CN106140225B - Kind of silica-supported catalysts and their preparation and use - Google Patents

Kind of silica-supported catalysts and their preparation and use Download PDF

Info

Publication number
CN106140225B
CN106140225B CN201510135845.6A CN201510135845A CN106140225B CN 106140225 B CN106140225 B CN 106140225B CN 201510135845 A CN201510135845 A CN 201510135845A CN 106140225 B CN106140225 B CN 106140225B
Authority
CN
China
Prior art keywords
catalyst
content
bromide
silica
hydrogen
Prior art date
Application number
CN201510135845.6A
Other languages
Chinese (zh)
Other versions
CN106140225A (en
Inventor
张舒冬
张信伟
孙晓丹
李�杰
倪向前
张喜文
刘继华
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司抚顺石油化工研究院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司抚顺石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CN201510135845.6A priority Critical patent/CN106140225B/en
Publication of CN106140225A publication Critical patent/CN106140225A/en
Application granted granted Critical
Publication of CN106140225B publication Critical patent/CN106140225B/en

Links

Abstract

本发明公开种以二氧化硅为载体的催化剂及其制备方法和应用,包括如下过程:(1)制备二氧化硅载体;(2)将氧化锌和/或助剂氧化物引入至二氧化硅载体;(3)对引入氧化锌后的二氧化硅载体进行溴化处理。 Species present invention discloses silica supported catalysts and preparation method and applications, including the following procedure: (1) Preparation of silica support; (2) zinc oxide and / or oxide additives introduced to the silica carriers; (3) after the introduction of the silica support is brominated zinc oxide. 所述催化剂含有氧化锌、溴化锌及二氧化硅载体,按催化剂重量含量计,氧化锌含量为0.5%‑20%,溴化锌含量为10%‑50%,二氧化硅载体含量为40%‑90%。 The catalyst contains zinc oxide, zinc bromide, and the silica carrier, by weight content of the catalyst, the zinc oxide content of 0.5% to 20%, zinc bromide content of 10% -50%, the silica content of the carrier is 40 % -90%. 该催化剂用于溴甲烷制异丁烯反应,能够明显提高异丁烯的选择性。 The catalyst for the reaction of methyl bromide isobutene, isobutene selectivity can be significantly improved.

Description

一种以二氧化硅为载体的催化剂及其制备方法和应用 Kind of silica-supported catalysts and their preparation and use

技术领域 FIELD

[0001] 本发明涉及一种以二氧化硅为载体的催化剂及其制备方法和应用。 [0001] The present invention relates to a catalyst supported on silica and a preparation method and application.

背景技术 Background technique

[0002] 异丁烯是一种重要的基本有机化工原料,其衍生产品众多,上下游产业链复杂,消费结构呈多元化趋势。 [0002] isobutylene is an important basic organic chemicals, many of its derivatives, the downstream chain complex, the structure was diversified consumer trend. 以异丁烯为原料可以制备多种高附加值的产品,如:丁基橡胶、聚异丁烯、甲基叔丁基醚、异戊二烯和有机玻璃等多种有机化工原料和精细化学产品。 Isobutylene feedstock can be prepared by a variety of high value-added products, such as: butyl rubber, polyisobutylene, methyl tert-butyl ether, isoprene, and plexiglass and other organic chemicals and fine chemicals. 由于异丁烯下游产品的市场规模不断扩大,其供需矛盾将逐渐突出,特别是在石油资源日益枯竭的背景下,异丁烯的产量已成为制约下游产业发展的关键瓶颈。 As the size of the market isobutylene downstream products continues to expand its supply and demand will become more apparent, especially in the context of oil resources are depleted, isobutene production has become a key bottleneck in the development of downstream industries. 因此,开发非石油路线的异丁烯制备路线,已经迫在眉睫。 Thus, development of non-petroleum routes isobutene preparative route is imminent.

[0003] 甲烷是天然气的主要成分,因此甲烷转化利用就成为天然气化工技术中的重要研究内容。 [0003] Methane is the main component of natural gas, methane conversion and therefore the use of technology has become an important research content in natural gas chemical industry. 特别是近年来,在页岩气开发利用的大背景下,如果能够实现从甲烷出发制取异丁烯,就会为获取异丁烯提供一条新的途径。 Especially in recent years, shale gas exploitation in the background can be achieved if the preparation of isobutene starting from methane, will provide a new way to obtain isobutene. 但是甲烷性质稳定,不易活化,成为甲烷化工利用的瓶颈。 However, methane stable, not easily activated, become the bottleneck of the technology for the utilization of methane. 国内外许多研究者纷纷开展甲烷活化、转化研究,这其中,甲烷经卤素官能团化后再转化的技术,有望成为解决甲烷转化技术难题的一个重要突破口。 Many researchers at home and abroad have launched methane activation, translational research, which, methane halogen-functionalized after conversion technology, is expected to become a major breakthrough in the conversion of methane to solve technical problems.

[0004] 从卤代甲烷出发可以制备许多化工产品。 [0004] From the halogenated methane can be prepared by a number of chemical products. 中国专利CN 101041609A、CN 101284232A公开了一种将甲烷在氧气和HBr/H20的作用下转化为溴代甲烷,然后溴代甲烷进一步反应生成C3〜C13混合高碳烃的方法,C5以上的烃类选择性为70%。 Chinese Patent CN 101041609A, CN 101284232A discloses a method for converting methane to oxygen gas and at HBr / H20 methyl bromide, methyl bromide and then reacted further method of generating a mixed C3~C13 higher hydrocarbons, hydrocarbons than C5 selectivity of 70%. 其中,HBr在第一个反应器内用于甲烷溴化,然后在第二个反应器内释放,经回收后再用于前一步反应中,实现HBr 的循环使用。 Wherein, HBr is used in the first reactor, methyl bromide, and then released in the second reactor, and then recovered through a pre-step reaction, the use of HBr to achieve recycling. 王野等〇^ 102527427厶,了1611!^,1^叫乂11,211让1^如叫,6^&1· Angew. Chem. Int. Ed. 2012,51,2438-2442)公开了一种卤代甲烷制丙烯的改性分子筛催化剂及其制备方法。 Wang Ye and other 102 527 427 billion ^ Si, the 1611 ^ 1 ^ 1 ^ called Yi in 11,211 to make such call, 6 ^ & amp;!.... 1 · Angew Chem Int Ed 2012,51,2438-2442) discloses a haloalkyl methane to propylene modified molecular sieve catalyst and a preparation method. 通过使用含氟化合物修饰处理分子筛,得到一种含有合适微孔结构及酸性的催化剂,该催化剂可以有效催化卤代甲烷转化生成丙烯的反应。 By using fluorine-containing compound treated zeolite modified, to obtain a suitable porous structure and containing an acidic catalyst, the catalyst may be effective to catalyze the conversion of methyl halide reaction of propylene. 所制备的催化剂在溴甲烷转化制丙烯的反应中单程溴甲烷转化率为35〜99%,丙烯的选择性为27〜70%;在氯甲烷转化制丙烯的反应中单程氯甲烷转化率为30〜99%,丙烯的选择性为15〜70%。 Selectively pass 35~99% conversion rate of methyl bromide in the reaction of methyl bromide conversion to propylene, the propylene of the prepared catalyst was 27~70%; single pass conversion in the reaction of methyl chloride in methyl chloride to propylene conversion was 30~99 %, selectivity of propylene was 15~70%. I van M. Lorkovic等人(Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004,98,317-322)也提出用溴与天然气中的烷烃反应生成溴代烃, 然后在金属氧化物催化剂上将溴代烃转化为二甲醚、甲醇和金属溴化物,金属溴化物用氧气再生后得到金属氧化物并释放出单质溴,完成了溴的循环。 I van M. Lorkovic et al (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004,98,317-322) to generate bromocarbon also made by reaction of bromine with alkanes in the natural gas, then the metal oxide catalyst on brominated hydrocarbons into dimethyl ether, methanol and a metal bromide, the metal bromide with oxygen to give regenerated metal oxide and the release of elemental bromine, bromine complete cycle.

