI95A002396 | 1995-11-21 | ||
| CN 96123308 CN1154873A (en) | 1995-11-21 | 1996-11-21 | Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154873A true CN1154873A (en) | 1997-07-23 |
Family
ID=5127619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96123308 Pending CN1154873A (en) | 1995-11-21 | 1996-11-21 | Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154873A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105392561A (en) * | 2013-07-17 | 2016-03-09 | 东曹株式会社 | Heterogeneous catalyst and catalyst system for manufacturing 1,2-dichloroethane |
-
1996
- 1996-11-21 CN CN 96123308 patent/CN1154873A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105392561A (en) * | 2013-07-17 | 2016-03-09 | 东曹株式会社 | Heterogeneous catalyst and catalyst system for manufacturing 1,2-dichloroethane |
| CN105392561B (en) * | 2013-07-17 | 2018-04-03 | 东曹株式会社 | The catalyst for producing system of heterogeneous catalysis and 1,2 dichloroethanes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1198688C (en) | Formed catalyst | |
| CN1085951C (en) | Catalyst for preparation of styrene by ethylbenzene dehydrogenation | |
| US4510263A (en) | Catalyst with high geometric surface area alumina extrudate and catalyst with high geometric surface area | |
| CN1044573C (en) | Catalyst granules, in particular for the oxidative dehydrogenation of methanol in order to yield formaldehyde | |
| EP0732146B1 (en) | Catalysts obtained by tabletting | |
| KR100451661B1 (en) | A catalyst for oxychlorination of ethylene, a method for producing the catalyst, and an oxychlorination method using the catalyst | |
| JP3781453B2 (en) | Granular catalyst for the synthesis of 1,2-dichloroethane and fixed bed process for oxychlorination of ethylene using the catalyst | |
| JPS621779B2 (en) | ||
| KR20100070293A (en) | Catalysts for oxychlorination of ethylene to 1,2-dichloroethane | |
| TWI642481B (en) | Catalyst system for the production of heterogeneous catalysts and 1,2-dichloroethane | |
| CN1154873A (en) | Catalysts for oxichlorination of ethylene, method for preparing them, and oxichlorination method using the same | |
| KR20140010363A (en) | Catalyst system, comprising catalyst pellets and diluent beads with predefined dimensions and physicochemical properties | |
| CA2288364A1 (en) | Catalysts for the oxi-chlorination of ethylene to 1,2-dichloroethane | |
| CN1039917C (en) | Pt-Sn-Ti multi-metal reforming catalyst | |
| RU2172211C2 (en) | Ethylene oxidative chlorination catalyst, method of preparation thereof, and oxidative chlorination process utilizing this catalyst | |
| JP6766602B2 (en) | Catalyst system for producing 1,2-dichloroethane and method for producing 1,2-dichloroethane | |
| CA1189052A (en) | High porosity catalyst | |
| HUT58564A (en) | Catalyzer body for separating inorganic contaminations particularly in the course of hydrorefining hydrocarbon fractions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1001382 Country of ref document: HK |