CN106140227A - Catalyst with modified alumina as carrier, and preparation method and application thereof - Google Patents

Catalyst with modified alumina as carrier, and preparation method and application thereof Download PDF

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CN106140227A
CN106140227A CN201510135852.6A CN201510135852A CN106140227A CN 106140227 A CN106140227 A CN 106140227A CN 201510135852 A CN201510135852 A CN 201510135852A CN 106140227 A CN106140227 A CN 106140227A
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catalyst
gas
content
hydrogen
desert
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CN106140227B (en
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李�杰
张信伟
张舒冬
孙晓丹
倪向前
尹泽群
刘全杰
张喜文
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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
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Abstract

The invention discloses a catalyst with modified alumina as a carrier, and a preparation method and an application thereof. The catalyst is prepared by the following steps: (1) carrying out saturated impregnation of an alumina carrier with a nitrogen-containing organic compound aqueous solution with equal volume, after impregnation, immediately drying for 0.5-1 h at the temperature of 95-110 DEG C, drying until the adsorption amount of the nitrogen-containing organic compound aqueous solution is 30-60% of the saturated absorption solution amount of the alumina carrier, and then aging, drying and roasting to obtain a modified alumina carrier; (2) carrying out saturated impregnation of the modified alumina carrier prepared in the step (1) with a manganese salt solution, and then drying and roasting, wherein the manganese salt solution contains 2-15% by mass of ammonium thiocyanate; and (3) carrying out bromination treatment of the material roasted in the step (2), making the weight content of manganese oxide in the catalyst be 0.5%-5%, preferably 1%-3%, and making the weight content of manganese bromide be 5%-40%, preferably 10%-30%. The catalyst can significantly improve the selectivity of isobutene.

Description

-种w改性氧化锅为载体的催化剂及其制备方法和应用 Catalyst and preparation method and application of modified species w pot oxide as carrier -

技术领域 FIELD

[0001] 本发明设及一种W改性氧化侣为载体的催化剂及其制备方法和应用,具体地说设及一种W漠甲烧为原料高选择性制异下締的W改性氧化侣为载体的催化剂及其制备方法和应用。 [0001] The present invention is provided, and one W companion oxide modified supported catalysts and preparation method and applications, particularly modified set W W Mo oxide, and one association of the raw material A is burned with high selectivity to isobutyric Lu supported catalysts and preparation method and application.

背景技术 Background technique

[0002] 异下締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] Under different association is an important basic organic chemicals, many of its derivatives, the downstream chain complex, the structure was diversified consumer trend. W异下締为原料可W制备多种高附加值的产品,如:下基橡胶、聚异下締、甲基叔下基酸、异戊二締和有机玻璃等多种有机化工原料和精细化学产品。 Association may be prepared by a variety of high added value W of the product raw material W is different, such as: lower base rubber, polyisoprene next association, under acid methyl t, isoprene and association plexiglass and other organic chemical raw materials and fine chemical product. 由于异下締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,异下締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 association under the different downstream products continues to expand, its supply and demand will become more apparent, especially in the context of oil resources are depleted, under different production association has become a key bottleneck in the development of downstream industries. 因此,开发非石油路线的异下締制备路线,已经迫在眉睫。 Therefore, the development of non-petroleum routes under different association preparative route is imminent.

[0003] 甲烧是天然气的主要成分,因此甲烧转化利用就成为天然气化工技术中的重要研究内容。 [0003] A burn is the main component of natural gas, so A burning conversion and utilization has become an important research Natural Gas Chemical Industry. 特别是近年来,在页岩气开发利用的大背景下,如果能够实现从甲烧出发制取异下締,就会为获取异下締提供一条新的途径。 Especially in recent years, shale gas exploitation in the background can be achieved if the starting preparation for methane at different association, will be provided to obtain the exclusive association of a new way. 但是甲烧性质稳定,不易活化,成为甲烧化工利用的瓶颈。 A burning but stable, easy to activate to become a bottleneck for methane chemical use. 国内外许多研究者纷纷开展甲烧活化、转化研究,运其中,甲烷烃面素官能团化后再转化的技术,有望成为解决甲烧转化技术难题的一个重要突破口。 Many researchers at home and abroad have carried armor burn activation, translational research, transport which methane hydrocarbons prime functionalized surface after conversion technology, is expected to become a major breakthrough in solving technical problems for methane conversion.

[0004] 从面代甲烧出发可制备许多化工产品。 [0004] A burning departure from the surface can be made on behalf of a number of chemical products. 中国专利CN 101041609AXN 101284232A 公开了一种将甲烧在氧气和皿r/UO的作用下转化为漠代甲烧,然后漠代甲烧进一步反应生成C3~C13混合高碳控的方法,巧W上的控类选择性为70%。 Chinese Patent CN 101041609AXN 101284232A discloses a method for methane and oxygen under the action of dishes r / UO of substituting for methane into desert and desert substituting A burning method further reacted C3 ~ C13 carbon controlled mixing, W skillfully the control class selectivity of 70%. 其中,皿r在第一个反应器内用于甲烧漠化,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,实现皿r的循环使用。 Wherein r dish in the first reactor is used for methane desertification, and then released in the second reactor, and then recovered through a pre-step reaction, the dish implement recycling of r. 王野等(CN 10化27427A,Jieli He, Ting Xu, Zhihui Wang, et. al. Angew. Qiem. Int. Ed. 2012,51,2438-2442)公开了一种面代甲烧制丙締的改性分子筛催化剂及其制备方法。 Wang et Ye (CN 10 of 27427A, Jieli He, Ting Xu, Zhihui Wang, et. Al. Angew. Qiem. Int. Ed. 2012,51,2438-2442) discloses a prop associated surfaces of fired-generation A modified molecular sieve catalysts and their preparation methods. 通过使用含氣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W有效催化面代甲烧转化生成丙締的反应。 By using a compound gas containing molecular sieves modification treatment, to obtain a suitable porous structure and containing an acidic catalyst, the catalyst may be effective to catalyze surface W substituting for methane conversion reaction to generate the associated prop. 所制备的催化剂在漠甲烧转化制丙締的反应中单程漠甲烧转化率为35~99%,丙締的选择性为27~70% ;在氯甲烧转化制丙締的反应中单程氯甲烧转化率为30~99%,丙締的选择性为15~70%。 The selectivity of the catalyst prepared in the way desert for methane conversion was 35% to 99% for methane conversion in desert C system reaction in association, the association prop 27 to 70%; single pass conversion reaction flask chloromethyl propionate prepared in association a burning chlorine conversion rate 30 to 99% and the selectivity is associated propan 15 to 70%. Ivan M. Lorkovic等人(Ivan Μ. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004,98,317-322)也提出用漠与天然气中的烧控反应生成漠代控,然后在金属氧化物催化剂上将漠代控转化为二甲酸、甲醇和金属漠化物,金属漠化物用氧气再生后得到金属氧化物并释放出单质漠,完成了漠的循环。 Ivan M. Lorkovic et al (Ivan Μ. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004,98,317-322) also made substituting the reaction of desert and desert control by burning natural gas control, then converted to the acid on the metal oxide catalyst desert control generation of, methanol and desertification metal, metal compound desert after regeneration of oxygen to give a metal oxide and elemental release desert, complete cycle of the desert.

