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Publication numberCN1173168 A
Publication typeApplication
Application numberCN 95197457
PCT numberPCT/EP1995/004516
Publication date11 Feb 1998
Filing date15 Nov 1995
Priority date24 Nov 1994
Also published asCN1051071C, DE69508426D1, DE69508426T2, EP0793633A1, EP0793633B1, US5821394, WO1996016003A1
Publication number95197457.2, CN 1173168 A, CN 1173168A, CN 95197457, CN-A-1173168, CN1173168 A, CN1173168A, CN95197457, CN95197457.2, PCT/1995/4516, PCT/EP/1995/004516, PCT/EP/1995/04516, PCT/EP/95/004516, PCT/EP/95/04516, PCT/EP1995/004516, PCT/EP1995/04516, PCT/EP1995004516, PCT/EP199504516, PCT/EP95/004516, PCT/EP95/04516, PCT/EP95004516, PCT/EP9504516
InventorsJ·P·肖布雷兹, F·詹森斯
Applicant索尔维公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Method for converting a chlorinated alkane into a less chlerinated alkene
CN 1173168 A
Abstract  translated from Chinese
催化剂存在下与氢气反应使氯代烷转化成至少一种较低度氯代的烯烃的方法,催化剂包含钯和选自下列金属中的一种及其混合物:银、镓、铟、铊、锗、锡、铅、砷、锑和铋。 In the presence of a catalyst and reacting the chlorinated alkane hydrogen is converted to a lower degree of at least one method of chlorinated olefins, the catalyst comprises palladium and one metal selected from and mixtures thereof: silver, gallium, indium, thallium, germanium , tin, lead, arsenic, antimony and bismuth.
Claims(13)  translated from Chinese
1.催化剂存在下氯代烷与氢气反应使氯代烷转化为至少一种较低度氯代的烯烃的方法,该催化剂沉积在载体上,包含VIII族的一种金属和金属M,其特征在于该VIII族的金属是钯,金属M选自银、镓、铟、铊、锗、锡、铅、砷、锑、铋及其混合物。 1. The presence of a catalyst reacting the chlorinated alkane with hydrogen chloride is converted to alkoxy method of at least one chlorinated lower olefins, the catalyst deposited on a support comprising a Group VIII metal and a metal M, wherein that the Group VIII metal is palladium, a metal M selected from silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof.
2.根据权利要求1的方法,其特征在于金属M选自银、锡、铅、铊和铋。 2. A method according to claim 1, wherein the metal M is selected from silver, tin, lead, thallium and bismuth.
3.根据权利要求2的方法,其特征在于金属M是锡或银。 3. The method according to claim 2, wherein the metal M is tin or silver.
4.根据权利要求1到3中任一项的方法,其特征在于氯代烷选自氯代丙烷。 4. A method according to any one of claims 1-3, characterized in that the chlorinated alkane is selected from propane chloride.
5.根据权利要求4的方法,其特征在于氯代丙烷是烯丙基氯和/或表氯醇生产中形成的副产物。 5. The method according to claim 4, wherein the chlorinated propane is a byproduct of allyl chloride and / or the production of epichlorohydrin formed.
6.根据权利要求4或5的方法,其特征在于氯代烷是1,2-二氯丙烷。 6. The method according to claim 4 or claim 5, characterized in that the chlorinated alkane is 1,2-dichloropropane.
7.根据权利要求1到6中任一项的方法,其特征在于载体是活性炭。 7. A method according to any one of claims 1-6, wherein the carrier is activated carbon.
8.根据权利要求1到7中任一项的方法,其特征在于载体上钯的重量相当于载体重量的0.05~10%。 8. A method according to any one of claims 1-7, wherein the equivalent weight of palladium on a support 0.05 to 10% by weight of the carrier.
9.根据权利要求1到8中任一项的方法,其特征在于载体上金属M的重量相当于载体重量的0.05%~10%。 9. A method according to any one of claims 1-8, characterized in that the metal M on the support is equivalent to 0.05% by weight to 10% by weight of the carrier.
10.根据权利要求1到9中任一项的方法,其特征在于钯对金属M的重量比为0.05~20。 10. A method according to any one of claims 1-9, characterized in that the metal M is palladium weight ratio of from 0.05 to 20.
11.根据权利要求1到10中任一项的方法,其特征在于反应在温度150~450℃、压力1~30bar的条件下进行。 11. A method according to any one of claims 1 to 10, characterized in that the reaction at a temperature of 150 ~ 450 ℃, under a pressure of 1 ~ 30bar performed.
12.根据权利要求1到11中任一项的方法,其特征在于氢气对氯代烷的摩尔比为0.1~40。 12. A method according to any one of claims 1 to 11, characterized in that the hydrogen to chlorinated alkane molar ratio of from 0.1 to 40.
13.根据权利要求1到12中任一项的方法,其特征在于反应在气相下进行,所用气体与催化剂的平均接触时间为0.5~30秒。 13. The method of 1 to 12 according to any one of the preceding claims, characterized in that the reaction is carried out in the gas phase, the average contact time of the gas with the catalyst is 0.5 to 30 seconds.
Description  translated from Chinese
将氯代烷转化为较低度氯代的烯烃的方法 Methods chloroalkane translate to lower the degree of chlorinated olefin

本发明涉及在催化剂存在下氯代烷与氢气反应使氯代烷转化为至少一种较低度氯化的烯烃的方法,催化剂包含载体上的VIII族的一种金属和另一种金属。 The present invention relates to a catalyst in the presence of hydrogen and reacting the chlorinated alkane into at least one chlorinated alkane of chlorinated lower olefins, the catalyst comprising a Group VIII metal supported on a carrier and another metal.