[0005] 目前,关于卤代甲烷转化的现有文献中目的产物主要为甲醇、二甲醚、醋酸、高碳烃类、乙烯与丙烯等等。 [0005] Currently, the existing literature on the object of halogenated methane conversion products primarily methanol, dimethyl ether, acetic acid, higher hydrocarbons, ethylene and propylene and the like. 在以较高附加值的低碳烯烃为目标产物的技术中,单一产物选择性不高,尚未发现溴甲烷高选择性合成异丁烯的相关报道。 In the lower olefins to higher value-added target product art, a single product selectivity is not high, dibromomethane has not been found highly selective synthesis reports isobutene.

发明内容 SUMMARY

[0006] 针对现有技术的不足,本发明提供了一种以二氧化硅为载体的催化剂及其制备方法和应用。 [0006] for the deficiencies of the prior art, the present invention provides a catalyst and its preparation method and application of silica as the carrier.

[0007] —种以二氧化硅为载体的催化剂的制备方法,包括如下过程:(1)制备二氧化硅载体;(2)将氧化锌和/或助剂氧化物引入至二氧化硅载体;(3)对引入氧化锌后的二氧化硅载体进行不完全溴化处理(不完全溴化处理指将部分氧化锌溴化为溴化锌)。 [0007] - preparation of the catalyst species in the silica carrier, the process comprising: (1) Preparation of silica support; (2) zinc oxide and / or oxide additives introduced into a silica support; (3) after the introduction of the silica support incompletely treated zinc oxide bromide (incomplete bromination refers to part of the zinc oxide to zinc bromide bromide).

[0008] 上述制备方法步骤(1)中,所述二氧化硅载体的具体制备方法如下:将适量的表面活性剂、均三甲苯(TMB)、硅源、去离子水搅拌均匀,得到澄清的溶液后,在搅拌状态下加入乙酸乙酯,在50°C-90°C下搅拌生成溶胶;在60°C-80°C下搅拌制成凝胶,凝胶再于空气中陈化12h-24h,于60°C-80°C干燥12h-24h,以l°C/min-3°C/min升温至500°C-700°C焙烧4h-10h 得到二氧化硅载体;上述表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基硫酸钠、十二烷基苯磺酸钠或聚乙二醇中的一种或多种,优选十六烷基三甲基溴化铵;硅源为正硅酸四甲酯、正硅酸四乙酯、硅溶胶或硅酸中的一种或多种,优选正硅酸四乙酯;各原料摩尔比为表面活性剂:TMB:硅元素:水:乙酸乙酯=1-5:0.1-2:1: 50-200:10-20; 所制备的载体可以根据使用的需要制成或选取适宜的颗粒形态,如制成条形、 [0008] The preparing step (1), the specific method of preparation of the silica support as follows: an appropriate amount of a surfactant, mesitylene (of TMB), a silicon source, deionized water, stir to give a clear after the solution, ethyl acetate was added under stirring, the sol was stirred generated at 50 ° C-90 ° C; at 60 ° C-80 ° C was stirred to make a gel, and then aging in air 12h- 24h, at 60 ° C-80 ° C was dried 12h-24h, at l ° C / min-3 ° C / min was heated to 500 ° C-700 ° C calcined silica support obtained 4h-10h; the surfactant as a cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, sodium lauryl sulfate, sodium dodecylbenzene sulfonate or polyethylene glycol, or more , preferably cetyl trimethyl ammonium bromide; source of silicon tetramethylorthosilicate, tetraethylorthosilicate, silicate or silica sol or more, preferably tetraethylorthosilicate ; molar ratio of the raw materials is a surfactant: of TMB: silicon element: water: ethyl acetate = 1-5: 0.1-2: 1: 50-200: 10-20; prepared vector can be made as required to use or select a suitable particle shape, such as strip made, 形、柱形、 球形等,成形可以按本领域一般知识进行。 Shaped, cylindrical, spherical, etc., can be formed according to the general knowledge in the art.

[0009] 上述制备方法步骤(2)中,所述氧化锌和/或助剂氧化物引入至二氧化硅载体的方法为本领域技术人员熟知的方法,如可以采用浸渍方式引入。 Method [0009] The preparing method step (2), the zinc oxide and / or oxide is introduced into the silica support adjuvants are known to those skilled in well known methods such as dipping method may be employed is introduced. 具体方法如下:采用锌盐、助剂金属盐溶液浸渍二氧化硅载体,经干燥、焙烧后得到溴甲烷制异丁烯催化剂前体。 Specific methods are as follows: The zinc salt, a metal salt solution impregnated silica support aids, and dried, to give methyl bromide isobutene catalyst precursor is calcined. 所述干燥条件为,温度60°C-150°C,优选为80 °C-120°C ;时间为lh-24h,优选为4h-8h;干燥时可以为真空干燥,也可以为惰性气体保护条件下干燥,还可以在空气气氛下干燥。 The drying conditions, a temperature of 60 ° C-150 ° C, preferably 80 ° C-120 ° C; time lh-24h, preferably 4h-8h; drying may be drying in vacuo, an inert gas may be protected under dry conditions can also be dried in an air atmosphere. 所述焙烧条件为,温度200°C-800°C,优选为400 °C-600°C ;时间为lh-24h,优选为4h-8h;焙烧时可以为惰性气体保护条件下焙烧,也可以在空气气氛下焙烧。 The firing conditions were a temperature of 200 ° C-800 ° C, preferably 400 ° C-600 ° C; time lh-24h, preferably 4h-8h; may be fired under an inert atmosphere during firing conditions, may be calcined in an air atmosphere. 上述方法中,锌盐可以为无机盐,也可以为有机盐,优选为硝酸盐、盐酸盐、醋酸盐、柠檬酸盐中的一种或几种。 The above-described method, the zinc salt may be inorganic salts, may also be one or more of nitrate, chloride, acetate, citrate is an organic salt, preferably.

[0010] 上述制备方法步骤(3)中,所述溴化处理,是指采用气相含溴化合物对负载氧化锌的样品进行处理。 [0010] The preparation process in step (3), the bromination process is a process using a bromine compound gas containing zinc oxide sample processing load. 含溴化合物是指溴甲烷、二溴甲烷、三溴甲烷中的一种或几种,优选为溴甲烷。 Bromine-containing compound refers to methyl bromide, dibromomethane, bromoform one or several, preferably methyl bromide. 还可以采用气相含溴化合物与惰性气体的混合气体进行溴化处理,采用混合气体溴化处理时,溴代甲烷体积浓度不小于20%,优选为不小于30%。 A mixed gas containing bromine compound gas and an inert gas may also be employed, is brominated using mixed gas processing bromide, methyl bromide concentration of not less than 20% by volume, preferably not less than 30%. 具体溴化过程如下:将负载氧化锌的样品置于连续流动固定床反应器中,惰性气氛下升温至150°C-40(TC,优选为180°C-350°C,更优选为200°C-300°C,通入气相含溴化合物气体,气体空速为50h_1-10()() h_1,优选为ΙΟΟΙΓίδΟΟΙΓ1;处理时可以在常压进行,也可以在一定压力下进行,体系压力为O.lMPa-0.5MPa (绝压),优选为0. IMPa-0.3MPa (绝压),处理时间为0.5h-8h,优选lh-4h。 DETAILED bromination process is as follows: The sample was placed load zinc oxide fixed bed continuous flow reactor under an inert atmosphere was warmed to 150 ° C-40 (TC, preferably 180 ° C-350 ° C, more preferably 200 ° C-300 ° C, a bromine compound-containing gas into gas, the gas space velocity 50h_1-10 () () h_1, preferably ΙΟΟΙΓίδΟΟΙΓ1; processing may be performed at atmospheric pressure, may be carried out under pressure, the pressure of the system O.lMPa-0.5MPa (absolute pressure), preferably 0. IMPa-0.3MPa (absolute pressure), the processing time was 0.5h-8h, preferably lh-4h.

