CN1280880A - Catalyst for preparing dichloroethane by oxychlorination of ethene with pure oxygen method and its preparing process - Google Patents
Catalyst for preparing dichloroethane by oxychlorination of ethene with pure oxygen method and its preparing process Download PDFInfo
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- CN1280880A CN1280880A CN 99109884 CN99109884A CN1280880A CN 1280880 A CN1280880 A CN 1280880A CN 99109884 CN99109884 CN 99109884 CN 99109884 A CN99109884 A CN 99109884A CN 1280880 A CN1280880 A CN 1280880A
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Abstract
A catalyst for preparing 1,2-dichloroethane by oxychlorination of ethene with pure oxygen process is prepared from the solution of copper chloride in hydrochloric acid (A), the solution of alkali metal, alkali-earth metal, or rare-earth metal or cerium chloride of carbonate in hydrochloric acid (B) and solution of sodium metaaluminate (C) through co-precipitation. Its phase structure is Cu2(OH)3Cl.M(OH)Cl.gamma-Al2O3, containing Cu 8-13% and other metals 0.5-3%. Its advantages include high transform rate of Hcl (up to 99.6%), high purity of dichloroethane (higher than 99%) and high productivity of reactor (increased by 3-5%).
Description
The present invention relates to a kind of with pure oxygen, hydrogen chloride and ethylene raw, by the oxi-chlorination of ethene, the preparation 1, fluid catalyst of 2-dichloroethanes and preparation method thereof.More particularly, the present invention be disclosed to CN1114594A be raw material with copper chloride hydrochloric acid solution A and sodium aluminate solution B, prepare alkene oxychlorination fluid catalyst preparation method's improvement through coprecipitation.
Ethylene oxychlorination is to be the production method of raw material preparing chloroethylene monomer with ethene.This method at first realized industrialization by U.S. B.F.Goodrich company in 1964.At present, according to the difference of raw material route, two kinds of different production methods of industrial employing: a kind of is to be the air method of representative with U.S. B.F.Goodrich company.This method is to be that raw material carries out oxi-chlorination with air, ethene and hydrogen chloride.Another kind is that to press KCC with Mitsui east be the oxygen method of representative.This method is to be that raw material carries out oxi-chlorination with pure oxygen, ethene and hydrogen chloride.The oxygen method has advantages such as discharge amount of exhaust gas is few, power consumption is low, catalyst loading is big, is the method for preferentially selecting for use at present.Because the difference of method for preparing catalyst, the fluid catalyst that ethylene oxychlorination is used can adopt two kinds of different preparation methods to prepare again.A kind of is to use infusion process, and another kind is to use coprecipitation.Infusion process is the carrier with certain rerum natura and particle diameter, immerses in the activity of such catalysts component solution as carriers such as silica, aluminium oxide, silica gel, and after stirring, catalyst is made in drying and roasting.
U.S. B.F.Goodrich company discloses a kind of method with the immersion process for preparing catalyst (being incorporated herein reference referring to CN1054764A-).This method is to be that 2-8 weight %, rare earth metal salt are that 0.2-10 weight % and alkali metal salt are 0.25-2.3 weight % solution with activity of such catalysts component mantoquita, is impregnated into altogether on the carriers such as aluminium oxide of high surface.Carrier plays an important role to improving activity of such catalysts, selectivity and mechanical strength and heat endurance.
It is that active component is carried out coprecipitation reaction with carrier mass that coprecipitation prepares catalyst, makes the gel coprecipitate earlier, spray-dried again moulding and make the catalyst with certain viscosity and certain particle size.The catalyst that makes in this way, active component and carrier mix, and the active component obscission can not take place, and also do not need carrier is carried out preliminary treatment.
The Japan clear 45-39616 of special permission communique JP-discloses a kind of preparation method of hydro carbons process for oxychlorination fluid catalyst in (on December 12nd, 1970).This catalyst prepares with coprecipitation.This method is to be raw material with the hydrochloric acid solution of copper chloride and sodium aluminate solution, makes the gel coprecipitate through coprecipitation reaction, makes catalyst again after aging, pulp, spray drying forming, washing and roasting.The shortcoming of this catalyst is that catalyst is subacidity, etching reactor.