国际申请WO-94/07828、WO-94/07827、WO-94/07823、WO-94/07821、WO-94/07820、WO-94/07819和WO-94/07818描述了在双金属催化剂存在下与氢气作用使不同的氯代烷转化为较低度氯代的烯烃的方法,该催化剂包含VIII族的一种金属和IB族的一种金属,置于一种载体上。 International Application WO-94/07828, WO-94/07827, WO-94/07823, WO-94/07821, WO-94/07820, WO-94/07819 and WO-94/07818 describes a bimetallic catalyst under the effect of hydrogen so that different chlorinated alkane conversion process of chlorinated lower olefins, which catalyst comprises a metal of a metal of Group IB and Group VIII placed on a carrier. 欧洲专利申请EP-A-0640574描述了在一种双金属催化剂存在下氯代烷向较低度氯代的烯烃的转化,该催化剂包含铂和第二种金属,如镧、钛、钒、铬、锰、铁、钴、镍、铜、锌、铟、锡或铋,它们置于一种载体上,在这些已知的方法中,当使用活性炭上的钯-铜催化剂时,能得到氯代烷的最高转化和烯烃生产的最高选择性。 European Patent Application EP-A-0640574 describes the conversion in the presence of a bimetallic catalyst of chlorinated alkane to chlorinated lower olefins, the catalyst comprising platinum and a second metal, such as lanthanum, titanium, vanadium, chromium , manganese, iron, cobalt, nickel, copper, zinc, indium, tin or bismuth, which is placed on a carrier, in these known methods, when using palladium on activated carbon - when copper catalyst, can be chlorinated alkyl highest selectivity highest conversion and olefin production. 国际申请WO-94/07819和欧洲专利申请EP-A-0640574描述了使1,2-二氯丙烷转化为丙烯的更明确的方法。 International Application WO-94/07819 and European Patent Application EP-A-0640574 describes making 1,2-dichloropropane into propylene clearer way. 明显地,上面特别提到的双金属催化剂不能同时获得1,2-二氯丙烷的高度转化率和丙烯的高选择性。 Obviously, the bimetallic catalysts specifically mentioned above can not be obtained with high selectivity of 1,2-dichloropropane height conversion and propylene simultaneously. 而且,这些催化剂关于丙烯的选择性开始很低,大量生成的是丙烷。 Furthermore, these catalysts begins on propylene selectivity is low, a large number of build is propane. 因此,这些已知催化剂不适于生产丙烯,该丙烯可以直接用作丙烯氯化生产烯丙基氯的生产线。 Thus, these known catalysts suitable for the production of propylene, the propylene can be directly used to produce propylene chlorination of allyl chloride production lines. 实际上,当包含丙烯和丙烷的混合物在烯丙基氯生产段再循环时,1-氯丙烷和/或2-氯丙烷由丙烷氯化产生,这些产物难以与烯丙基氯分离。 In fact, when the mixture comprises propylene and propane in the production of allyl chloride recycle section, 1-chloro-propane and / or 2-chloropropane produced by the chlorination of propane, the product is difficult to separate from allyl chloride. 这些已知催化剂的另一种不足是它们的快速减活。 These known catalysts Another disadvantage is their rapid deactivation. 因而,为了提高这些催化剂的初始选择性和它们的稳定性,用氯化氢预处理是必要的。 Thus, in order to improve the initial selectivity of these catalysts and their stability, it is necessary to pre-treatment with hydrogen chloride. 专利US-3892818透露了一种用氢气使1,2-二氯丙烷脱氯的方法,该方法在沉积于氧化铝上的双金属铑-金催化剂存在下进行的。 Patent US-3892818 discloses a 1,2-dichloropropane with hydrogen dechlorination method deposited on the alumina bimetallic rhodium - the presence of gold catalyst performed. 该催化剂有高活性和长寿命,但反应产物基本上是丙烷。 The catalyst has a high activity and a long life, but the reaction product is essentially propane.

现已找到一种方法,它没有了上述缺点,能使氯代烷转化为较低度氯代的烯烃时有好的选择性和优选的高度转化率,催化剂既不会随着时间快速减活,也不需要用氯化氢预处理。 Now find a way, it does not the above-mentioned disadvantages, can have a good selectivity and a high degree of conversion of preferred chlorinated alkane into less chlorinated alkene degree when neither catalyst deactivation with time fast It does not require pre-treatment with hydrogen chloride.

因而本发明涉及在催化剂存在下氯代烷与氢气反应使氯代烷转化为至少一种较低度氯代的烯烃的方法,该催化剂包含VIII族的一种金属和金属M沉积在一种载体上,其特征在于VIII族的金属是钯,金属M选自:银、镓、铟、铊、锗、锡、铅、砷、锑、铋及其混合物。 Thus, the present invention relates to a catalyst in the presence of hydrogen chloride and reacting the alkoxy chlorinated alkane into at least one method of chlorinated lower olefins, the catalyst comprises a Group VIII metal and a metal M deposited on a carrier , characterized in that the Group VIII metal is palladium, a metal M selected from: silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof.

用于本发明方法的氯代烷是一种包含至少一个氯原子的烷烃。 The method of the present invention is used is a chlorinated alkane alkane containing at least one chlorine atom. 对无环氯代烷已经得到的结果,更特别地,对于具有通式CnH2n+2-xClx的无环氯代烷,其中n是2~6的整数,x为1~(2n+2)的整数。 The results have been acyclic alkyl chloride, and more particularly, for having the general formula CnH2n + 2-xClx acyclic chlorinated alkane, wherein n is an integer of 2 to 6, x is 1 ~ (2n + 2) of the integer. 氯代丙烷特别有利,二氯丙烷和三氯丙烷更是尤其如此、1,2-二氯丙烷是非常特别有利的。 Chloropropane is particularly advantageous, trichloropropane dichloropropane and more particularly, 1,2-dichloropropane is very particularly advantageous.

术语较低度氯代的烯烃是指表示一种烯烃,该烯烃中碳原子数与所用氯代烷中的碳原子数相当,而氯原子至少少一个。 The term lower means of chlorinated olefin represents an olefin, the olefin used and the number of carbon atoms in alkyl chloride considerable number of carbon atoms, a chlorine atom and at least one less. 如本发明所定义的较低度氯代的烯烃中可能因而不含氯原子。 The present invention is defined as a lower degree of chlorinated olefins may thus no chlorine atoms. 就具有通式CnH2n+2-xClx的氯代烷(其中x=1~(2n+2))来说,根据本发明方法产生的烯烃因而相当于通式CnH2n-yCly,其中y在0~2n之间变化,不高于(x-1)。 It has the general formula CnH2n + 2-xClx chlorinated alkyl (where x = 1 ~ (2n + 2)), the method according to the present invention, the olefin thus generated corresponds to the general formula CnH2n-yCly, wherein y is 0 ~ 2n between changes, not higher than (x-1). 在本发明的方法中,氯代烷和氢气的反应可能产生一种单一的较低度氯代的烯烃或两种或多种较低度氯代的烯烃的混合物,其中较低度氯代的烯烃如上定义。 In the method of the present invention, the reaction of alkyl and hydrogen chloride may produce a single low degree chlorinated olefin or a mixture of two or more of chlorinated lower olefins, wherein the chlorinated lower degree of olefin as defined above.