[0011] 上述制备方法步骤(3)中,所涉及的惰性气体为氮气、氩气、氦气等在本发明所涉及条件下不发生化学反应的气体,优选为氮气。 [0011] The preparation process in step (3), the inert gas is directed to nitrogen, argon, helium and the like do not chemically react under the conditions of the present invention is a gas, preferably nitrogen.

[0012] —种以二氧化硅为载体的催化剂,所述催化剂含有氧化锌、溴化锌及二氧化硅载体,按催化剂重量含量计,氧化锌含量为〇. 5%-20%,优选为1%-15%,进一步优选为1%-9%,溴化锌含量为10%_50%,优选为15%-45%,进一步优选为18%-39%,二氧化硅载体含量为40%-90%,优选为50%-85%,进一步优选为55%-80%。 [0012] - species silica supported catalysts, the catalyst contains zinc oxide, zinc bromide, and the silica support, the count content of the catalyst by weight, the zinc oxide content of 5% -20% of square, preferably. 1% to 15%, more preferably from 1% to 9%, zinc bromide content of 10% _50%, preferably 15% -45%, more preferably 18% -39%, the silica content of the carrier was 40% -90%, preferably 50% to 85%, more preferably 55% -80%.

[0013] 本发明催化剂含有助剂氧化物,助剂氧化物以金属元素计在催化剂中的重量含量为0.1%-10%,优选为0.5%-5%,更优选为0.5%-3%,助剂选自Ti、Zr、Ce、La中的一种或几种,优选错。 [0013] The present invention is an oxide catalyst contain adjuvants, additives oxides in the catalyst metal element content of 0.1% by weight to 10%, preferably from 0.5% to 5%, more preferably 0.5% to 3%, additives selected from Ti, Zr, Ce, La, one or several, preferably wrong.

[00M] 本发明催化剂中,450 °C以下总酸量(NH3-TPD)为0 · 5mmo 1/g-1 · 3mmo Ι/g,优选O · 6mmol/g_l · 2mmol/g,进一步优选O · 7mmo1 -1 · lmmol/g,250°C-350°C 的酸含量占450°C 以下总酸量的20%-90%,优选30%-80%,进一步优选40%-80%。 [00M] The catalyst of the present invention, 450 ° C or less of the total acid content (NH3-TPD) of 0 · 5mmo 1 / g-1 · 3mmo Ι / g, preferably O · 6mmol / g_l · 2mmol / g, more preferably O · 7mmo1 -1 · lmmol / g, an acid content of 250 ° C-350 ° C accounts for 20% -90% 450 ° C or less of the total amount of acid, preferably 30% to 80%, more preferably 40% -80%.

[0015] 上述以二氧化硅为载体的催化剂在制异丁烯中的应用,包括对催化剂进行氢气还原活化,使催化剂中的卤素含量为还原前催化剂中卤素总含量的20%_90%,然后使卤代甲烷与上述氢气还原活化后的催化剂接触,以制备异丁烯。 [0015] Application of the above-described silica supported catalysts prepared in isobutene, including hydrogen reduction catalyst activation, the halogen content of the catalyst was 20% _90% reduction in the total amount of procatalyst halogen, then brine iodide and the hydrogen gas contacts the catalyst after reductive activation, to produce isobutene.

[0016] 上述应用中,所述氢气还原活化的条件使得催化剂中的卤素含量优选为还原前催化剂中卤素总含量的30%_80%,进一步优选40%-80%。 [0016] In the above application, the hydrogen reduction conditions such that the halogen content of the activated catalyst is preferably 30% _80% reduction of total halogen content of the catalyst precursor, more preferably 40% -80%.

[0017] 上述应用中,所述氢气还原活化的方式包括在惰性气氛下将催化剂升温至300°C-600°C;然后通入空速为200h_1-2000h_1的氢气或氢气与惰性气体的混合气体,在O.lMPa-0.5MPa保持2h-16h,混合气体中氢气体积百分含量为10%-95%;优选地,升温至350°C_550 °C;然后通入空速为Sooir1-IOOOir1的氢气或氢气与惰性气体的混合气体,在0. IMPa-0.3MPa保持4h-8h,所述混合气体中氢气体积百分含量为30%-90%。 [0017] In the above application, the hydrogen reduction means of activation comprises heating the catalyst under an inert atmosphere to 300 ° C-600 ° C; and then passed into a space velocity of the mixed gas 200h_1-2000h_1 hydrogen or hydrogen and inert gas held at O.lMPa-0.5MPa 2h-16h, the volume percentage of hydrogen in the mixed gas content of 10% to 95%; preferably, the temperature was raised to 350 ° C_550 ° C; then passed through a space velocity of hydrogen Sooir1-IOOOir1 or a mixed gas of hydrogen and inert gas, maintained at 0. IMPa-0.3MPa 4h-8h, the mixed gas of hydrogen gas volume percentage of 30% -90%.

[0018] 上述应用中,所述卤代甲烷可以为一卤代甲烷、二卤代甲烷、三卤代甲烷中的一种或多种,优选为溴甲烷、二溴甲烷、三溴甲烷中的一种或多种。 [0018] In the above application, the methyl halide may be a halogenated methane, a dihalomethane, a three or more methyl halide, preferably methyl bromide, dibromomethane, or bromoform one kind variety.

[0019] 上述应用中,所述接触的条件包括反应温度为150°c-350°c;反应压力为O.lMPa-5MPa;空速为50h_1-1000h_1;更优选地,反应温度为180°C-300°C更优选为200-270°C;反应压力为〇· IMPa-3MPa;空速为2〇Oh_1_5〇Oh_1。 Conditions [0019] In the above application, the contacting comprises a reaction temperature of 150 ° c-350 ° c; reaction pressure is O.lMPa-5MPa; airspeed 50h_1-1000h_1; more preferably, the reaction temperature was 180 ° C -300 ° C more preferably 200-270 ° C; reaction pressure is square · IMPa-3MPa; 2〇Oh_1_5〇Oh_1 airspeed.