[0005] 目前,关于面代甲烧转化的现有文献中目的产物主要为甲醇、二甲酸、醋酸、高碳控类、乙締与丙締等等。 [0005] Currently, the existing literature on the surface of substituting for methane conversion of the desired product are primarily methanol, acid, acetic acid, carbon-based control, and the like associated with malonic B associative. 在W较高附加值的低碳締控为目标产物的技术中,单一产物选择性不高,尚未发现漠甲烧高选择性合成异下締的相关报道。 W is lower in association with higher added value as the control target product art, high selectivity is not a single product has not been found to burn the desert A selective synthesis of the association of the different reports.

发明内容 SUMMARY

[0006] 针对现有技术的不足,本发明提供了一种W漠甲烧为原料高选择性制异下締的催化剂及其制备方法与应用。 [0006] for the deficiencies of the prior art, the present invention provides a catalyst and a preparation method and Application of a desert W high selectivity for methane as a raw material manufactured by the association of different.

[0007] -种漠甲烧制异下締催化剂的制备方法,其特征在于:包括如下步骤:(1)氧化侣载体等体积饱和浸溃含氮有机化合物水溶液,浸溃后立即在95-110°C下干燥0. 5-比,干燥至含氮有机化合物水溶液的吸附量为氧化侣载体饱和吸收溶液量的30-60%,然后经老化、 干燥、赔烧后制得改性氧化侣载体;(2)步骤(1)制备的改性氧化侣载体饱和浸溃儘盐溶液并进行干燥、赔烧,所述儘盐溶液中含有质量分数为2-15%的硫氯酸锭;(3)对步骤(2)赔烧后的物料进行漠化处理使催化剂中氧化儘重量含量为0. 5%-5%,优选1%-3% ;漠化儘重量含量为5%-40%,优选10%-30%。 [0007] - A desert species prepared under different firing association catalyst, characterized by: comprising the steps of: Volume (1) Lu et oxide support impregnated with saturated aqueous solution of a nitrogen-containing organic compound, immediately after dipping in 95-110 5- lower than 0.5 ° C and dried, and dried to the adsorption amount of aqueous solution containing organic compound oxide carrier companion saturable absorbing solution an amount of 30-60%, and then aged, dried and fired to obtain compensation companion oxide modified support ; (2) step (1) preparation of modified oxide support companion saturated salt solution make impregnation and drying, firing compensation, to make the ingot sulfur acid salt solution containing 2-15% of the mass fraction; (3 ) in step (2) after compensation for desert burning material so that the oxidation process to make the catalyst content of 0.5% by weight to 5%, preferably 1% to 3%; by weight do desertification content of 5% -40%, preferably 10% -30%.

[0008] 上述漠甲烧制异下締催化剂的制备方法中,步骤(1)中含氮有机化合物水溶液中含氮有机化合物为乙醇胺、二乙醇胺、Ξ乙醇胺和化晚中的一种或几种;含氮有机化合物水溶液中含氮有机化合物的重量浓度为1%-35% ;老化溫度为50-95°C,老化时间为0. 5-lOh, 老化后干燥溫度为90-150°C,干燥时间为0. 5-36h,赔烧在280-500°C下赔烧2-15小时。 [0008] A method for preparing the above-described firing desert isobutyl association catalyst, step (1) the nitrogen-containing organic compound in aqueous ethanolamine, diethanolamine, ethanolamine, and a Cascade of one or several nights ; weight concentration of the aqueous solution of a nitrogen-containing organic compound is 1% to 35%; aging temperature of 50-95 ° C, the aging time is 0. 5-lOh, the drying temperature after aging of 90-150 ° C, the drying time was 0. 5-36h, lose lose burn burn 2-15 hours at 280-500 ° C.

[0009] 上述漠甲烧制异下締催化剂的制备方法中,所述氧化侣载体可W采用现有氧化侣产品,也可W按本领域技术人员熟知的方法制备。 [0009] The method of preparing the catalyst association iso desert A firing, the oxide support may be Lu Lu W using conventional oxidation products, prepared by the method well known to those skilled in the art may be W. 载体可W根据使用的需要制成或选取适宜的颗粒形态,如制成条形、片形、柱形、球形等。 W The carrier may be made as appropriate particle morphology or choose to use such formed strip, sheet-shaped, cylindrical, spherical and the like. 成形可W按本领域一般知识进行。 W can be formed according to the general knowledge in the art.