用于本发明方法的催化剂包含钯和选自如下的金属M中的至少一种:银、镓、铟、铊、锗、锡、铅、砷、锑和铋中的至少一种金属M,它们沉积在载体上。 The catalyst for the process of this invention comprises palladium and a metal M selected from at least one of: silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony and bismuth at least one metal M, they deposited on the carrier. 金属M优选地从银、锡、铅、铊和铋中选取。 Metal M is preferably selected from silver, tin, lead, thallium and bismuth. 当金属M是锡时已经得到了好的结果。 When the metal M is tin've got good results. 当金属M是银时得到了极好的结果。 Excellent results obtained when the metal M is silver. 催化剂优选地基本上由钯和金属M沉积在载体上组成。 The catalyst preferably consists essentially of palladium and a metal M deposited on the carrier. 钯和金属M可能以元素状态存在或者以一种化合物的形式,例如盐或者氧化物存在。 Palladium and the metal M may exist in elemental form or in the form of a compound, e.g., salts or oxides. 催化剂优选地包含钯和金属M以元素状态存在。 The catalyst preferably comprises palladium and the metal M in elemental state.

作为催化剂载体,它们通常由多孔载体制成,例如那些直接用于氢化反应的催化剂一起使用的物质。 As a catalyst support, they are usually made of a porous carrier material such as those used directly in the hydrogenation reaction catalyst used with. 这些载体的例子有活性炭、氧化铝、二氧化硅、氧化钛、氧化锰、氧化锆、铝酸锂和硅胶-氧化铝。 Examples of such carriers are activated carbon, alumina, silica, titanium oxide, manganese oxide, zirconium oxide, lithium aluminate and silica - alumina. 优选载体是活性炭。 Preferred support is activated carbon.

按载体重量计,载体上有利的钯量至少为0.05%,优选地为至少为0.15%。 By weight of the carrier, the carrier advantageously a palladium content of at least 0.05%, preferably at least 0.15%. 通常,钯量不超过载体重量的10%。 Typically, an amount not exceeding 10% palladium by weight of the carrier. 优选地不超过5%。 Preferably not more than 5%.

载体上金属M的量至少相当于载体重量的0.05%有利,优选地为至少0.15%。 The amount of metal M on the support of at least the equivalent of 0.05% by weight of the carrier Advantageously, preferably at least 0.15%. 通常,该金属M的量不超过载体重量的10%。 Typically, the amount of the metal M is not more than 10% of the weight of the carrier. 优选不超过5%。 Preferably not more than 5%.

钯和金属M的重量比优选地至少为0.05。 Palladium and the weight ratio of the metal M is preferably at least 0.05. 该重量比特别优选地为至少0.1。 The ratio by weight and particularly preferably at least 0.1. 该重量比更特别优选地为至少0.25。 More particularly the weight ratio is preferably at least 0.25. 优选地,钯和金属M的重量比不超过20。 Preferably, the palladium and the metal M is not more than 20 weight ratio. 特别优选地,该比率不超过10。 Particularly preferably, the ratio is not more than 10. 更特别优选地不超过4。 More particularly preferably not more than 4.

根据本发明的具体实施方案,其中金属M为银,钯对银的重量比极特别优选地为至少0.4。 According to a particular embodiment of the present invention, wherein the metal M is silver, silver palladium weight ratio very particularly preferably at least 0.4. 在本发明的这种具体方案中,钯对银的重量比优选地不超过2.5。 In this particular embodiment of the invention, the palladium weight of silver is preferably not more than 2.5.

该催化剂任选另外含有至少另一种金属,该金属选自IB、IIB、IIIA、IVA、VA和VIII族,以元素状态或者以其化合物的形式存在(上述金属组根据《CRC化学物理手册》中的再版CAS命名法标示,该书第75版,1994-1995,DRLide,封面)。 The catalyst optionally further comprises at least one other metal, the metal is selected from IB, IIB, IIIA, IVA, VA and VIII, as elemental state or in the form of the presence of the compound (according to the above-described metal group "CRC Handbook of Chemistry Physics" The reprint CAS nomenclature mark, the first edition of the book 75, 1994-1995, DRLide, cover). 如果适当的话,该附加金属的量不应超过钯和金属M总重量的50%。 If appropriate, the amount of the additional metal should not exceed 50% of the palladium and the metal M of the total weight.

用于本发明方法的催化剂金属能沉积于载体上,方法是用一种或多种含催化剂金属组分的溶液浸渍后者。 The method of the present invention for the catalyst metal can be deposited on the carrier, it is to use one or more catalytic metal components impregnated with a solution containing the latter. 浸渍溶液优选盐的水溶液。 Impregnating solution is preferably an aqueous solution of the salt. 特别地,用于此目的的盐为氯化物、硝酸盐、醋酸盐或氨络合物。 In particular, for this purpose the salt is chloride, nitrate, acetate or ammine complex. 根据本发明方法的一种优选方案,由两次连续浸渍获得的催化剂得到使用。 According to one preferred embodiment of the method of the present invention, a catalyst obtained by the two consecutive impregnation be used. 在这种情况下,载体首先用含钯溶液浸渍,干燥,然后用含金属M的溶液浸渍,再干燥。 In this case, the support is first impregnated with a palladium-containing solution, dried, and then impregnated with a solution containing metal M, and then dried. 通常,浸渍和干燥后的载体在还原气氛中进行热处理,例如在至少100℃和优选地小于或等于400℃的温度下用氢气处理。 Typically, impregnation and drying the carrier after heat treatment in a reducing atmosphere, e.g., at least 100 ℃ and preferably less than or equal to 400 ℃ temperature treatment with hydrogen. 浸渍后载体的热处理可以在催化剂用于本方法之前进行,或者在氯代烷和氢气用于本方法的同时进行。 After heat treatment of the carrier may be impregnated prior to the present method for performing a catalyst, or simultaneously chlorinated alkane and hydrogen was used in the present method.

本发明的方法中,氢气对氯代烷的摩尔比优选地为至少0.1,更具体地至少为0.5。 The method of the present invention, the hydrogen to chlorinated alkane molar ratio is preferably at least 0.1, more particularly at least 0.5. 该比率优选地不超过40。 The ratio is preferably not more than 40. 特别优选,它不超过20。 Particularly preferably it does not exceed 20.