[0020] 上述应用中的一种具体实施方式,包括惰性气氛下将催化剂升温至300°C_600°C, 优选为350°C-550°C;然后通入空速为200h_1-2000h_1,优选为δΟΟΡ-ΙΟΟΟΙΓ1的氢气或氢气与惰性气体的混合气体,在〇. IMPa-0.5MPa (绝压),优选为0. IMPa-0.3MPa (绝压)处理2h-16h,优选为4h-8h后,降至反应温度通入卤代甲烷进行反应。 [0020] A particular embodiment of the above applications, including the catalyst under inert atmosphere was warmed to 300 ° C_600 ° C, preferably 350 ° C-550 ° C; and then passed into a space velocity 200h_1-2000h_1, preferably δΟΟΡ -ΙΟΟΟΙΓ1 hydrogen mixed gas with an inert gas or hydrogen,. IMPa-0.5MPa (absolute pressure) in the square, preferably 0. IMPa-0.3MPa (absolute pressure) for 2h-16h, preferably after 4h-8h, drop the reaction temperature is fed to the methyl halide reaction. 所述混合气中氢气体积百分含量为10%-95%,优选为30%-90%,更优选为50%-90%。 The mixed volume percentage of hydrogen gas of 10% to 95%, preferably 30% to 90%, more preferably 50% to 90%.

[0021] 上述应用中,原料也可以为卤代甲烷与惰性气体的混合气体,混合气体中卤代甲烷的体积浓度为10%_90%,优选为30%-80%。 [0021] In the above application, the feedstock mixed gas may be a halogenated methane and inert gas, the volume concentration of the mixed gas is 10% methyl halide _90%, preferably 30% -80%.

[0022] 上述应用中所涉及的惰性气体为氮气、氩气、氦气等在本发明所涉及条件下不发生化学反应的气体,优选为氮气。 [0022] Application of the inert gas is a gas involved in nitrogen, argon, helium and the like does not chemically react under the conditions of the present invention, preferably nitrogen.

[0023] 上述应用中,卤代甲烷制异丁烯反应可以在现有任何形式反应器中进行,如固定床、流化床、固定流化床、移动床,浆态床或沸腾床等形式的反应器,优选为固定床、流化床反应器。 [0023] In the above application, isobutene methyl halide reaction can be any form of conventional reactors, such as in the form of a fixed bed, fluidized bed, fixed bed, moving bed, ebullating bed or slurry bed reactor, etc. , preferably a fixed bed, a fluidized bed reactor.

[0024] 与现有技术相比,本发明制备的催化剂可以将溴甲烷高选择性的转化为异丁烯。 [0024] Compared with the prior art, the catalyst of the present invention can be prepared with high selectivity to isobutene conversion of methyl bromide. 按本发明方法进行溴甲烷转化制异丁烯反应,溴甲烷转化率85%以上,异丁烯选择性75%以上。 The method of the present invention is carried out in isobutene conversion reaction of methyl bromide, methyl bromide conversion rate of 85% or more, more than 75% selectivity to isobutene. 本发明涉及溴甲烷转化制异丁烯催化剂制备方法简单,易于工业化。 The present invention relates to conversion of isobutene to methyl bromide catalyst preparation method is simple, easy to industrialize. 本发明溴甲烷转化制异丁烯方法具有反应条件温和、产物选择性高等优点,容易实现工业化,应用前景非常广阔。 The present invention is dibromomethane isobutene conversion method having mild reaction conditions, product selectivity advantages, easy to industrialize, very broad application prospects.

具体实施方式 Detailed ways

[0025] 下面结合实施例进一步说明本发明的技术内容和效果,但不因此限制本发明。 [0025] The following examples further illustrate embodiments in conjunction with the technical content and effect of the present invention, without thereby limiting the present invention.

[0026] 以下实施例及比较例中酸量测定采用NH3-TPD法,采用的仪器型号为美国MICR0MERITICS公司AutoChem 2920化学吸附仪,具体测定过程如下:将样品在450°C用氦气吹扫1小时后降温至150°C,引入氨与氦气的混合气体,氨体积含量10%,脉冲吸附五次达到平衡;氦气吹扫2小时,然后以HTC/分钟的升温速度程序升温进行氨脱附至450°C;脱附后的氨采用TCD检测器检测,定量计算催化剂表面酸量。 [0026] The following Examples and Comparative Examples the amount of acid determined by NH3-TPD method used instrument model MICR0MERITICS U.S. company AutoChem 2920 chemisorption instrument, particular assay procedure is as follows: The sample was purged with helium at 1 450 ° C h after cooling to 150 ° C, introducing a mixed gas of ammonia and helium, ammonia content of 10% by volume, five pulse adsorption reached equilibrium; helium purge for 2 hours and then HTC / minute heating rate of ammonia temperature-programmed de attached to 450 ° C; after ammonia desorbed using TCD detector, the amount of the acid catalyst surface quantitative calculation.

[0027] 实施例1 [0027] Example 1

[0028] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,在80°C下搅拌生成凝胶,所得凝胶于空气中陈化15h,于80°C干燥18h,以rC/min升温至500°C焙烧6h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=1:0.1:1:80: 10。 [0028] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 sol generated under stirring ° C, stirred at 80 ° C for gel formation, the gel obtained in air aging 15H, dried at 80 ° C for 18 h, at rC / min was heated to 500 ° C calcined 6h, i.e., to obtain dioxide a silicon carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 1: 0.1: 1: 80: 10.

[0029] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 100 °C干燥6h,500 °C焙烧6h,制得催化剂前体Zn0/Si02。 [0029] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 100 ° C drying 6h, 500 ° C firing 6h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为CI。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, the catalyst was prepared methyl bromide isobutene, referred to as CI. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,ZnO以氧化物计重量含量为4%,催化剂中450°C以下总酸量为0.96mmol/g,250°C_350°C的酸含量占450°C以下总酸量的73.25%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 30%, ZnO content by weight in terms of oxide 4%, 450 ° C or less in the catalyst in an amount of total acid 0.96mmol / g, an acid content of 250 ° C_350 ° C accounting for 73.25% 450 ° C or less of the total amount of acid.

[0030] 溴甲烷转化制异丁烯反应在连续流动微型固定床反应器中进行。 [0030] Conversion of isobutene bromide reaction is carried out in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氢气与氮气的混合气活化,还原条件为400°C,0.3MPa(绝压),800h_1, 还原时间4h,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的75.36%。 Activated gas mixture, reducing the amount of a catalyst loading 5g, using the catalyst in hydrogen and nitrogen prior to use is 400 ° C, 0.3MPa (absolute pressure), 800h_1, reduction time 4h, the halogen content in the catalyst after reduction of the catalyst before reduction 75.36% of the total halogen content. ;活化结束后,降至反应温度,通入原料气,原料气为溴甲烷与氮气混合气体,其中溴甲烷体积含量为70%,反应温度为230°C,反应压力为2MPa (绝压),空速为200h_1。 ; After activation, the reaction temperature is lowered, the raw material gas into the raw material gas was mixed with nitrogen gas bromide, wherein the bromide content is 70% by volume, the reaction temperature was 230 ° C, a reaction pressure of 2MPa (absolute pressure), a space velocity as 200h_1. 反应稳定一小时后,采样分析。 One hour after the reaction stabilization, sampling and analysis. 反应结果见表1。 The reaction results are shown in Table 1.

[0031] 实施例2 [0031] Example 2

[0032] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在60°C下搅拌生成溶胶,在70°C下搅拌生成凝胶,所得凝胶于空气中陈化20h,于60°C干燥24h,以3°C/min升温至700°C焙烧8h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=5:2:1:200:20。 [0032] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 60 generating the sol was stirred at ° C, stirred at 70 ° C for gel formation, the gel obtained in air aging for 20 h, dried at 60 ° C 24h, at 3 ° C / min was heated to 700 ° C calcination 8h, to obtain a silica support, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 5: 2: 1: 200: 20.