[0010] 上述漠甲烧制异下締催化剂的制备方法步骤(2)中干燥条件为,溫度60°C -150°C,优选为80°C -120°C ;时间为比-2地,优选为4h-她;干燥时可W为真空干燥, 也可W为惰性气体保护条件下干燥,还可W在空气气氛下干燥。 [0010] The fired at different desert A method for preparing a catalyst association step (2) in the drying conditions, a temperature of 60 ° C -150 ° C, preferably 80 ° C -120 ° C; time than -2, the preferably 4h- she; W is vacuum drying may be drying, may be W is dried under inert gas conditions, W may be dried in an air atmosphere. 所述赔烧条件为,溫度300°C -600°C,优选为400°C -500°C;时间为比-2地,优选为4h-她;赔烧时可W为惰性气体保护条件下赔烧,也可W在空气气氛下赔烧。 The firing condition is lost, the temperature of 300 ° C -600 ° C, preferably 400 ° C -500 ° C; time than -2, the preferable 4h- she; W may be protected under an inert gas firing conditions lose compensation burning, W may be fired in an air atmosphere compensable.

[0011] 上述方法中,儘盐可W为无机盐,也可W为有机盐,优选为硝酸盐、盐酸盐、醋酸盐、巧樣酸盐中的一种或几种。 [0011] In the above method, although the salt may be inorganic salts W, W may be an organic salt, preferably a nitrate, one or more of hydrochloride, acetate, Qiao kind of salt.

[0012] 上述漠甲烧制异下締催化剂的制备方法步骤(3)中所述漠化处理,是指采用气相含漠化合物对负载氧化儘的样品进行处理。 [0012] The method for preparing desert A firing step under different associated catalyst (3) in the desert treatment, refers to the use of the load gas indifferent compound oxide containing samples treated to make. 含漠化合物是指漠甲烧、二漠甲烧、Ξ漠甲烧中的一种或几种,优选为漠甲烧。 Refers to a compound containing Mo desert for methane, bis desert A burning, a Cascade desert A burning one or several, preferably methyl burning desert. 还可W采用气相含漠化合物与惰性气体的混合气体进行漠化处理,采用混合气体漠化处理时,漠代甲烧体积浓度不小于20%,优选为不小于30%。 W may also be a mixed gas with an inert gas containing a compound gas desert desertification process is performed, when the mixed gas treatment desert, desert substituting for methane concentration of not less than 20% by volume, preferably not less than 30%. 具体漠化过程如下:将负载氧化儘的样品置于连续流动固定床反应器中,惰性气氛下升溫至150°C -400°C,优选为180°C -350°C,更优选为200°C -300°C,通入气相含漠化合物气体,气体空速为50h 1-1000 h 1,优选为10化1-50化1;处理时可W在常压进行,也可W在一定压力下进行,体系压力为0. lMPa-0. 5MPa (绝压),优选为0. lMPa-0. 3MPa (绝压),处理时间为0.化-她,优选比-地。 DETAILED desertification process is as follows: The sample was placed in the load do oxide fixed bed continuous flow reactor under an inert atmosphere was warmed to 150 ° C -400 ° C, preferably 180 ° C -350 ° C, more preferably 200 ° C -300 ° C, Mo-containing compound gas into gas, the gas space velocity of 50h 1-1000 h 1, preferably of 1 to 10 of 1-50; W may be carried out at normal pressure process, but also a certain pressure W carried out under, pressure of the system 0. lMPa-0 5MPa (absolute), preferably 0. lMPa-0 3MPa (absolute pressure), the processing time of 0.5 - she, preferably more than - the.

[0013] 上述漠甲烧制异下締催化剂的制备方法中所设及的惰性气体为氮气、氣气、氮气等在本发明所设及条件下不发生化学反应的气体,优选为氮气。 [0013] The gas fired at different desert A method of preparing the catalyst in association established and the inert gas is nitrogen gas, air gas, such as nitrogen which does not react chemically under conditions and established the present invention, preferably nitrogen.

[0014] 所述漠甲烧制异下締催化剂,催化剂中氧化儘重量含量为0. 5%-5%,优选1%-3% ; 漠化儘重量含量为5%-40%,优选10%-30% ;氧化姉重量含量为0. 1%-2%,优选为0. 5%-1. 5% ; 氧化侣载体重量含量60%-95%,优选65%-90%。 [0014] The association of the desert methyl isobutyl fired catalyst, an oxidation catalyst to make the weight content of 0.5% to 5%, preferably 1% to 3%; desertification best content of 5% -40 wt%, preferably 10 % -30%; percent oxide content of 0.1% by weight to 2%, preferably 0.5% -15%; oxidation companion carrier content 60% -95% by weight, preferably 65% ​​to 90%.

[0015] 上述催化剂在制异下締中的应用,包括对催化剂进行氨气还原活化,使催化剂中的面素含量为还原前催化剂中面素总含量的20%-90%,然后使面代甲烧与上述氨气还原活化后的催化剂接触,w制备异下締。 [0015] The application of the catalyst in association isobutyric, including reductive activation of the catalyst is ammonia, so that the surface element content in the catalyst was 20% -90% reduction of the total content of the front surface of the catalyst element, and then the generation of surface a burn in contact with the reduction catalyst after activation of the above-described ammonia, prepared under different associated w.

[0016] 上述应用中,所述氨气还原活化的条件使得催化剂中的面素含量优选为还原前催化剂中面素总含量的30%-80%,进一步优选40%-80%。 [0016] In the above application, the ammonia gas such that the surface conditions of reductive activation element content in the catalyst is preferably 30% -80% reduction of the total amount of the catalyst surface before the element, more preferably 40% -80%.