根据本发明的方法,氢气与氯代烷反应产生至少一种较低度氯代的烯烃,如上文所述。 The method according to the present invention, hydrogen chloride is reacted with an alkyl of producing at least one chlorinated lower olefins, as described above. 如果适当,氢气可以与另一种气体混合,该气体在氯代烷转化为较低度氯代的烯烃的反应条件下是惰性的。 If appropriate, hydrogen can be mixed with another gas, under the reaction conditions of the gas is converted to a lower alkyl chloride of the chlorinated olefin is inert. 使用的另一种气体可以是严格意义上的惰性气体组中的一种,如氦气,或者是不干扰上述反应的一种气体,如氢氯酸或一种烯烃。 Another gas used may be an inert gas in the strict sense of the group A, such as helium, or a gas does not interfere with the above reaction, such as hydrochloric acid or an olefin. 在该惰性气体选用烯烃情况下,优选氯代烷与氢气反应产生的烯烃或产生的多种烯烃中的一种。 In the case of an inert gas selected olefin, the olefin or olefins to produce a variety of preferred chlorinated alkane with hydrogen in a reaction. 氢气体积占氢气与另一种气体的总体积的分数优选为至少5%。 Volume of the total volume of the hydrogen gas with another gas, hydrogen fraction is preferably at least 5%. 特别优选地,氢气占总体积的分数至少10%。 Particularly preferably at least 10%, of the total hydrogen volume fraction.

本发明的方法可以在液相或气相中进行,优选地于气相中进行。 The method of the present invention can be carried out in a liquid phase or gas phase, preferably carried out in the gas phase. 本方法优选地于至少150℃下进行,更特别地至少200℃。 The method is preferably carried out in at least 150 ℃, more particularly at least 200 ℃. 湿度通常不超过450℃。 Humidity is usually no more than 450 ℃. 优选地它不超过400℃。 Preferably it does not exceed 400 ℃. 本方法进行时的压力本身没有严格要求。 Stress in itself is not critical when the present method. 通常使用至少1bar的压力。 Usually at least 1bar pressure. 通常,压力不超过30bar。 Typically, the pressure does not exceed 30bar. 优选地不超过10bar。 Preferably not more than 10bar.

本发明的方法在气相进行的情况下,所用气体与催化剂的平均接触时间,即催化剂所占体积与总物料流率的比值,在反应温度和压力下测定,优选地至少0.5秒,更特别地至少1秒。 The method of the present invention, the average contact time in the case of the gas phase, the gas with the catalyst, i.e., the ratio of the catalyst to the total volume occupied by the material flow rate, measured at the reaction temperature and pressure, preferably at least 0.5 seconds, more particularly at least one second. 该接触时间不超过30秒。 The contact time is not more than 30 seconds. 特别优选地,接触时间不超过20秒。 Particularly preferably, the contact time is less than 20 seconds.

本发明方法使同时获得氯代烷的高度转化率和生成较低度氯代的烯烃的很大选择性成为可能。 The method of the present invention allows to obtain simultaneously highly chloroalkane low conversion rate and generate a lot of chlorinated alkene selectivity possible. 本发明方法也使获得较低度氯代的烯烃的高选择性而没有任何烷烃或氯代烷显著生成成为可能,它在催化剂第一次使用时就能达到此优点而无需对催化剂用氯化氯预处理。 The method of the present invention also enables a high degree of selectivity for lower olefins and chlorinated alkanes or chloro alkoxy without any significant generation becomes possible, when it is first used catalyst can achieve this advantage without the catalyst with a chlorinating chlorine pretreatment. 而且,本发明方法有下列好处即催化剂随时间的减活化作用比现有技术的已有催化剂的减活化作用要慢得多。 Further, the method of the present invention has the following advantages i.e. much slower catalyst deactivation with time than the prior art deactivation of the catalyst has been.

在本发明方法中使用的氯代烷为1,2-二氯丙烷的特殊情况下,丙烯的获得有高选择性和高转化率。 Chlorinated alkane used in the process of the present invention is the special case of the 1,2-dichloropropane, propylene is obtained with a high selectivity and high conversion rates. 本发明因而特别涉及获得丙烯的方法,即催化剂存在下1,2-二氯丙烷与氢气反应,该催化剂包含钯和金属M,它们沉积在载体上,金属M选自银、镓、铟、铊、锗、锡、铅、砷、锑、铋、及其混合物。 The present invention thus relates to a method for obtaining particularly propylene, i.e. the presence of a catalyst under the reaction of 1,2-dichloropropane and hydrogen gas, the catalyst comprising palladium and a metal M, which is deposited on a support, the metal M is selected from silver, gallium, indium, thallium , germanium, tin, lead, arsenic, antimony, bismuth, and mixtures thereof.

本发明方法发现了在氯化丙烷转化中非常有利的应用,尤其是作为下列生产的副产生形成的氯化丙烷:由丙烯氯化生产烯丙基氯和/或由烯丙基氯过量氯化生产表氯醇。 The method of the present invention is found in chlorinated propane conversion in a very advantageous application, especially as propane chlorination by-product formed following the production: from the production of allyl chloride, chlorine propylene and / or an excess of allyl chloride by the chlorination production of epichlorohydrin. 作为这些生产过程副产物的氯化丙烷,其特例是1,2-二氯丙烷和1,2,3-三氯丙烷。 As the production process of chlorination by-products of propane, the exception is 1,2-dichloropropane and 1,2,3-trichloropropane. 用于本发明方法的这种应用的氯化丙烷可以含少量其它产物,通常低于5%(重量),尤其是烯丙基氯和/或表氯醇的生产中得到的产物,更特殊地是氯化丙烯,如1,3-二氯丙烯、2-氯丙烯和烯丙基氯。 Chlorinated Propane this application for a method of the present invention may contain minor amounts of other products, generally less than 5% (by weight), in particular allyl chloride and / or epichlorohydrin product obtained in the production, more particularly chlorinated propylene, such as 1,3-D, 2-chloropropene and allyl chloride. 本发明方法的这种特殊应用格外有益,因为它使获得这种丙烯成为可能,该丙烯仅含很少量丙烷,通常低于3%,更常见地是低于1%,因而能直接再循环至丙烯氯化生产烯丙基氯段。 This particular application of the method of the present invention is particularly advantageous, since it makes it possible to obtain the propylene, the propylene oxide containing only a very small amount, usually less than 3%, more usually less than 1%, which can be directly recycled allyl chloride to propylene dichloride production segment. 含少量丙烷的丙烯在烯丙基氯生产段的这种利用使限制1-氯丙烷和/或2-氯丙烷的量成为可能,它们由丙烷氯化生成,难以从烯丙基氯中分离出来。 Propylene oxide containing a small amount of allyl chloride produced in this section use the restriction 1- chloropropane and / or amount of 2-chloro-propane as possible, they are generated by propane chloride, it is difficult to separate from the allyl chloride .