[0033] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 80°C干燥8h,400°C焙烧8h,制得催化剂前体Zn0/Si02。 [0033] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 80 ° C and dried 8h, 400 ° C firing 8h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为C-2。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, methyl bromide to obtain isobutene catalyst, denoted as C-2. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,ZnO以氧化物计重量含量为4%,催化剂中450°C以下总酸量为0.98臟〇1/^,250°0350°(:的酸含量占450°(:以下总酸量的75.21%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 30%, ZnO content by weight in terms of oxide 4%, 450 ° C or less in the catalyst in an amount of 0.98 total acid dirty 〇1 / ^, 250 ° 0350 ° (: acid content accounted for 450 ° (: 75.21% or less of the total amount of acid.

[0034] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的70.18%。 [0034] Evaluation of catalyst activation and the same conditions as in Example 1, the halogen content in the catalyst after reduction of the catalyst prior to reduction of 70.18% of the total halogen content. 反应结果见表1。 The reaction results are shown in Table 1.

[0035] 实施例3 [0035] Example 3

[0036] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0036] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0037] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 120 °C干燥4h,600°C焙烧4h,制得催化剂前体Zn0/Si02。 [0037] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 120 ° C drying 4h, 600 ° C firing 4h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为C-3。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, the catalyst was prepared methyl bromide isobutene, referred to as C-3. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,ZnO以氧化物计重量含量为4%,催化剂中450°C以下总酸量为1.01臟〇1/^,250°0350°(:的酸含量占450°(:以下总酸量的77.12%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 30%, ZnO content by weight in terms of oxide 4%, 450 ° C or less in the catalyst in an amount of 1.01 total acid dirty 〇1 / ^, 250 ° 0350 ° (: acid content accounted for 450 ° (: 77.12% or less of the total amount of acid.

[0038] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中齒素总含量的68.82%。 [0038] Evaluation of catalyst activation and the conditions were the same as in Example 1, the halogen content of the catalyst after reduction of the catalyst before reduction is 68.82% of the total pigment content of the teeth. 反应结果见表1。 The reaction results are shown in Table 1.

[0039] 实施例4 [0039] Example 4

[0040] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0040] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0041] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 100 °C干燥6h,500 °C焙烧6h,制得催化剂前体Zn0/Si02。 [0041] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 100 ° C drying 6h, 500 ° C firing 6h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为300°C,0. IMPa (绝压),5001Γ1,时间4h,制得溴甲烷制异丁烯催化剂,记为C-4。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 300 ° C, 0. IMPa (absolute pressure), 5001Γ1, time 4h, dibromomethane isobutene prepared catalyst, denoted as C-4. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为33%,ZnO以氧化物计重量含量为2%,催化剂中450°C以下总酸量为1.03臟〇1/^,250°0350°(:的酸含量占450°(:以下总酸量的79.52%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 33%, ZnO content by weight of oxide in terms of 2%, 450 ° C or less in the catalyst in an amount of 1.03 total acid dirty 〇1 / ^, 250 ° 0350 ° (: acid content accounted for 450 ° (: 79.52% or less of the total amount of acid.

[0042] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中齒素总含量的77.64%。 [0042] Evaluation of catalyst activation and the conditions were the same as in Example 1, the halogen content of the catalyst after reduction of the catalyst before reduction is 77.64% of the total pigment content of the teeth. 反应结果见表1。 The reaction results are shown in Table 1.

[0043] 实施例5 [0043] Example 5

[0044] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0044] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0045] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 100 °C干燥6h,500 °C焙烧6h,制得催化剂前体Zn0/Si02。 [0045] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 100 ° C drying 6h, 500 ° C firing 6h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为200°C,0.3MPa (绝压),100h_1,时间Ih,制得溴甲烷制异丁烯催化剂,记为C-5。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 200 ° C, 0.3MPa (absolute pressure), 100h_1, time ih, methyl bromide to obtain isobutene catalyst, denoted as C-5. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为27%,ZnO以氧化物计重量含量为6%,催化剂中450°C以下总酸量为0.95mmol/g,250°C_350°C的酸含量占450°C以下总酸量的72.11%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 27%, ZnO content by weight in terms of oxide 6%, 450 ° C or less in the catalyst in an amount of total acid 0.95mmol / g, an acid content of 250 ° C_350 ° C accounting for 72.11% 450 ° C or less of the total amount of acid.

[0046] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的67.23%。 [0046] Evaluation of catalyst activation and the same conditions as in Example 1, the halogen content in the catalyst after reduction was 67.23% reduction of total halogen content of the catalyst precursor. 反应结果见表1。 The reaction results are shown in Table 1.

[0047] 实施例6 [0047] Example 6

[0048] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0048] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0049] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 100 °C干燥6h,500 °C焙烧6h,制得催化剂前体Zn0/Si02。 [0049] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 100 ° C drying 6h, 500 ° C firing 6h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为C-6。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, methyl bromide to obtain isobutene catalyst, denoted as C-6. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为18%,ZnO以氧化物计重量含量为2%,催化剂中450°C以下总酸量为0.93mmol/g,250°C_350°C的酸含量占450°C以下总酸量的66.81%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 18%, ZnO content by weight of oxide in terms of 2%, 450 ° C or less in the catalyst in an amount of total acid 0.93mmol / g, an acid content of 250 ° C_350 ° C accounting for 66.81% 450 ° C or less of the total amount of acid.

[0050] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的59.73%。 [0050] Evaluation of catalyst activation and the same conditions as in Example 1, the halogen content in the catalyst after reduction was 59.73% reduction of total halogen content of the catalyst precursor. 反应结果见表1。 The reaction results are shown in Table 1.

[0051] 实施例7 [0051] Example 7

[0052] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0052] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0053] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 100 °C干燥6h,500 °C焙烧6h,制得催化剂前体Zn0/Si02。 [0053] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 100 ° C drying 6h, 500 ° C firing 6h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为C-7。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, methyl bromide to obtain isobutene catalyst, denoted as C-7. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为39%,ZnO以氧化物计重量含量为6%,催化剂中450°C以下总酸量为1.08臟〇1/^,250°0350°(:的酸含量占450°(:以下总酸量的80.29%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 39%, ZnO content by weight in terms of oxide 6%, 450 ° C or less in the catalyst in an amount of 1.08 total acid dirty 〇1 / ^, 250 ° 0350 ° (: acid content accounted for 450 ° (: 80.29% or less of the total amount of acid.

[0054] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的80.12%。 [0054] Evaluation of catalyst activation and the same conditions as in Example 1, the halogen content in the catalyst after reduction of the catalyst prior to reduction of 80.12% of the total halogen content. 反应结果见表1。 The reaction results are shown in Table 1.

[0055] 实施例8 [0055] Example 8

[0056] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0056] A weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0057] 称取适量硝酸锌、硝酸锆溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体,HKTC干燥6h,500°C焙烧6h,制得催化剂前体Zn〇-Zr/Si02。 [0057] The weighed amount of zinc nitrate, zirconium nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, drying HKTC 6h, 500 ° C calcined 6h, the catalyst precursor was prepared Zn〇-Zr / si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250 °C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为C-8。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, methyl bromide to obtain isobutene catalyst, denoted as C-8. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,Zn0以氧化物计重量含量为4%, Zr以元素计重量含量为2%,催化剂中450°C以下总酸量为1.03mmol/g,250°C-350°C的酸含量占450 °C以下总酸量的81.24%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 30%, Zn0 content by weight in terms of oxide 4%, Zr element in terms of the content of 2% by weight, 450 ° C or less in the catalyst in an amount of total acid 1.03mmol / g, the acid content of 250 ° C-350 ° C accounted for 81.24% 450 ° C or less of the total amount of acid.