[0017] 上述应用中,所述氨气还原活化的方式包括在惰性气氛下将催化剂升溫至300°C -600°C ;然后通入空速为20化i-2000h 1的氨气或氨气与惰性气体的混合气体,在0. lMPa-0. 5MI^保持化-1化,混合气体中氨气体积百分含量为10%-95% ;优选地,升溫至350°C -550°C ;然后通入空速为50化i-lOOOh 1的氨气或氨气与惰性气体的混合气体,在0. lMPa-0. 3M化保持4h-她,所述混合气体中氨气体积百分含量为30%-90%。 [0017] In the above application, the ammonia reductive activation methods include heating the catalyst under an inert atmosphere to 300 ° C -600 ° C; 20 and then passed into a space velocity of ammonia gas or ammonia i-2000h 1 . mixed with inert gas in 0. lMPa-0 5MI ^ -1 of the holding of the mixed gas of ammonia volume percentage of 10% to 95%; preferably, the temperature was raised to 350 ° C -550 ° C ; then passed through a space velocity of 50 i-lOOOh mixed gas of ammonia gas or an ammonia gas with an inert gas, maintaining 4h- she 0. lMPa-0 3M of the mixed gas in volume percent ammonia. content of 30% -90%.

[0018] 上述催化剂的应用,还包括面代甲烧与催化剂接触获取异下締。 [0018] Application of the above catalyst, further comprising a surface contact with the catalyst substituting for methane acquired under different association. 所述接触的条件包括反应溫度为150°C -350°C ;反应压力为0. lMPa-5MPa ;空速为50h 1-100化1;更优选地,反应溫度为180°C -300°C更优选为200-270°C ;反应压力为0. lMPa-3MPa ;空速为200h i-500h 1。 The contacting conditions include a reaction temperature of 150 ° C -350 ° C; reaction pressure is 0. lMPa-5MPa; a space velocity of 1 to 50h 1-100; more preferably, the reaction temperature is 180 ° C -300 ° C more preferably 200-270 ° C; reaction pressure is 0. lMPa-3MPa; a space velocity of 200h i-500h 1.

[001引上述应用中,所述面代甲烧可W为一面代甲烧、二面代甲烧、S面代甲烧中的一种或多种,优选为漠甲烧、二漠甲烧、Ξ漠甲烧中的一种或多种,更优选为漠甲烧。 [001 application cited above, the surface may be substituting for methane generation of side A and W is burned, burning dihedral behalf A, S A burning surface behalf of one or more, preferably methyl desert burn, burn two desert A , a Cascade desert a burning one or more, more preferably methyl burning desert.

[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溫至300°C -600°c, 优选为350°C -550°C;然后通入空速为20化1-200化1,优选为50化i-lOOOh 1的氨气与惰性气体的混合气体,在0. lMPa-0. 5MPa (绝压),优选为0. lMPa-0. 3MPa (绝压)处理化-1化,优选为4h-化后,降至反应溫度通入面代甲烧进行反应。 [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; 20 and then passed into a space velocity of 1-200 of 1, preferably 50 i-lOOOh mixed gas of ammonia gas and an inert gas is 1 (absolute pressure) at 0. lMPa-0 5MPa, preferably 0. lMPa-0 3MPa (absolute pressure) of the process. - 1, it is preferable 4h- of after, the reaction temperature is lowered to the surface through the generation of A burning reaction. 所述混合气中氨气体积百分含量为10%-95%,优选为30%-90%,更优选为50%-90%。 The mixture of ammonia gas volume percentage of 10% to 95%, preferably 30% to 90%, more preferably 50% to 90%.

[0021] 上述应用中,原料也可W为面代甲烧与惰性气体的混合气体,混合气体中面代甲烧的体积浓度为10%-90%,优选为30%-80%。 [0021] In the above application, the feedstock mixed gas may be W is a surface burning Generation A and an inert gas, a mixed gas of the surface of substituting for methane concentration between 10% to 90%, preferably 30% -80%.

[0022] 上述应用中所设及的惰性气体为氮气、氣气、氮气等在本发明所设及条件下不发生化学反应的气体,优选为氮气。 [0022] and the inert gas is nitrogen established applications, gas gas, such as nitrogen which does not react chemically under the conditions established by the present invention and the above-described gas, preferably nitrogen.

[0023] 上述应用中,面代甲烧制异下締反应可W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, generation of surface A may be fired at different association reaction carried out in any conventional form W reactor, fixed bed, fluidized bed, fixed bed, moving bed, ebullating bed or slurry bed other forms of reactor, preferably a fixed bed, a fluidized bed reactor.

[0024] 与现有技术相比,本发明设及的方法可W将漠甲烧高选择性的转化为异下締。 [0024] Compared with the prior art, the present invention is provided a method and W can be highly selective for methane desert into the different association. 在本发明方法中采用不均匀改性法,含氮有机物经部分蒸发后,改性溶液主要集中在载体的内部,使催化剂的内外性质产生差异,提高催化剂内部的催化活性,抑制了扩散的异下締进行再次反应。 In the process of the invention uses non-uniform modification process, after partial evaporation of the nitrogen-containing organic compounds, mainly modified solution in the carrier, so that a difference in internal and external nature of the catalyst, improving the catalytic activity of the catalyst inside the suppressed proliferation of different the association reaction again. 采用加入了含硫氯酸锭的儘盐溶液能够提高活性组分的分散度,制备出小晶粒的活性组分儘催化剂,从而明显提高低碳締控的选择性。 Using a sulfur-containing acid is added to make the salt solution of the ingot can be improved dispersion of the active ingredient, the active ingredient prepared small grains make the catalyst, thereby significantly increasing the selectivity associated controlled lower. 按本发明方法进行漠甲烧转化制异下締反应,漠甲烧转化率50% W上,异下締选择性60% W上。 A desert performed according to the method of the present invention under different firing Conversion association reaction, the conversion rate of burning desert A 50% W, the association of the different selectivity of 60% W. 本发明设及漠甲烧转化制异下締催化剂制备方法简单,易于工业化。 The present invention is provided to burn and desert A simple method of preparing the catalyst association isobutyl Conversion easy industrialization. 本发明漠甲烧转化制异下締方法具有反应条件溫和、产物选择性高等优点,容易实现工业化,应用前景非常广阔。 A burning desert Conversion of the present invention under different method associated with 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] 实施例1 称取市售氧化侣讶L容为0. 96ml/g,比表面积为286. 81mVg,饱和吸水量为145ml/g,由中国石化催化剂有限公司抚顺分公司提供,w下实施例及比较例均使用该氧化侣),将质量浓度为5%的化晚水溶液饱和喷淋浸溃氧化侣,结束后立即在95°C下干燥Ih,干燥制化晚水溶液的吸附量为氧化侣载体饱和吸收溶液量的60%,60°C下老化化,在100°C中干燥24小时,然后在300°C赔烧5小时制得改性氧化侣载体。 [0026] Example 1 weighed oxidation of commercially available L volume was surprised companion 0. 96ml / g, a specific surface area of ​​286. 81mVg, saturated water absorption of 145ml / g, the catalyst provided by the China Petrochemical Co. Fushun branch, the w Examples and Comparative Examples are the use of oxidation Lu), a concentration of 5% by mass of a saturated aqueous spray dipping late companion oxidation, immediately after adsorption Ih is dried, drying of the aqueous solution is in the late 95 ° C for Lu carrier oxidizing solution saturated absorption amount 60%, 60 ° C aging, drying at 100 ° C for 24 hours, and then fired at 300 ° C for 5 hours to obtain compensation modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为2%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,l〇(TC干燥化,45(TC赔烧化,制得催化剂前体。将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为250°C,0. 2MPa(绝压),30化1,时间化,制得漠甲烧制异下締催化剂,记为C-1。得到催化剂Μη化2¾漠化物计重量含量为18%,MnO W氧化物计重量含量为2%。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution of 2% saline solution to make equal volume impregnation method companion oxide supported on said carrier, l〇 (TC desiccation, 45 (TC compensation burnt, to prepare a catalyst precursor. the catalyst precursor was placed in a continuous flow fixed bed reactor, using desert for methane and nitrogen mixed gas catalyst precursor for methane desert volume concentration 60%, the processing conditions are 250 ° C, 0. 2MPa (absolute), 30 for 1, the time of the prepared desert A firing associative catalyst isobutyl, referred to as C-1. obtain a catalyst Μη of 2¾ desert compound Total weight content of 18%, MnO W oxides content of 2 wt%.