本发明通过下述实施例更详细地描述。 The present invention is described in more detail by the following embodiment Examples.

实施例1(根据本发明)本实施例中,使用钯-银催化剂,沉积在活性炭上。 Example 1 (according to the present invention) In this example, the use of palladium - silver catalyst deposited on the activated carbon.

a)沉积在载体上的催化剂的制备微孔体积0.5ml/g的10g活性炭(NC35级,CECA公司销售)用3.5ml水和1.5ml含0.10g Pd/ml的溶液(PdCl2溶于6N HCl的溶液)导入圆底烧瓶。 a) Preparation of pore volume of the catalyst deposited on the carrier of 0.5ml / g of 10g of activated carbon (NC35 level, CECA sales) with 3.5ml and 1.5ml water containing 0.10g Pd / ml of solution (PdCl2 was dissolved in 6N HCl solution) into the round bottom flask. 室温下15分钟后,将浸渍活性炭于80℃下真空干燥。 After 15 minutes at room temperature, the impregnated activated carbon was dried in vacuo at 80 ℃. 冷却至室温后,含0.05g Ag/ml的溶液6ml(AgCl溶于含NH325%(重量)的氨水溶液)导入烧瓶。 After cooling to room temperature, containing 0.05g Ag / 6ml ml of solution (AgCl containing dissolved NH325% (by weight) aqueous ammonia solution) was introduced into the flask. 室温下15分钟,浸渍活性炭首先在80℃下干燥,然后在氦气气氛下120℃干燥1h再在280℃下1h。 At room temperature for 15 minutes, at first impregnated activated carbon was dried at 80 ℃, and then dried under a helium atmosphere at 120 ℃ 1h and then at 280 ℃ 1h. 浸渍且干燥后的活性炭然后在280℃下用氢气处理4h。 Impregnated activated carbon and dried and then treated with hydrogen at 280 ℃ 4h. 催化剂由此制得,包含相当于所用催化剂重量1.5%的Pd和3%的Ag。 The catalyst thus obtained, containing the equivalent of 1.5% by weight of the catalyst 3% Pd and Ag. 催化剂的X射线衍射分析显示金属部分以合金形式存在,该合金含20~50%银原子,粒径为3~10nm。 X-ray diffraction analysis of the catalyst showed the form of the metal alloy part, the alloy contains 20 to 50% silver atom, a particle diameter of 3 ~ 10nm.

b)1,2-二氯丙烷的转化3.43g(7.50cm3)上述催化剂导入一反应管中(内径=0.8cm)。 b) 1,2- dichloropropane transformed 3.43g (7.50cm3) introducing said catalyst in a reaction tube (inner diameter = 0.8cm). 然后在345℃、1.5bar条件下向含催化剂的反应管连续进料数小时以2.6Nl/h的速度加入1,2-二氯丙烷和10.3Nl/h的氢气。 Then at 345 ℃, 1.5bar conditions of the reaction tube containing the catalyst for several hours continuously fed to 2.6Nl / h added at a rate of 1,2-dichloropropane and 10.3Nl / h of hydrogen. 停留时间估计为1.39S;在不同的时间间隔,不断从反应器中取出产物样品并用气相层析进行分析,测1,2-二氯丙烷的转化率和生成丙烯的选择性(定义为参与反应的1,2-二氯丙烷中转化为丙烯的摩尔份)。 The residence time is estimated to be 1.39S; at various time intervals, continuously sample of the product taken from the reactor and analyzed by gas chromatography, selective measurement of 1,2-dichloro-propane conversion rate and generate propylene (defined as involved in the reaction 1,2-dichloropropane is converted to propylene molar parts). 测试结果整理于表I中。 The test results finishing in Table I below. 由表可见,反应进行超过150h以后,催化剂仍然如开始一样有活性和选择性。 Seen from the table, reaction was carried out after more than 150h, the catalyst is still as active and selective as it began. 进行约8天以后,催化剂仍然使获得超过约95%的转化率成为可能。 For about eight days later, so as to obtain a catalyst is still more than about 95% conversion rate possible. 此时,每千克催化剂使约711kg 1,2-二氯丙烷得到转化。 In this case, per kilogram of catalyst to about 711kg 1,2- dichloropropane get transformed.

实施例2(不根据本发明)1,2-二氯丙烷在如实施例1所述一样的操作条件下转化,但是使用3.67g(7.50cm3)催化剂,该催化剂包含相当于所用活性炭重量2.7%的Pt和1.8%的Cu。 Example 2 (not according to the invention) 1,2-dichloro-1-propane conversion at the same operating conditions as in Example, but using 3.67g (7.50cm3) catalyst which comprises activated carbon used is equivalent to 2.7% by weight Pt and 1.8% Cu. 催化剂应用在同实施例1一样的载体上和相同操作条件下,使用H2PtCl6·6H2O和CuCl2·2H2O的水溶液。 On the catalyst used in Example 1 with the same carrier to implement and operate under the same conditions, using an aqueous solution H2PtCl6 · 6H2O and CuCl2 · 2H2O in.

不同的时间间隔以后,同实施例1一样测1,2-二氯丙烷的转化率和丙烯的选择性。 After various time intervals, the same as in Example 1 measured selectivity of 1,2-dichloro-propane conversion and propylene. 测试结果也整理于表I中。 The test results also finishing in Table I below.

表I Table I

</tables>比较所得结果可以观察到,在相同的操作条件下和催化剂包含分别选自VIII族和IB的金属有相同的原子数量时,实施例1中使用的催化剂(根据本发明)包含钯和银,首先明显地此实施例2中使用的基于铂和铜的催化剂(不根据本发明)更有选择性。 </ Tables> Compare the results can be observed under the same operating conditions and a catalyst comprising a Group VIII and IB are independently selected from the same amount of metal atoms, the catalyst used in Example 1 contains palladium (according to the present invention) and silver, the first obviously in this case based on platinum and copper catalysts (not according to the present invention) more selective in the use of the second embodiment. 而且,生成丙烯的选择达到90%之间Pt-Cu催化剂需要40多小时的操作,而Pd-Ag催化剂仅3.50小时后即可达到90%的选择性。 Moreover, the choice to propylene reaches Pt-Cu catalyst required more than 40 hours of operation between 90% and Pd-Ag catalyst can only reach 90% selectivity after 3.50 hours.