[0058] 催化剂活化及评价条件同实施例I,还原后催化剂中的卤素含量为还原前催化剂中齒素总含量的61.79%。 [0058] The catalyst activation conditions and evaluated as in Example I, the halogen content of the catalyst after reduction of the catalyst before reduction is 61.79% of the total pigment content of the teeth. 反应结果见表1。 The reaction results are shown in Table 1.

[0059] 比较例1 [0059] Comparative Example 1

[0060] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0060] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0061] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 120 °C干燥4h,600°C焙烧4h,制得催化剂前体Zn0/Si02。 [0061] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 120 ° C drying 4h, 600 ° C firing 4h, before the catalyst precursor prepared Zn0 / Si02. 将催化剂前体置于连续流动固定床反应器中,使用溴甲烷与氮气的混合气体处理催化剂前体,溴甲烷体积浓度为80%,处理条件为250°C,0.2MPa (绝压),300h_1,时间2h,制得溴甲烷制异丁烯催化剂,记为DI。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using a mixed gas of nitrogen and methyl bromide catalyst precursor, methyl bromide concentration of 80% by volume, the processing conditions are 250 ° C, 0.2MPa (absolute pressure), 300h_1, time 2h, the catalyst was prepared methyl bromide isobutene, referred to as a DI. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,ZnO以氧化物计重量含量为4%,催化剂中450°C以下总酸量为1.01臟〇1/^,250°0350°(:的酸含量占450°(:以下总酸量的77.12%。 By weight to obtain a catalyst composition as a bromide ZnBr2 basis weight content of 30%, ZnO content by weight in terms of oxide 4%, 450 ° C or less in the catalyst in an amount of 1.01 total acid dirty 〇1 / ^, 250 ° 0350 ° (: acid content accounted for 450 ° (: 77.12% or less of the total amount of acid.

[0062] 溴甲烷转化制异丁烯反应在连续流动微型固定床反应器中进行。 [0062] Conversion of isobutene bromide reaction is carried out in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 原料气为溴甲烷与氮气混合气体,其中溴甲烷体积含量为70%,反应温度为230°C,反应压力为2MPa (绝压),空速为2001^。 The amount of catalyst loading 5g, dibromomethane feed gas was mixed with nitrogen gas, wherein the bromide content is 70% by volume, the reaction temperature was 230 ° C, a reaction pressure of 2MPa (absolute pressure), a space velocity of 2001 ^. 反应稳定一小时后,采样分析。 One hour after the reaction stabilization, sampling and analysis. 反应结果见表1。 The reaction results are shown in Table 1.

[0063] 比较例2 [0063] Comparative Example 2

[0064] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0064] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0065] 称取适量硝酸锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 120°C干燥4h,600°C焙烧4h,制得催化剂Zn0/Si02,记为D-2。 [0065] The weighed amount of zinc nitrate dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 120 ° C drying 4h, 600 ° C calcining 4h, to prepare a catalyst Zn0 / Si02, referred to as D- 2. 得到催化剂重量组成为ZnO以氧化物计重量含量为20%,催化剂中450 °C以下总酸量为0.4 Immo Ι/g,250 °C-350 °C的酸含量占450 °C以下总酸量的34.3%。 To obtain a ZnO weight of the catalyst composition in terms of oxide content of 20% by weight, 450 ° C or less in the catalyst in an amount of total acid 0.4 Immo Ι / g, an acid content of 250 ° C-350 ° C to 450 ° C or less accounted for total acid content of 34.3%.

[0066] 催化剂活化及评价条件同实施例1,反应结果见表1。 [0066] Evaluation of catalyst activation and the same conditions as in Example 1, the reaction results are shown in Table 1.

[0067] 比较例3 [0067] Comparative Example 3

[0068] 称取适量的十六烷基三甲基溴化铵、TMB、正硅酸四乙酯加入适量的去离子水中, 搅拌均匀,得到澄清溶液后,加入适量的乙酸乙酯,在70°C下搅拌生成溶胶,继续搅拌直至生成凝胶,所得凝胶于空气中陈化18h,于70°C干燥18h,以2°C/min升温至600°C焙烧7h,即得二氧化硅载体,其中,十六烷基三甲基溴化铵:TMB:硅元素:水:乙酸乙酯=3:1.2:1:120: 15。 [0068] The weighed amount of cetyl trimethyl ammonium bromide, of TMB, tetraethyl orthosilicate was added an appropriate amount of deionized water, stir, after a clear solution, adding an appropriate amount of ethyl acetate, in 70 ° C under stirring to generate a sol, and stirring was continued until the gel formation, the resultant gel was aged in air for 18 h, dried at 70 ° C for 18 h, at 2 ° C / min was heated to 600 ° C calcined 7H, i.e., to obtain silica carrier, wherein cetyl trimethyl ammonium bromide: of TMB: silicon element: water: ethyl acetate = 3: 1.2: 1: 120: 15.

[0069] 称取适量溴化锌溶于去离子水中,采用等体积浸渍法负载于上述二氧化硅载体, 80°C氮气气氛干燥4h,500°C氮气气氛焙烧4h,制得催化剂ZnBr2/Si02,记为D-3。 [0069] The weighed amount of zinc bromide dissolved in deionized water, using the incipient wetness impregnation of the silica supported on a carrier, 80 ° C atmosphere of dry nitrogen 4h, 500 ° C nitrogen atmosphere for calcination 4h, to prepare a catalyst ZnBr2 / Si02 , referred to as D-3. 得到催化剂重量组成为ZnBr2以溴化物计重量含量为30%,催化剂中450°C以下总酸量为0.82mmol/g, 250 °C -350 °C的酸含量占450 °C以下总酸量的58.4%。 The catalyst composition by weight ZnBr2 obtained as a bromide content of 30% by weight terms, 450 ° C or less in the catalyst in an amount of total acid 0.82mmol / g, an acid content of 250 ° C -350 ° C to 450 ° C or less accounts for the total amount of acid 58.4%.

[0070] 催化剂活化及评价条件同实施例1,还原后催化剂中的卤素含量为还原前催化剂中卤素总含量的92.91%。 [0070] Evaluation of catalyst activation and the same conditions as in Example 1, the halogen content in the catalyst after reduction was 92.91% reduction of total halogen content of the catalyst precursor. 反应结果见表1。 The reaction results are shown in Table 1.

[0071] 表1催化剂反应性能 [0071] Table 1 Catalysts

Figure CN106140225BD00111

Claims (26)