Chinese patent CN1114594A (be incorporated herein with reference to) washes catalyst with water and causes catalytic component to run off for overcoming in the above-mentioned Japan Patent, and remaining acid is difficult for the shortcoming of wash-out, has proposed a kind of method with the alkaline aqueous solution washing.So both can wash acid and sodium ion remaining in the catalyst off, mantoquita is not run off, the catalyst after washing has neutrality, not etching apparatus.
But, no matter be Japan's special permission communique (the clear 45-39616 of JP-) disclosed method, or the disclosed method of Chinese patent (CN1114594A), adopting the catalyst of coprecipitation preparation all is that single copper chloride is the activity of such catalysts component.Therefore when catalyst is used for ethylene oxychlorination, the loss of copper chloride can take place under the pyroreaction condition all, and separate out because of copper chloride catalyst is clamminess, thereby make the fluidisation situation variation of catalyst, selectivity decline.In order to overcome the shortcoming that single copper chloride component produces, ethylene oxychlorination catalyst patent (US.P.5202511, US.P.3862996 etc.) with immersion process for preparing all is with the copper chloride on the basis of main active component that is catalyst, add second components such as a spot of potassium, magnesium or calcium, thereby improve the fluidized state of catalyst and improve selection of catalysts.Because catalyst prepared is the carrier that preparation earlier has suitable pore volume and specific area, can adopt single-steeping then or flood step by step the various active component is immersed on the carrier, makes catalyst after drying.And coprecipitation is when preparing catalyst, because several active components will form precipitation simultaneously, and after precipitation generates, also need wash, because in conjunction with insecure, some component is when sediment washs, run off easily, therefore can not get estimating the catalyst of forming.
For this reason, the inventor has found the preparation method of preparation ethylene oxychlorination with fluid catalyst three component coprecipitates, thereby has finished the present invention through research in depth for a long time.
The objective of the invention is described to CN1114594A is raw material with copper chloride hydrochloric acid solution A and sodium aluminate solution B, preparing the alkene oxi-chlorination through coprecipitation improves with the Preparation of catalysts method, promptly on the basis of the one pack system copper chloride catalyst that CN1114594A prepares, add metallic elements such as lithium, potassium, calcium, magnesium, lanthanum or cerium by coprecipitation and make the Catalysts and its preparation method that a kind of performance is better than the prior art catalyst.
Coprecipitation prepares the multicomponent ethylene oxychlorination catalyst and does not appear in the newspapers at present.It is exploitation co-precipitation legal system ethylene oxychlorination catalyst a company the earliest that Japan's catalyst changes into Co., Ltd..The said firm is still the co-precipitation preparation method of one pack system copper chloride catalyst in preparation method's (Japanese kokai publication hei 9-117666 is incorporated herein reference) of recent disclosed ethylene oxychlorination catalyst.The main points of this method just change the Cu/Al of catalyst
2O
3The specific area of ratio and carrier.The invention solves the technical barrier in the multicomponent co-precipitation, thereby make the multicomponent catalyst of high selectivity.
The preparation method of multicomponent catalyst of the present invention comprises following several steps:
1. the preparation of co-precipitation solution
Press the ratio of the required composition of catalyst, copper chloride is dissolved in the hydrochloric acid solution A that concentration is preparation copper chloride in the 25-33 weight % hydrochloric acid; It is that 25-33 weight % hydrochloric acid prepares alkali-metal hydrochloric acid solution, to be dissolved in concentration be that 25-33 weight % hydrochloric acid prepares the hydrochloric acid solution of alkaline-earth metal or the chloride of rare earth metal such as lanthanum or cerium or carbonate are dissolved in concentration is the hydrochloric acid solution B that 25-33 weight % hydrochloric acid prepares rare earth metal with the chloride of alkaline-earth metal such as calcium or magnesium or carbonate that the chloride of alkali metal such as lithium or potassium or carbonate are dissolved in concentration; Alumina powder is added in the liquid caustic soda,, generate Al 100-120 ℃ of reaction
2O
3/ NaOH is the sodium aluminate solution C of 1.2-1.8 weight %; A, B solution are mixed, and the pH value of control mixed solution is 0.1-3, is preferably 1-2, make many metal chloride solutions.