此外,转化度比较表明随时间进行,实施例1中使用的pd-Ag催化剂比例2的Pt-Cu催化剂更稳定。 In addition, the degree of conversion comparison shows that over time, the proportion of the catalyst of Pt-Cu catalyst 2 is more stable pd-Ag used in Example 1 embodiment.

实施例3(根据本发明)如实施例1所述相似的步骤且使用相同的载体制备催化剂,该催化剂包含相当于所用活性炭重量0.5%的Pd和0.5%的Ag。 Example (according to the invention) similar steps as described in Example 1 and using the same preparation of the catalyst support, the catalyst comprises activated carbon used is equivalent to 0.5% by weight of Pd and 0.5% Ag 3 embodiment.

3.61g(7.50cm3)这种催化剂导入反应管中(内径=0.8cm)。 3.61g (7.50cm3) of this catalyst introduced into the reaction tube (inner diameter = 0.8cm). 接着在350℃、1.5bar下向含催化剂的反应器中以2.6Nl/h的速度加入1,2-二氯丙烷和以10.3Nl/h的速度通入氢气。 Then at 350 ℃, 1.5bar to the reactor containing the catalyst to 2.6Nl / h added at a rate of 1,2-dichloropropane and to 10.3Nl / h speed through hydrogen. 停留时间估计为1.4S. The residence time is estimated to be 1.4S.

不同的时间间隔后,测1,2-二氯丙烷的转化率和生成丙烯的选择性及生成丙烷的选择性(定义为参与反应的1,2-二氯丙烷中分别转化为丙烯和丙烷的摩尔份数)。 After various time intervals, selective measurement of 1,2-dichloro-propane conversion and selectivity to propylene and propane (defined as 1,2-dichloropropane participating in the reaction are converted to propylene and propane mole fraction). 这些测试结果整理于表II中。 These test results finishing in Table II.

实施例4(不根据本发明)1,2-二氯丙烷在如实施例3所述的相同操作条件下转化,但使用3.53g(7.50cm3)的一种催化剂,该催化剂包含相当于所用活性炭重量1%的Pt和0.5%Ag。 4 (not according to the invention) 1,2-dichloropropane under the same operating conditions as in Example 3 Example Conversion, but using 3.53g (7.50cm3) a catalyst which comprises activated carbon used is equivalent to 1% by weight of Pt and 0.5% Ag. 这种催化剂应用在与实施例1中一样的载体上和相同的操作条件下,使用H2PtCl6·6H2O的水溶液。 This catalyst in the same manner as in Example 1, the carrier under the same operating conditions, the use of an aqueous solution of H2PtCl6 · 6H2O.

不同的时间间隔后,测1,2-二氯丙烷的转化率及生成丙烯和丙烷的选择性。 After different time intervals, measuring the conversion rate of 1,2-dichloropropane to propylene and propane and selectivity. 这些测试结果同样地整理于表II中。 These test results also organize in Table II.

实施例5(不根据本发明)1,2-二氯丙烷在如实施例3所述的相同操作条件下转化,但使用包含相当于所用活性炭重量1%的Pt和0.3%的Cu的催化剂。 Example 5 (not according to the invention) 1,2-dichloropropane under the same operating conditions as in Example 3 the conversion, but containing the equivalent of 1% by weight of activated carbon and 0.3% of Cu Pt catalyst. 这种催化剂应用在与实施例1中一样的载体上和相同的操作条件下,使用H2PtCl6·6H2O和CuCl2·2H2O的水溶液。 This catalyst in the same manner as in Example 1, the carrier under the same operating conditions, using an aqueous solution H2PtCl6 · 6H2O and CuCl2 · 2H2O in.

不同的时间间隔后,测1,2-二氯丙烷的转化率及生成丙烯和丙烷的选择性。 After different time intervals, measuring the conversion rate of 1,2-dichloropropane to propylene and propane and selectivity. 这些测试结果同样地整理于表II中。 These test results also organize in Table II.

表II Table II

</tables>比较在相同操作条件下和催化剂包含分别选自VIII族和IB族的金属有相同原子数量时得到的结果,包含钯和银的催化剂首先明显地比基于铂和银或铜的催化剂对生成丙烯更有选择性。 Results </ tables> comparison under the same operating conditions and catalysts are selected from the group comprising Group IB and Group VIII metals have the same number of atoms obtained when the catalyst contains palladium and silver catalyst significantly than the first platinum and silver or copper on the for more selective to propylene. 在上述操作条件下,使用Pt-Cu催化剂,生成丙烯的选择性达到95%时需要多于70h的操作。 Under these operating conditions, using the Pt-Cu catalyst, the operation requires more than 70h propylene selectivity of 95%. 此时,产生的丙烷数量仍然约为4%。 At this time, the number of propane produced is still about 4%. 使用Pd-Ag催化剂,仅1.55h后生成丙烯的选择性即达到约95%。 Using Pd-Ag catalyst, selectivity to propylene 1.55h after only about 95% is reached. 产生的丙烷数量在反应开始时即非常小,操作少于20h后可忽略。 Quantity of propane produced in the beginning of the reaction that is very small, less than 20h after operation can be ignored. 实施例6(根据本发明)用类似于实施例1所述的步骤制备催化剂,该催化剂包含相当于所用载体重量0.5%的Pd和0.5%的Ag,用二氧化钛作载体(HARSHAWn°Ti-0720T 1/8″级)。 Example 6 (according to the invention) A catalyst was prepared using steps similar to Example 1, the catalyst carrier containing the equivalent of 0.5% by weight of Pd and 0.5% Ag, with titanium dioxide as the carrier (HARSHAWn ° Ti-0720T 1 / 8 "level).