[0027] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0027] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的71. 91%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 71.91% of the total pigment content in the catalyst surface.

[0028] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为2MPa (绝压),空速为35化1。 After [0028] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 2MPa ( absolute pressure), a space velocity of 1 to 35. 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.

[002引实施例2 称取市售氧化侣,将质量浓度为20%二乙醇胺水溶液饱和喷淋浸溃氧化侣,结束后立即在110°C下干燥0.化,干燥至二乙醇胺水溶液的吸附量为氧化侣载体饱和吸收溶液量的40%,80°C下老化4小时,在120°C中干燥8小时,然后在400°C中赔烧3小时得改性氧化侣载体。 [Example 2 002 Primer weighed commercial oxidation couple, the mass concentration of 20% saturated aqueous solution of diethanolamine oxide companion spray dipping, immediately after drying of 0.5 at 110 ° C, the aqueous solution was dried to two adsorption ethanolamine Lu oxide support in an amount of 40% saturated absorption amount of the solution, aged 4 hours at 80 ° C, dried 120 ° C for 8 hours, and then burned lose 400 ° C range 3 hours to obtain the modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为15%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,100°C干燥化,400°C赔烧化, 制得催化剂前体。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution of 15% saline solution to make equal volume impregnation method companion oxide supported on said carrier, 100 ° desiccation C, 400 ° C lost burnt before prepared catalyst precursor. 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为250°C,0. 2MPa (绝压),30化1, 时间2h,制得漠甲烧制异下締催化剂,记为C-2。 The catalyst precursor was placed in a continuous flow fixed bed reactor, a mixed gas before the catalyst used for methane and nitrogen desert body, burning desert A concentration of 60% by volume, the processing conditions are 250 ° C, 0. 2MPa (abs. ), of 30 1, time 2h, prepared at different firing associative desert A catalyst, denoted as C-2. 得到催化剂Μη化拟漠化物计重量含量为18%,ΜηΟ W氧化物计重量含量为2%。 Μη intended to obtain a catalyst of desertification matter basis weight content of 18%, ΜηΟ W oxides content of 2 wt%.

[0030] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0030] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的78. 37%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 78.37% of the total pigment content in the catalyst surface.

[0031] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为2MPa (绝压),空速为35化1。 After [0031] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 2MPa ( absolute pressure), a space velocity of 1 to 35. 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.

[00础实施例3 称取市售氧化侣,将质量浓度为20%二乙醇胺水溶液饱和喷淋浸溃氧化侣,结束后立即在110°C下干燥0.化,干燥至二乙醇胺水溶液的吸附量为氧化侣载体饱和吸收溶液量的40%,80°C下老化4小时,在120°C中干燥8小时,然后在400°C中赔烧3小时得改性氧化侣载体。 Said Example 3 [Embodiment 00 taken commercial basis companion oxide, the mass concentration of 20% saturated aqueous solution of diethanolamine oxide companion spray dipping, immediately after drying of 0.5 at 110 ° C, the aqueous solution was dried to two adsorption ethanolamine Lu oxide support in an amount of 40% saturated absorption amount of the solution, aged 4 hours at 80 ° C, dried 120 ° C for 8 hours, and then burned lose 400 ° C range 3 hours to obtain the modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为10%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,120°C干燥地,500°C赔烧地, 制得催化剂前体。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 10%, although an equal volume of saline solution using the impregnation method companion oxide supported on said carrier, 120 ° drying the C, 500 ° C firing compensation, the front prepared catalyst precursor. 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为250°C,0. 2MPa (绝压),30化1, 时间2h,制得漠甲烧制异下締催化剂,记为C-3。 The catalyst precursor was placed in a continuous flow fixed bed reactor, a mixed gas before the catalyst used for methane and nitrogen desert body, burning desert A concentration of 60% by volume, the processing conditions are 250 ° C, 0. 2MPa (abs. ), of 30 1, time 2h, prepared at different firing associative desert A catalyst, denoted as C-3. 得到催化剂Μη化拟漠化物计重量含量为18%,ΜηΟ W氧化物计重量含量为2%。 Μη intended to obtain a catalyst of desertification matter basis weight content of 18%, ΜηΟ W oxides content of 2 wt%.