1. 一种以二氧化硅为载体的溴甲烷制异丁烯催化剂的制备方法,包括如下过程:(1)制备二氧化硅载体;(2)将氧化锌和/或助剂氧化物引入至二氧化硅载体,助剂选自Ti、Zr、Ce、 La中的一种或几种;(3)对引入氧化锌后的二氧化硅载体进行不完全溴化处理; 按最终催化剂重量含量计,不含有助剂氧化物时催化剂中氧化锌含量为0.5%-20%,溴化锌含量为10%_50%;含有助剂氧化物时催化剂中氧化锌含量为0.5%-20%,溴化锌含量为10%-50%,助剂氧化物以金属元素计在催化剂中的重量含量为0.1 %-10%。 1. A method for preparing isobutene bromide catalyst to the silica carrier, the process comprising: (1) Preparation of silica support; (2) zinc oxide and / or oxide additives introduced to the silica carriers, adjuvants selected from Ti, Zr, Ce, La in one or more of; (3) after the introduction of the silica support incompletely treated zinc oxide bromide; by weight content of the final catalyst, containing no when aid oxide content of zinc oxide in the catalyst is 0.5% to 20%, zinc bromide content of 10% _50%; aid oxide catalyst containing zinc oxide content of 0.5% to 20%, an amount of zinc bromide 10% -50%, calculated as elemental metal to aid oxide in the catalyst is 0.1 wt% -10%.
2. 根据权利要求1所述的方法,其特征在于:步骤(1)中二氧化硅载体的具体制备方法如下:将表面活性剂、均三甲苯、硅源、去离子水搅拌均匀,得到澄清的溶液后,在搅拌状态下加入乙酸乙酯,在50°C-90°C下搅拌生成溶胶;在60°C-80°C下搅拌制成凝胶,凝胶再于空气中陈化12h-24h,于60 °C-80 °C 干燥12h-24h,以1°C/min-3 °C/min升温至500 °C-700 °C 焙烧4h-1 Oh得到二氧化硅载体。 The method according to claim 1, wherein: specific preparation method step (1) in the silica support as follows: surfactant, mesitylene, silicon source, deionized water was stirred uniformly, to give a clear after the solution was added ethyl acetate under stirring, the sol was stirred generated at 50 ° C-90 ° C; at 60 ° C-80 ° C was stirred to make a gel, and then aging in air for 12h -24h, at 60 ° C-80 ° C was dried 12h-24h, at 1 ° C / min-3 ° C / min was heated to 500 ° C-700 ° C to obtain calcined 4h-1 Oh silica carrier.
3. 根据权利要求2所述的方法,其特征在于:表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基硫酸钠、十二烷基苯磺酸钠或聚乙二醇中的一种或多种;硅源为正硅酸四甲酯、正硅酸四乙酯、硅溶胶或硅酸中的一种或多种;各原料摩尔比为表面活性剂:均三甲苯:硅元素:水:乙酸乙酯=1-5:0.1-2:1:50-200:10-20。 3. The method according to claim 2, wherein: the surfactant is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, sodium lauryl sulfate, dodecyl one or more sulphonate or polyethylene glycol; silicon source is tetramethylorthosilicate, tetraethylorthosilicate, colloidal silica or silicic acid in one or more; each molar feed ratio of surfactant: mesitylene: silicon element: water: ethyl acetate = 1-5: 0.1-2: 1: 50-200: 10-20.
4. 根据权利要求1所述的方法,其特征在于:步骤(2),所述氧化锌和/或助剂氧化物引入至二氧化硅载体采用浸渍法。 4. The method according to claim 1, wherein: step (2), the zinc oxide and / or oxide additives introduced into the silica support by impregnation.
5. 根据权利要求4所述的方法,其特征在于:采用锌盐、助剂金属盐溶液浸渍二氧化硅载体,并进行干燥、焙烧。 The method according to claim 4, characterized in that: the use of zinc, a metal salt solution impregnated silica support aids, and dried, calcined.
6. 根据权利要求5所述的方法,其特征在于:干燥温度60°C-150°C,时间为lh-24h,焙烧温度200°C-800°C,时间为lh-24h。 6. The method according to claim 5, wherein: the drying temperature of 60 ° C-150 ° C, time lh-24h, the firing temperature 200 ° C-800 ° C, time lh-24h.
7. 根据权利要求4所述的方法,其特征在于:锌盐为硝酸盐、盐酸盐、醋酸盐、柠檬酸盐中的一种或几种。 7. The method as claimed in claim 4, wherein: the zinc salt is a nitrate, chloride, acetate, citrate, one or several.
8. 根据权利要求1所述的方法,其特征在于:步骤(3)中所述溴化处理是指采用气相含溴化合物对负载氧化锌的样品进行处理。 8. The method according to claim 1, wherein: step (3) refers to the use of the brominated compounds containing bromine gas sample processing load zinc oxide.
9. 根据权利要求8所述的方法,其特征在于:含溴化合物是指溴甲烷、二溴甲烷、三溴甲烷中的一种或几种。 9. The method according to claim 8, wherein: the bromine-containing compound refers to methyl bromide, dibromomethane, bromoform one or more of.
10. 根据权利要求8所述的方法,其特征在于:采用气相含溴化合物与惰性气体的混合气体进行溴化处理,采用混合气体溴化处理时,溴代甲烷体积浓度不小于20%。 10. The method according to claim 8, wherein: a mixed gas containing bromine compound gas and an inert gas, is brominated using mixed gas processing bromide, methyl bromide concentration of not less than 20% by volume.
11. 根据权利要求8所述的方法,其特征在于:具体溴化过程如下:将负载氧化锌的样品置于连续流动固定床反应器中,惰性气氛下升温至150°C-40(TC,通入气相含溴化合物气体,气体空速为50h_1-1000 h_1,体系压力为0.1MPa-0.5MPa,处理时间为0.5h-8h。 11. The method according to claim 8, wherein: the specific bromination process is as follows: The sample was placed load zinc oxide fixed bed continuous flow reactor under an inert atmosphere was warmed to 150 ° C-40 (TC, bromine-containing compound gas into gas, the gas space velocity 50h_1-1000 h_1, system pressure is 0.1MPa-0.5MPa, the processing time was 0.5h-8h.
12. 权利要求1至11任一方法制备的催化剂,其特征在于:所述催化剂含有氧化锌、溴化锌及二氧化硅载体,按催化剂重量含量计,氧化锌含量为〇. 5%-20%,溴化锌含量为10%-50%, 二氧化硅载体含量为40%_90%。 12. The catalyst prepared by a method according to any of claims 1 to 11, wherein: the catalyst contains zinc oxide, zinc bromide, and the silica support, the count content of the catalyst by weight, the zinc oxide content of 5% to 20 billion. %, zinc bromide content of 10% -50%, the silica content of the carrier was 40% _90%.
13. 根据权利要求12所述的方法,其特征在于:氧化锌含量为1%-15%,溴化锌含量为15%-45%〇 13. The method according to claim 12, wherein: the zinc oxide content of 1% to 15%, zinc bromide content of 15% -45% billion
14. 根据权利要求13所述的方法,其特征在于:氧化锌含量为1%-9%,溴化锌含量为18%- 39% 〇 14. The method according to claim 13, wherein: the zinc oxide content of from 1% to 9%, zinc bromide content of 18% - 39% square
15. 根据权利要求12所述的方法,其特征在于:催化剂含有助剂氧化物,助剂氧化物以金属元素计在催化剂中的重量含量为0.1%_1〇%,助剂选自Ti、Zr、Ce、La中的一种或几种。 15. The method according to claim 12, wherein: the catalyst contains an oxide additives, adjuvants oxides in the catalyst metal element content of 0.1% by weight _1〇% additives selected from Ti, Zr , of Ce, La one or more.
16. 根据权利要求12所述的方法,其特征在于:催化剂中450°C以下总酸量为O . 5mmol/ g-1 · 3mmo I /g,250 °C -350 °C 的酸含量占450 °C 以下总酸量的20%-90%。 16. The method according to claim 12, wherein: the catalyst 450 ° C or less in an amount of total acid O 5mmol / g-1 · 3mmo I / g, an acid content of 250 ° C -350 ° C accounted 450 20% -90% ° C or less of the total amount of acid.
17. 权利要求12所述催化剂的应用,其特征在于:包括对催化剂进行氢气还原活化,使催化剂中的卤素含量为还原前催化剂中卤素总含量的20%_90%,然后使卤代甲烷与氢气还原活化后的催化剂接触,以制备异丁烯。 12 17. The use of the catalyst as claimed in claim, characterized in that: comprising hydrogen reduction catalyst activation, the halogen content of the catalyst is from 20% reduction _90% of the total halogen content in the catalyst precursor, and halogenated methane and hydrogen reducing the contact activated catalyst, to produce isobutene.
18. 根据权利要求17所述催化剂的应用,其特征在于:所述氢气还原活化的条件使得催化剂中的卤素含量为还原前催化剂中卤素总含量的30%_80%。 17 Application of the catalyst according to claim 18, wherein: said activation conditions such that the hydrogen reduction of the halogen content in the catalyst was 30% _80% reduction of total halogen content of the catalyst before.
19. 根据权利要求17所述催化剂的应用,其特征在于:所述氢气还原活化的方式包括在惰性气氛下将催化剂升温至300°C-600°C;然后通入空速为2001^-200011-1的氢气或氢气与惰性气体的混合气体,在〇. IMPa-0.5MPa保持2h_16h,混合气体中氢气体积百分含量为10%-95%〇 17 Application of the catalyst according to claim 19, wherein: said means of activation comprises a reduction with hydrogen, the catalyst was heated to 300 ° C-600 ° C under an inert atmosphere; and a space velocity of 2001 passed ^ -200011 -1 or a mixed gas of hydrogen with an inert gas, hydrogen gas, in the square. IMPa-0.5MPa holding 2h_16h, a mixed gas of hydrogen volume percentage of 10% to 95% square
20. 根据权利要求19所述催化剂的应用,其特征在于:升温至350°C-550°C ;然后通入空速为500h_1-1000h_1的氢气或氢气与惰性气体的混合气体,在0. IMPa-0.3MPa保持4h-8h,所述混合气体中氢气体积百分含量为30%_90%。 20. Application of the catalyst according to claim 19, wherein: heated to 350 ° C-550 ° C; and a space velocity of the mixed gas into hydrogen 500h_1-1000h_1 or hydrogen and inert gas in 0. IMPa -0.3MPa holding 4h-8h, the mixed gas of hydrogen volume percentage of 30% _90%.
21. 根据权利要求17所述催化剂的应用,其特征在于:卤代甲烷为一卤代甲烷、二卤代甲烷、三卤代甲烷中的一种或多种。 21. Application of the catalyst according to claim 17, characterized in that: a halogenated methane, halogenated methane, dihalomethane, trihalomethanes one or more.
22. 根据权利要求17所述催化剂的应用,其特征在于:卤代甲烷为溴甲烷、二溴甲烷、三溴甲烷中的一种或多种。 22. Application of the catalyst according to claim 17, characterized in that: methyl halide is methyl bromide, dibromomethane, bromoform one or more.
23. 根据权利要求17所述催化剂的应用,其特征在于:接触的条件包括反应温度为150 。 17 Application of the catalyst according to claim 23, wherein: the contacting conditions include a reaction temperature of 150. (:-350 °C ;反应压力为0 · lMPa-5MPa;空速为50h_1- 1000h_1。 (: -350 ° C; reaction pressure is 0 · lMPa-5MPa; airspeed 50h_1- 1000h_1.
24. 根据权利要求23所述催化剂的应用,其特征在于:反应温度为180°C_300°C ;反应压力为0 · lMPa-3MPa;空速为200h_1-500h_1。 24. Use of the catalyst according to claim 23, wherein: the reaction temperature is 180 ° C_300 ° C; reaction pressure is 0 · lMPa-3MPa; airspeed 200h_1-500h_1.
25. 根据权利要求17所述催化剂的应用,其特征在于:包括惰性气氛下将催化剂升温至300°C_600°C;然后通入空速为2001^-20001^1的氢气或氢气与惰性气体的混合气体,在 25. Application of the catalyst according to claim 17, wherein: a catalyst under inert atmosphere was warmed to 300 ° C_600 ° C; then passed through a space velocity of 2001 -20001 ^ ^ 1 is hydrogen or hydrogen and inert gas a mixed gas, in
0. IMPa-0.5MPa处理2h-16h,降至反应温度通入卤代甲烷进行反应,所述混合气中氢气体积百分含量为1〇%_95%。 0. IMPa-0.5MPa treated 2h-16h, the reaction temperature dropped to methyl halide reaction, said mixed gas volume percentage of hydrogen 1〇% _95%.
CN201510135845.6A 2015-03-27 2015-03-27 Kind of silica-supported catalysts and their preparation and use CN106140225B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510135845.6A CN106140225B (en) 2015-03-27 2015-03-27 Kind of silica-supported catalysts and their preparation and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510135845.6A CN106140225B (en) 2015-03-27 2015-03-27 Kind of silica-supported catalysts and their preparation and use