2.16g(2.5cm3)这种催化剂导入反应管中(内径=1.0cm)。 2.16g (2.5cm3) of this catalyst introduced into the reaction tube (inner diameter = 1.0cm). 接着350℃、1.5bar下向含催化剂的反应器中以0.4Nl/h的速度加入1,2-二氯丙烷,以0.8Hl/hr的速度通入氢气和2.7Nl/h的氦气。 Then 350 ℃, under 1.5bar the reactor containing the catalyst to 0.4Nl / h added at a rate of 1,2-dichloropropane to 0.8Hl / hr through at a rate of hydrogen and 2.7Nl / h of helium. 停留时间估计为1.5s。 The residence time is estimated to be 1.5s.

1,2-二氯丙烷的转化率为100%,生成丙烯的选择性为82%,生成氯化丙烯的选择性(1-、2-、3-氯化丙烯的摩尔份数之和)为18%。 1,2-dichloropropane was converted by 100% and the selectivity to propylene was 82%, selectivity to propylene dichloride (1-, 2-, 3- molar fraction of propylene and chlorinated) as 18%. 实施例7(根据本发明)对于1,2,3-三氯丙烷的转化,使用一种包含相当于活性炭重量1.5%的Pd和3%的Ag的催化剂,它如实施例1所述方法制备。 Example 7 (according to the present invention) for the conversion of 1,2,3-trichloropropane, using an activated carbon containing the equivalent of 1.5% by weight of Pd and 3% Ag catalyst, which method of preparation as described in Example 1 .

1.3lg(2.5cm3)的这种催化剂导入反应管中(内径=1.0cm)。 1.3lg (2.5cm3) of this catalyst introduced into the reaction tube (inner diameter = 1.0cm). 然后在300℃、3bar下向含催化剂的反应器中以0.78Nl/h的速度加入1,2,3-三氯丙烷,以3.12Nl/h的速度通入氢气和以3.9Nl/h的速度通入氦气。 Then the reactor containing the catalyst to 0.78Nl / h speed 1,2,3-trichloropropane at 300 ℃, 3bar, with 3.12Nl / h speed the flow of hydrogen and to 3.9Nl / h speed pass into helium. 停留时间估计为1.7s。 The residence time is estimated to be 1.7s.

1,2,3-三氯丙烷的转化率为93%,生成丙烯的选择性为99%。 1,2,3-trichloro-propane conversion was 93%, selectivity to propylene was 99%. 实施例8(根据本发明)在本实施例中,使用Pd-Sn催化剂,沉积在载体活性炭上。 Example 8 (according to the present invention) In this example, the use of Pd-Sn catalyst deposited on the carrier activated carbon.

a)沉积在载体上的催化剂的制备微孔体积0.5ml/g的50.0g活性炭(NC35级,CECA公司销售)用18.0ml水和17.0ml含0.0147g Pd/ml的溶液(PdCl2溶于6M HCl中的溶液)导入圆底烧瓶中。 Preparation of pore volume 0.5ml a) deposited on the carrier catalyst / g of 50.0g of activated carbon (NC35 level, CECA sales) with 18.0ml and 17.0ml water containing 0.0147g Pd / ml of solution (PdCl2 dissolved in 6M HCl solution) into a round bottom flask. 室温下60分钟后,将浸渍活性炭真空干燥,先在80℃下,然后在100℃。 After 60 minutes at room temperature, the impregnated activated carbon was dried in vacuo, first at 80 ℃, then at 100 ℃. 冷却至室温后,16.08ml含0.017lg Sn/ml的溶液(SnCl4·5H2O的水溶液)导入烧瓶中。 After cooling to room temperature, 16.08ml containing 0.017lg Sn / ml solution (SnCl4 · 5H2O aqueous solution) into the flask. 室温下60分钟后,将浸渍活性炭真空干燥,先在80℃下,然后在100℃,浸渍且干燥后的活性炭然后在350℃下用氢气处理4h。 After 60 minutes at room temperature, the impregnated activated carbon was dried in vacuo, first at 80 ℃, then at 100 ℃, impregnated activated carbon and dried and then treated with hydrogen at 350 ℃ 4h. 催化剂由此制得,含相当于所用活性炭重量0.5%(4.7mmoles)的Pd和0.55%(4.6mmoles)的Sn。 The catalyst thus obtained, containing the equivalent of the weight with charcoal 0.5% (4.7mmoles) of Pd and 0.55% (4.6mmoles) of Sn.

b)1,2-二氯丙烷的转化4.5g(10cm3)上述催化剂导入反应管(内径=0.8cm)。 b) 1,2- dichloropropane conversion 4.5g (10cm3) the catalyst introduced into the reaction tube (inner diameter = 0.8cm). 然后在300℃、3bar下向含催化剂的反应器连续进料数小时,以3.0Nl/h的速度加入1,2-二氯丙烷,以21.0 Nl/h的速度通入氦气和6Nl/h的氢气。 Then at 300 ℃, 3bar-containing catalyst to the reactor for several hours continuously fed to 3.0Nl / h 1,2-dichloropropane added at a rate to 21.0 Nl / h and a rate of helium 6Nl / h hydrogen. 停留时间估计为1.7s。 The residence time is estimated to be 1.7s.

8.5小时和14.5小时的操作后,从反应器取出产物样品,用气相色谱法分析,测1,2-二氯丙烷的转化率和生成丙烯的选择性,测试结果整理于表III。 After 8.5 hours and 14.5 hours of operation, is removed from the reactor product samples were analyzed by gas chromatography to measure the selectivity of 1,2-dichloro-propane propylene conversion rate and generate test results finishing in Table III. 从该表可见,转化率大于或等于95%,生成丙烯的选择性为96%,且14.5小时的操作后,催化剂仍然与8.5小时操作后有一样的活性和选择性。 Seen from the table, the conversion rate is greater than or equal to 95% and the selectivity to propylene was 96% and after 14.5 hours of operation, the catalyst still had the same operation with 8.5 hours of activity and selectivity. 实施例9和10(不根据本发明)1,2-二氯丙烷在如例实施8所述相同的操作条件下转化,但使用包含重1%的Pt和重0.3%的Cu的催化剂(实施例9)和包含重0.5%的Pt和重0.3%的Sn的催化剂(实施例10),该含量是相对于活性炭重量来表示的。 Examples 9 and 10 (not according to the invention) 1,2-dichloropropane as in Example 8 in the same operating conditions the conversion, but containing 1% weight of Pt and 0.3% by weight of Cu catalyst (Embodiment Example 9) and contains 0.5% by weight of Pt and 0.3% by weight of Sn catalyst (Example 10), with respect to the content of the activated carbon is represented by weight. 这些催化剂应用在如实施例8中一样的载体上和在相当的操作条件下,使用H2PtCl6·6H2O,CuCl2·2H2O和SnCl4·5H2O的水溶液。 These catalysts are used in the as described in Example 8 as the carrier and under comparable operating conditions using aqueous H2PtCl6 · 6H2O, CuCl2 · 2H2O and SnCl4 · 5H2O in.