2. co-precipitation is neutralized into glue
Adopt Chinese patent (CN1114594A) disclosed method to carry out co-precipitation and be neutralized into glue, it becomes the adhesive tape part to be: becoming the glue temperature is 20-60 ℃, is preferably 45-55 ℃; Mixing speed is 300-800 rev/min; During neutralization reaction, pH value is controlled to be 5.5-9.5, is preferably 7.0-9.0.In and the time, A, B mixed solution with metering adds in the reactor earlier, and the maintenance temperature is 20-40 ℃, the C solution that slowly adds metering carries out neutralization reaction then, want the variation of strict control pH value in the course of reaction, when treating that pH value reaches 9-9.5, stop reaction, reaction finishes the back and continues to stir one hour.
3. pulp and spray-drying
The filter cake that press filtration is good is incorporated as in the gel volume 2-4 deionized water doubly, at room temperature slurrying 4-6 hour, carry out the glue homogenizing, send into then and carry out spray drying forming in the press spray drying tower, the operating condition of drying tower is: drying tower hot blast inlet temperature is 400-500 ℃, and outlet temperature is 80-150 ℃.The particle mean size of the microspherical catalyst that makes after the drying is 50-70 μ, wherein is less than or equal to 30 μ≤15 weight %, is less than or equal to 90 μ 〉=80 weight %.
4. alkaline aqueous solution washing
For copper and other metal in the catalyst are not run off, can wash simultaneously harmful substance sodium chloride and remaining acid in the catalyst again off, method of the present invention still adopts disclosed washing methods in the Chinese patent (CN1114594), promptly under agitation wash with alkaline solution, remove the sodium ion in the catalyst microballoon, and copper ion and other metal ion become in alkaline solution under the precipitation of hydroxide, remove acid residual in the catalyst simultaneously, it is neutral that the catalyst of preparation is, not etching reactor.
5. calcination
Microspherical catalyst after the washing after 100-120 ℃ of drying, through 300-700 ℃ of calcination 1-3 hour, makes catalyst have stable phase structure earlier again.
Adopt the catalyst of method preparation of the present invention, have following rerum natura.
(1) copper content 8-13 weight %
(2) other metal (M) content 0.5-3.0 weight %
(3) phase structure Cu
2(OH)
3.ClM (OH) Cl-γ-Al
2O
3
(4) bulk density 0.8-1.2g/ml
(5) pore volume 0.3-0.4ml/g
(6) specific area 130-200m
2/ g
(7) particle mean size 50-70 μ.
Below, further describe the present invention with embodiment.
Embodiment 1
40 gram copper chlorides and 2.5 gram magnesium chlorides are dissolved in respectively in 408 milliliters of hydrochloric acid that concentration is 33 weight %, make co-precipitation solution A and B, and, under agitation, slowly add Al in the above-mentioned solution adding and in the still
2O
3Content is that 165/g/l, NaOH content are the sodium aluminate solution C of the equivalent of 247g/l, is 9.5 times in the pH value, carries out coprecipitation reaction one hour, and the mixing speed when becoming glue is 400 rev/mins.After precipitation reaction finished, with the gel press filtration, the filter cake that obtains was through pulp, spray drying forming, ammonia wash and 600 ℃ of calcinations after make microspherical catalyst.Its rerum natura row are as table 1.
Embodiment 2
50 gram copper chlorides, 2.5 gram magnesium chlorides and 0.8 gram cerium chloride are dissolved in respectively in 348 milliliters of hydrochloric acid that concentration is 25 weight %, are mixed with co-precipitation solution A and B.Other preparation condition is identical with embodiment 1.The rerum natura row of the catalyst that makes are as table 1.
Embodiment 3
50 gram copper chlorides, 2.9 gram potassium chloride and 0.7 gram cerium chloride are dissolved in respectively in 348 milliliters of hydrochloric acid that concentration is 33 weight %, are mixed with co-precipitation solution A and B, other is identical with embodiment 1.The catalyst rerum natura that makes is listed in table 1.