Publications (2)

Publication Number Publication Date
CN106140225A CN106140225A (en) 2016-11-23
CN106140225B true CN106140225B (en) 2018-10-12

Family

ID=57340457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510135845.6A CN106140225B (en) 2015-03-27 2015-03-27 Kind of silica-supported catalysts and their preparation and use

Country Status (1)

Country Link
CN (1) CN106140225B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154969A (en) * 1977-03-24 1979-05-15 Monsanto Company Production of dihydroxydiphenyl alkanes
CN101484406A (en) * 2006-02-03 2009-07-15 Grt公司 Continuous process for coN. V.erting natural gas to liquid hydrocarbons

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154969A (en) * 1977-03-24 1979-05-15 Monsanto Company Production of dihydroxydiphenyl alkanes
CN101484406A (en) * 2006-02-03 2009-07-15 Grt公司 Continuous process for coN. V.erting natural gas to liquid hydrocarbons

Also Published As

Publication number Publication date
CN106140225A (en) 2016-11-23

Similar Documents

Publication Publication Date Title
DeBoy et al. The oxidative coupling of methane over alkali, alkaline earth, and rare earth oxides
CN100548945C (en) Process of methanol conversion for preparing arene and catalyst and catalyst preparation method
Wieland et al. Side-chain alkylation of toluene with methanol over alkali-exchanged zeolites X, Y, L, and β
EP0227750A1 (en) Method and catalyst for the conversion of methane
EP0031243B1 (en) Preparation of methanol from synthesis gas with promoted palladium catalysts
WO2007107081A1 (en) Conversion of methane into c3~c13 hydrocarbons
CN102471181A (en) Process for the oxidative coupling of methane
CN102452878B (en) Method for preparing low-carbon olefin by synthetic gas one-step technology
CN101628242A (en) Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof
CN1083415A (en) Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction
US20040110973A1 (en) Olefin oxide catalysts
CN101284232B (en) Bromomethane prepared by bromine oxidation of methane and catalyst for conversing the bromomethane into hydrocarbon
CN102040459A (en) Toluene methanol methylation reaction method
CN101015802A (en) Catalyst for preparing propylene by propane dehydrogenation and its prepn.
CN102441383A (en) Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas
CN101456791A (en) Method for producing 1,2-propanediol by using biological base glycerol
JP2006501066A (en) Calcium carbonate carriers for the production of epoxidation catalysts containing silver as a main component
CN102145306B (en) Method for adjusting properties of alumina carrier by selecting hydrated alumina with different grain size, carrier obtained by method and application
CN103480375A (en) Carbon monoxide methanating catalyst and preparation method thereof
CN101623649B (en) Alkaline molecular sieve catalyst for preparing styrene
CN1260324A (en) Preparation method for zirconium dioxide
JP2003533348A (en) Its use in the solid base catalyst and base catalysis
CN1232720A (en) Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process
CN101380587A (en) Propane dehydrogenation catalyst to produce propylene and preparation method thereof
JP2003326169A (en) Oligomerization catalyst and manufacturing method for oligomer using the same

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
GR01