[0033] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0033] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的56. 97%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 56.97% of the total pigment content in the catalyst surface.

[0034] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为0. 2MPa (绝压),空速为35化1。 After [0034] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 0. 2MPa (absolute pressure), a space velocity of 1 to 35. 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.

[00对实施例4 称取市售氧化侣,将质量浓度为20%二乙醇胺水溶液饱和喷淋浸溃氧化侣,结束后立即在110°C下干燥0.化,干燥至二乙醇胺水溶液的吸附量为氧化侣载体饱和吸收溶液量的40%,80°C下老化4小时,在120°C中干燥8小时,然后在400°C中赔烧3小时得改性氧化侣载体。 [00 Adsorption take commercially oxidized companion Example 4 that the mass concentration of 20% saturated aqueous solution of diethanolamine oxide companion spray dipping, immediately after drying of 0.5 at 110 ° C, the aqueous solution was dried to two ethanolamine Lu oxide support in an amount of 40% saturated absorption amount of the solution, aged 4 hours at 80 ° C, dried 120 ° C for 8 hours, and then burned lose 400 ° C range 3 hours to obtain the modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为5%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,100°C干燥化,450°C赔烧化,制得催化剂前体。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 5% saline solution to make equal volume impregnation method companion oxide supported on said carrier, 100 ° desiccation C, 450 ° C lost burnt before prepared catalyst precursor. 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为30%,处理条件为250°C,0. 2MPa (绝压),30化1,时间2h,制得漠甲烧制异下締催化剂,记为C-4。 The catalyst precursor was placed in a continuous flow fixed bed reactor, a mixed gas before the catalyst used for methane and nitrogen desert body, burning desert A concentration of 30% by volume, the processing conditions are 250 ° C, 0. 2MPa (abs. ), of 30 1, time 2h, prepared at different firing associative desert A catalyst, denoted as C-4. 得到催化剂Μη化2¾漠化物计重量含量为150/0, MnO W氧化物计重量含量为3%。 Μη 2¾ obtain a catalyst of desertification matter basis weight content of 150/0, MnO W oxides content was 3% by weight.

[0036] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0036] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为50%,活化条件为550°C,0.1 MPa (绝压),lOOOh 1,活化时间地;还原后催化剂中的面素含量为还原前催化剂中面素总含量的68. 21%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 50% by volume, activation conditions of 550 ° C, 0.1 MPa (absolute pressure), lOOOh 1, the activation time ; pigment content after the reduction surface of the catalyst before reduction of the total pigment content of the catalyst surface 68. 21%.

[0037] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为30%,反应溫度为250°C,反应压力为3MPa (绝压),空速为50化1。 After [0037] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein the burning desert A content of 30% by volume, the reaction temperature was 250 ° C, a reaction pressure of 3MPa ( absolute pressure), a space velocity of 1 to 50. 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.

[00測实施例5 称取市售氧化侣,将质量浓度为20%二乙醇胺水溶液饱和喷淋浸溃氧化侣,结束后立即在110°C下干燥0.化,干燥至二乙醇胺水溶液的吸附量为氧化侣载体饱和吸收溶液量的40%,80°C下老化4小时,在120°C中干燥8小时,然后在400°C中赔烧3小时得改性氧化侣载体。 Example [00 Oxidation of commercially available test weighed 5 Lu, the mass concentration of 20% saturated aqueous solution of diethanolamine oxide companion spray dipping, immediately after drying of 0.5 at 110 ° C, the aqueous solution was dried to two adsorption ethanolamine Lu oxide support in an amount of 40% saturated absorption amount of the solution, aged 4 hours at 80 ° C, dried 120 ° C for 8 hours, and then burned lose 400 ° C range 3 hours to obtain the modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为10%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,l00°C干燥化,450°C赔烧化, 制得催化剂前体。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 10%, although an equal volume of saline solution using the impregnation method companion oxide supported on said carrier, l00 ° desiccation C, 450 ° C lost burnt before prepared catalyst precursor. 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧气体处理催化剂前体,处理条件为250°C,0. 2MPa (绝压),30化1,时间化,制得漠甲烧制异下締催化剂,记为C-5。 The catalyst precursor was placed in a continuous flow fixed bed reactor, using the process gas prior to burning desert A catalyst precursor under conditions of a 250 ° C, 0. 2MPa (absolute), 1 of 30, of the time to prepare desert A associated at the firing different catalyst, denoted as C-5. 得到催化剂Μη化2¾漠化物计重量含量为24%,MnO W氧化物计重量含量为2%。 Μη 2¾ obtain a catalyst of desertification matter basis weight content of 24%, MnO W oxides content of 2 wt%. [0039] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0039] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为90%,活化条件为350°C,0. 3MPa (绝压),50化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的58. 56%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 90% by volume, activation conditions of 350 ° C, 0. 3MPa (absolute), 50 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 58.56% of the total pigment content in the catalyst surface.

[0040] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为80%,反应溫度为210°C,反应压力为0.1 MPa (绝压),空速为20化1。 After [0040] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein the burning desert A content of 80% by volume, the reaction temperature was 210 ° C, a reaction pressure of 0.1 MPa (absolute pressure), a space velocity of 1 to 20. 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.