Embodiment 4
50 gram copper chlorides, 2.2 gram potassium chloride and 0.6 gram cerium chloride are dissolved in respectively in 348 milliliters the hydrochloric acid that concentration is 33 weight %, are mixed with co-precipitation solution A and B, other is identical with embodiment 1.The catalyst rerum natura that makes is listed in table 1.
Comparative Examples
With causticity than (NaOH/Al
2O
3-weight ratio) be 1.5, Al
2O
3Content is that B solution 900ml and the 45 gram copper chlorides (containing two water) of 165g/l are dissolved in 408.5 grams, 33% hydrochloric acid, be made into copper content and be 15.5% A solution 900ml, at PH is to react for 9.5 times, it is 400 rev/mins that control is neutralized into the glue mixing speed, and the gel of generation is after press filtration, and filter cake is directly used acidic aqueous solution slurrying, spray drying forming, article shaped is made the microballoons catalyst 600 ℃ of calcinations after being 11 ammonia spirit washing drying with pH value again, and its rerum natura is listed in table 1.
The rerum natura of the catalyst that the different preparation methods of table 1 make
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples |
| Weight of copper % | ????11．80 | ????11．87 | ????11．77 | ????12．38 |
| Magnesium weight % | ????1．30 | ????1．28 | ||
| Potassium weight % | ????1．16 | |||
| Cerium weight % | ????0．68 | ????0．65 | ||
| Bulk density g/ml | ????0．93 | ????0．97 | ????0．95 | ????0．96 |
| Pore volume ml/g | ????0．3 | ????0．29 | ????0．29 | ????0．30 |
| Specific area m2/g | ????178 | ????175 | ????168 | ????188 |
| Sodium oxide molybdena weight % | ???＜0．05 | ???＜0．05 | ???＜0．05 | ???＜0．05 |
| Particle mean size μ | ????57 | ????57 | ????58 | ????56 |
The catalyst of the catalyst of embodiment 1-3 and Comparative Examples is respectively got 10 grams, carry out activity rating with the pressurised fluidized bed reactor of φ 25 * 400mm, its appreciation condition is: reaction pressure is 0.2Mpa, and reaction temperature is 220 ± 5 ℃, and gas space velocity is 1500hr
-1Resulting reaction result is listed in table 2.
The reaction result of table 2 different catalysts
| The embodiment numbering | ????1 | ????2 | ????3 | Comparative Examples |
| Reaction temperature ℃ | ????222 | ????221 | ????223 | ????224 |
| Reaction pressure MPa | ????0．2 | ????0．2 | ????0．2 | ????0．2 |
| HCl conversion ratio % | ????99．68 | ????99．72 | ????99．86 | ????99．6 |
| Dichloroethanes yield Grams Per Hour | ????15．28 | ????15．56 | ????15．94 | ????14．9 |
| Dichloroethanes purity % | ????99．6 | ????99．6 | ????99．65 | ????99．6 |
Find out by above three embodiment and Comparative Examples, adopt the catalyst of method preparation of the present invention, owing in main active component copper chloride, add a spot of co-catalyst lithium, potassium, calcium, magnesium, lanthanum or cerium etc., catalyst selectivity is had significantly improve, purpose product dichloroethanes yield increases significantly.Adopt the catalyst of the inventive method preparation, can make the production capacity of pre-existing reactors improve 1-5%.
Claims (7)
1. a hydrochloric acid solution B and the sodium aluminate solution C by hydrochloric acid solution A, alkali metal chloride or carbonate, alkaline earth metal chloride or carbonate, rare-earth metal chloride or the carbonate of copper chloride is raw material, with the alkene oxi-chlorination catalyst of coprecipitation preparation, the feature of this catalyst is that phase structure is Cu
2(OH)
3ClM (OH) Cl γ-Al
2O
3, and step preparation in the following order:
(1) prepares hydrochloric acid solution B, the sodium aluminate solution C of copper chloride hydrochloric acid solution A, alkali metal chloride or carbonate, alkaline earth metal chloride or carbonate, rare-earth metal chloride or carbonate respectively, and above-mentioned solution mixed be neutralized into glue, obtain coprecipitate;
(2) isolated by filtration coprecipitate;
(3) with spray drying forming after the pulp of coprecipitate water;
(4) article shaped is washed with alkaline solution;
(5) calcination.