在8.5小时和14.5小时的时间间隔后,如实施例8中一样测1,2-二氯丙烷的转化率和生成丙烯的选择性。 After 8.5 hours and 14.5 hours of time intervals, the same as in Example 8, 1,2-dichloropropane measure conversion and selectivity to propylene. 这些测试结果同样地整理于表III中。 These test results also organize in Table III. 实施例11、12和13(根据本发明)1,2-二氯丙烷在如实施例8所述相同的操作条件下转化,但使用包含重0.5%的Pd和重0.97%的Pb的催化剂(实施例11),包含重0.5%的Pd和重0.96%的Tl的催化剂(实施例12)和包含重0.5%的Pd和重0.98%的Bi的催化剂(实施例13),该含量是相对于活性炭重量来表示的。 Example 11, 12 and 13 (according to the invention) 1,2-dichloropropane under the same operating conditions of Example 8 as described in the conversion, but containing 0.5% by weight of Pd and 0.97% of the weight of Pb in the catalyst ( Example 11), containing 0.5% by weight of Pd and 0.96% weight Tl catalyst (Example 12) and comprising 0.5% by weight of Pd and 0.98% of the weight of the catalyst Bi (Example 13), with respect to the content Activated carbon weight represented. 这些催化剂应用在如实施例8中一样的载体上和相同的操作条件下,使用Pd(CH3CO2)2·3H2O、Tl(CH3CO2)3和Bi(NO3)3·5H2O的水溶液。 The catalyst in the same as described in Example 8 and the carrier under the same operating conditions, using Pd (CH3CO2) 2 · 3H2O, Tl (CH3CO2) 3 and Bi (NO3) 3 · 5H2O in water.

在8.5小时和14.5小时的时间间隔后,如例8中一样测1,2-二氯丙烷的转化率和生成丙烯的选择性。 After 8.5 hours and 14.5 hours interval, as measured as in Example 8 1,2-dichloro-propane conversion and selectivity to propylene. 这些测试结果同样地整理于表III中。 These test results also organize in Table III.

表III Table III

比较所得结果可以观察到,在相同的操作条件下,实施例8、11、12和13(根据本发明)中使用的含钯催化剂使得到1,2-二氯丙烷非常好的转化成为可能,同时就生成丙烯而论,它明显地比实施例9和实施例10(不根据本发明)中使用的铂基催化剂更有选择性。 Comparison results can be observed, under the same operating conditions, in Example 8,11,12 and 13 (according to the invention) for use in a palladium-containing catalyst to obtain a very good conversion of 1,2-dichloropropane is possible, At the same time it generates in terms of propylene, it is clear than in Example 9 and Example 10 (not according to the invention) more selective use of platinum-based catalysts. 实施例14(根据本发明)本实施例中,使用Pd-Sn催化剂,沉积在氧化铝载体上。 Example 14 (according to the present invention) In this example, the use of Pd-Sn catalyst deposited on alumina support.

催化剂在如实施例8中相同的操作条件下制备,使用一种氧化铝载体(α-氧化铝,微孔体积0.43ml/g,比表面积3m2/g)。 The catalyst as described in Example 8 was prepared the same operating conditions, using an alumina support (α- alumina pore volume 0.43ml / g, specific surface area of 3m2 / g).

1,2-二氯丙烷在如实施例8所述相同的操作条件下转化,但使用9.1g(10cm3)催化剂,该催化剂包含相当于氧化铝重量0.5%的Pd和0.55%的Sn。 1,2-dichloropropane under the same operating conditions of Example 8 as described in the conversion, but using 9.1g (10cm3) catalyst which comprises an alumina equivalent of Pd and 0.5% by weight 0.55% of Sn.

8.5小时和14.5小时间隔后,如实施例8中一样测1,2-二氯丙烷的转化率和生成丙烯的选择性。 After 8.5 hours and 14.5 hours interval, as measured as in Example 8 1,2-dichloro-propane conversion and selectivity to propylene. 这些测试结果整理于表IV中。 These test results finishing in Table IV. 实施例15(不根据本发明)1,2-二氯丙烷在如实施例14中所述的操作条件下转化,但使用一种包含相当于氧化铝重量0.5%的Pt和0.3%的Sn的催化剂。 Example 15 (not according to the invention) 1,2-dichloropropane converted under the operating conditions as described in Example 14, but using an equivalent to 0.5% of alumina containing Pt and 0.3% by weight of Sn catalyst. 这种催化剂应用在如实施例14一样的载体上和相同的操作条件下,使用H2PtCl6·6H2O水溶液。 Such catalysts at 14 on the same carrier and the same operating conditions as example 1 using H2PtCl6 · 6H2O solution.

在相同的时间间隔后,如实施例14中一样测试1,2-二氯丙烷的转化率和生成丙烯的选择性。 After the same time interval, the same as in Test Example 14 1,2-dichloropropane conversion and selectivity to propylene. 这些测试结果同样地整理于表IV中。 These test results also organize in Table IV.

表IV Table IV

比较所得结果可以观察到,在相同的操作条件下,实施例14(根据本发明)中使用的含钯催化剂就生成丙烯而论明显地比实施例15(不根据本发明)中使用的铂基催化剂更有选择性。 Comparison results can be observed, under the same operating conditions, Example 14 (according to the invention) a palladium-containing catalyst used is generated in terms of propylene significantly EXAMPLE 15 (not according to the present invention) used in the platinum group The catalyst more selective.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
CN100388976C7 Jul 200621 May 2008宁夏大学Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method
CN103502193A *2 Feb 20128 Jan 2014索尔维特殊聚合物意大利有限公司Method for manufacturing perfluorvinylethers
CN103502193B *2 Feb 201218 May 2016索尔维特殊聚合物意大利有限公司生产全氟乙烯基醚的方法
Classifications
International ClassificationC07C11/06, C07C21/04, B01J23/44, C07C1/26, C07C17/25, C07C17/23
Cooperative ClassificationC07C2523/50, C07C1/26, C07C17/23, C07C2521/18, B01J23/44, C07C2523/62
European ClassificationC07C1/26, C07C17/23, B01J23/44
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