[00川实施例6 称取市售氧化侣,将质量浓度为5%的化晚水溶液饱和喷淋浸溃氧化侣,结束后立即在95°C下干燥比,干燥制化晚水溶液的吸附量为氧化侣载体饱和吸收溶液量的60%,60°C下老化化,在100°C中干燥24小时,然后在300°C赔烧5小时制得改性氧化侣载体。 Example 6 said [00 take commercially oxidized Lu Chuan embodiment, the mass concentration of 5% by spraying a saturated aqueous solution of dipping late companion oxide, than immediately after drying at 95 ° C, the amount of adsorption drying an aqueous solution of Night Lu oxide carrier saturable absorbing 60% of the amount of the solution, 60 ° C for aging, drying at 100 ° C for 24 hours, and then fired at 300 ° C for 5 hours to obtain compensation modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为6%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,100 °C干燥化,450°C赔烧化,制得催化剂前体。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 6%, the best salt solution equal volume impregnation method companion oxide supported on said carrier, 100 ° desiccation C, 450 ° C lost burnt before prepared catalyst precursor. 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为250°C,0. 2MPa (绝压),30化1,时间化,制得漠甲烧制异下締催化剂,记为C-6。 The catalyst precursor was placed in a continuous flow fixed bed reactor, a mixed gas before the catalyst used for methane and nitrogen desert body, burning desert A concentration of 60% by volume, the processing conditions are 250 ° C, 0. 2MPa (abs. ), 1 of 30, of the time to prepare the associative desert methyl isobutyl fired catalyst, denoted as C-6. 得到催化剂Μ址漠化物计重量含量为30%,MnO W氧化物计重量含量为1%。 The catalyst obtained was counted Μ access desertification weight content of 30%, MnO W oxides content of 1% by weight.

[0042] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0042] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的78. 89%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 78.89% of the total pigment content in the catalyst surface.

[0043] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为2MPa (绝压),空速为35化1。 After [0043] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 2MPa ( absolute pressure), a space velocity of 1 to 35. 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.

[0044] 实施例7 称取市售氧化侣,将质量浓度为5%的化晚水溶液饱和喷淋浸溃氧化侣,结束后立即在95°C下干燥比,干燥制化晚水溶液的吸附量为氧化侣载体饱和吸收溶液量的60%,60°C下老化化,在100°C中干燥24小时,然后在300°C赔烧5小时制得改性氧化侣载体。 [0044] Example 7 weighed commercial oxidation couple, the mass concentration of 5% by spraying a saturated aqueous solution of dipping late companion oxide, than immediately after drying at 95 ° C, drying of the aqueous solution adsorption Night Lu oxide carrier saturable absorbing 60% of the amount of the solution, 60 ° C for aging, drying at 100 ° C for 24 hours, and then fired at 300 ° C for 5 hours to obtain compensation modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为10%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,l〇〇°C干燥化,45(TC赔烧化,制得催化剂前体。 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为250°C,0. 2MPa (绝压),30化1,时间化,制得漠甲烧制异下締催化剂,记为C-7。得到催化剂Μη化2¾漠化物计重量含量为l〇%,MnO W氧化物计重量含量为1%。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 10%, although an equal volume of saline solution using the impregnation method companion oxide supported on said carrier, l〇 square desiccation ° C, 45 (TC compensation burnt, to prepare a catalyst precursor. the catalyst precursor was placed in a continuous flow fixed bed reactor, using desert for methane and nitrogen mixed gas catalyst precursor for methane by volume desert concentration of 60%, the processing conditions are 250 ° C, 0. 2MPa (absolute), 1 of 30, time of, desert prepared catalyst a fired associated isobutyl, referred to as C-7. the catalyst obtained Μη of 2¾ desert count content thereof by weight l〇%, MnO W oxides content of 1% by weight.

[0045] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0045] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的69. 21%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 69.21% of the total pigment content in the catalyst surface.

[0046] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为2MPa (绝压),空速为35化1。 After [0046] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 2MPa ( absolute pressure), a space velocity of 1 to 35. 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.

[0047] 实施例8 称取市售氧化侣,将质量浓度为5%的化晚水溶液饱和喷淋浸溃氧化侣,结束后立即在95°C下干燥比,干燥制化晚水溶液的吸附量为氧化侣载体饱和吸收溶液量的60%,60°C下老化化,在100°C中干燥24小时,然后在300°C赔烧5小时制得改性氧化侣载体。 [0047] Oxidation of commercially available taken companion Example 8 that the mass concentration of 5% by spraying a saturated aqueous solution of dipping late companion oxide, than immediately after drying at 95 ° C, the amount of adsorption drying an aqueous solution of Night Lu oxide carrier saturable absorbing 60% of the amount of the solution, 60 ° C for aging, drying at 100 ° C for 24 hours, and then fired at 300 ° C for 5 hours to obtain compensation modified companion oxide support. 称取适量硝酸儘溶于去离子水,加入硫氯酸锭使硫氯酸锭在溶液中的质量分数为5%,儘盐溶液采用等体积浸溃法负载于上述氧化侣载体上,l〇〇°C干燥化,45(TC赔烧化,制得催化剂前体。 将催化剂前体置于连续流动固定床反应器中,使用漠甲烧与氮气的混合气体处理催化剂前体,漠甲烧体积浓度为60%,处理条件为200°C,0. 3MPa (绝压),50化1,时间比,制得漠甲烧制异下締催化剂,记为C-8。得到催化剂Μη化2¾漠化物计重量含量为18%,Mn0 W氧化物计重量含量为2%。 Do weighed amount of nitric acid dissolved in deionized water, sulfuric acid was added starter ingot acid content of sulfur in the solution was 5% saline solution to make equal volume impregnation method companion oxide supported on said carrier, l〇 square desiccation ° C, 45 (TC compensation burnt, to prepare a catalyst precursor. the catalyst precursor was placed in a continuous flow fixed bed reactor, using desert for methane and nitrogen mixed gas catalyst precursor for methane by volume desert concentration of 60%, the processing conditions are 200 ° C, 0. 3MPa (absolute), 1 of 50, than the time to prepare the associative desert methyl isobutyl fired catalyst, denoted as C-8. the catalyst obtained Μη of 2¾ desert Total weight content thereof is 18%, Mn0 W oxides content of 2 wt%.