2. method for preparing claim 1 catalyst is characterized in that this method comprises several steps in the following order:
(1) prepares salt ester solution B, the sodium aluminate solution C of copper chloride hydrochloric acid solution A, alkali metal chloride or carbonate, alkaline earth metal chloride or carbonate, rare-earth metal chloride or carbonate respectively, and above-mentioned solution mixed by a certain percentage, in temperature is that 35-70 ℃, mixing speed are that 300-800 rev/min, pH value are controlled under the condition of 5-10, be neutralized into glue, obtain coprecipitate;
(2) isolated by filtration coprecipitate;
(3) with after the pulp of coprecipitate water, spray drying forming;
(4) article shaped is washed with alkaline solution;
(5) calcination.
3. by the method for claim 2, it is characterized in that being neutralized into glue and adopt one-dimensional method, or adopt cocurrent process.
4. by the method for claim 2, it is characterized in that mixing speed is 400-600 rev/min.
5. by the method for claim 2 or 3, it is characterized in that the pH value that is neutralized into glue is 7-9.
6. by the method for claim 2 or 3, it is characterized in that washing soda solution is ammonium hydroxide aqueous solution.
7. press the method for claim 2, it is 8-13 weight % that the ratio that it is characterized in that the hydrochloric acid solution B of copper chloride hydrochloric acid solution A, alkali metal chloride or carbonate, alkaline earth metal chloride or carbonate, rare-earth metal chloride or carbonate and sodium aluminate solution C makes the catalyst cupric of preparation, and other metal M is 0.5-3 weight %.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109884A CN1101266C (en) | 1999-07-20 | 1999-07-20 | Catalyst for preparing dichloroethane by oxychlorination of ethene with pure oxygen method and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109884A CN1101266C (en) | 1999-07-20 | 1999-07-20 | Catalyst for preparing dichloroethane by oxychlorination of ethene with pure oxygen method and its preparing process |
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|---|---|
| CN1280880A true CN1280880A (en) | 2001-01-24 |
| CN1101266C CN1101266C (en) | 2003-02-12 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457260C (en) * | 2006-01-10 | 2009-02-04 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
| CN102463116A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method thereof and preparation method of dichloroethane |
| CN103657664A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method and application for olefin oxychlorination catalyst, and preparation method for dichloroethane |
| CN103657663A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst and preparation method for same, and preparation method for dichloroethane |
| CN110961161A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for olefin oxychlorination reaction and preparation method and application thereof |
| CN112675827A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Alumina carrier and ethylene oxychlorination catalyst prepared from same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1202538B (en) * | 1987-02-13 | 1989-02-09 | Enichem Sintesi | OXYCHLORATION CATALYST AND PROCEDURE FOR ITS PREPARATION |
| CN1045727C (en) * | 1994-07-05 | 1999-10-20 | 化学工业部北京化工研究院 | Fluidized bed oxygen method hydrocarbons oxychlorination reaction catalyst and preparation method thereof |
-
1999
- 1999-07-20 CN CN99109884A patent/CN1101266C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457260C (en) * | 2006-01-10 | 2009-02-04 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
| CN102463116A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method thereof and preparation method of dichloroethane |
| CN103657664A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method and application for olefin oxychlorination catalyst, and preparation method for dichloroethane |
| CN103657663A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst and preparation method for same, and preparation method for dichloroethane |
| CN103657664B (en) * | 2012-09-07 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of preparation method of olefin oxychlorination catalyst and its preparation method and application and dichloroethanes |
| CN103657663B (en) * | 2012-09-07 | 2016-09-21 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst and preparation method thereof and the preparation method of dichloroethanes |
| CN110961161A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for olefin oxychlorination reaction and preparation method and application thereof |
| CN112675827A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Alumina carrier and ethylene oxychlorination catalyst prepared from same |
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|---|---|
| CN1101266C (en) | 2003-02-12 |
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