[0048] 漠甲烧转化制异下締反应在连续流动微型固定床反应器中进行。 [0048] A firing desert Conversion reaction is conducted under heterotrophic association in a continuous flow fixed-bed micro reactor. 催化剂装量5g, 催化剂在使用前使用氨气与氮气的混合气活化,混合气体中氨气体积含量为70%,活化条件为450°C,0. 2MPa (绝压),75化1,活化时间化;还原后催化剂中的面素含量为还原前催化剂中面素总含量的67. 41%。 The catalyst loading amount 5g, catalyst using ammonia gas and nitrogen gas mixed prior to activation, a mixed gas of ammonia content of 70% by volume, activation conditions of 450 ° C, 0. 2MPa (absolute), 75 1 of activated of time; after reduction plane pixel content of the catalyst prior to reduction of 67.41% of the total pigment content in the catalyst surface.

[0049] 活化结束后,降至反应溫度,通入原料气,原料气为漠甲烧与氮气混合气体,其中漠甲烧体积含量为70%,反应溫度为230°C,反应压力为2MPa (绝压),空速为35化1。 After [0049] the end of the activation, down to the reaction temperature, the feed gas into the feed gas is mixed with nitrogen desert for methane gas, wherein a volume content of desert for methane is 70%, reaction temperature is 230 ° C, a reaction pressure of 2MPa ( absolute pressure), a space velocity of 1 to 35. 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.

[0050] 对比例1 按实施例1制备催化剂,制备过程中不采用漠化处理。 [0050] Comparative Example 1 the catalyst preparation process are not used in preparation of a desert. 评价条件同实施例1。 Evaluation conditions were the same as in Example 1. 反应结果见表1。 The reaction results are shown in Table 1.

[00川对比例2 取催化剂C-1不经还原活化,直接进行漠甲烧转化反应。 [00 Chuan Comparative Catalyst C-1 2 taken without reductive activation, direct conversion reaction for methane desert. 反应条件同实施例1。 The reaction conditions were the same as in Example 1. 反应结果见表1。 The reaction results are shown in Table 1.

[00閲对比例3 同实施例1,不同之处在于进行漠甲烧转化反应过程中,漠化儘完全还原。 [Comparative Example 3 00 read in Example 1, except that the reaction was carried out desert for methane conversion process, to make complete reduction desertification.

[0053] 反应结果见表1。 [0053] The results of the reaction are shown in Table 1.

[0054] 表1催化剂反应性能 [0054] Table 1 Catalysts

Figure CN106140227AD00101

Claims (21)

1. 一种溴甲烷制异丁烯催化剂的制备方法,其特征在于:包括如下步骤:(1)氧化铝载体等体积饱和浸渍含氮有机化合物水溶液,浸渍后立即在95-1KTC下干燥0. 5-lh,干燥至含氮有机化合物水溶液的吸附量为氧化铝载体饱和吸收溶液量的30-60%,然后经老化、干燥、焙烧后制得改性氧化铝载体;(2)步骤(1)制备的改性氧化铝载体饱和浸渍锰盐溶液并进行干燥、焙烧,所述锰盐溶液中含有质量分数为2-15%的硫氰酸铵;(3)对步骤(2)焙烧后的物料进行溴化处理使催化剂中氧化锰重量含量为〇. 5%-5%,优选1%-3% ;溴化锰重量含量为5%-40%,优选10%-30%。 1. A method of preparing isobutene bromide catalyst, characterized by: comprising the steps of: impregnating a volume of saturated (1) an aqueous solution of a nitrogen-containing organic compound like an alumina support, dried immediately after impregnation 0. 5-lh in 95-1KTC dried to an aqueous solution of a nitrogen-containing organic compound adsorbed to the alumina support in an amount 30 to 60% saturated absorption amount of the solution, then aged, dried and calcined to obtain the modified alumina support; (2) step (1) preparation of modified alumina support impregnated with a saturated solution of a manganese salt and drying and firing, said manganese salt solution contains 2-15% of the mass fraction of ammonium thiocyanate; (3) the material of step (2) the calcination is carried bromo process the catalyst manganese oxide in an amount of square 5% by weight to 5%, preferably 1% to 3%; manganese bromide content of 5 wt% -40%, preferably 10% -30%.
2. 根据权利要求1所述的方法,其特征在于:步骤(1)中含氮有机化合物水溶液中含氮有机化合物为乙醇胺、二乙醇胺、三乙醇胺和吡啶中的一种或几种;含氮有机化合物水溶液中含氮有机化合物的重量浓度为1%_35% ;老化温度为50-95°C,老化时间为0. 5-10h,老化后干燥温度为90-150°C,干燥时间为0. 5-36h,焙烧在280-500°C下焙烧2-15小时。 The method according to claim 1, wherein: step (1) in the nitrogen-containing organic compound in aqueous ethanolamine, diethanolamine, triethanolamine and pyridine is one or more; nitrogen by weight concentration of the aqueous organic compound containing organic compound is from 1% _35%; aging temperature of 50-95 ° C, the aging time is 0. 5-10h, after aging drying temperature is 90-150 ° C, the drying time is 0 . 5-36h, calcined calcined at 280-500 ° C 2-15 hours.
3. 根据权利要求1所述的方法,其特征在于:步骤(2)干燥条件为,温度60°C -150°C, 时间为lh_24h,焙烧条件为,温度300°C _600°C,时间为lh-24h。 3. The method according to claim 1, wherein: step (2) for the drying conditions, a temperature of 60 ° C -150 ° C, time lh_24h, calcination conditions of temperature of 300 ° C _600 ° C, time lh-24h.
4. 根据权利要求1所述的方法,其特征在于:步骤(2)锰盐为硝酸盐、盐酸盐、醋酸盐、 柠檬酸盐中的一种或几种。 4. The method according to claim 1, wherein: step (2) of manganese nitrate salt, hydrochloride, acetate, citrate, one or several.
5. 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锰的样品进行处理。 The method according to claim 1, wherein: step (3) in the bromination process, refers to the use of a sample gas containing bromine compound is manganese oxide load process.
6. 根据权利要求5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。 6. The method as claimed in claim 5, wherein: the bromine-containing compound refers to methyl bromide, dibromomethane, bromoform one or more of.
7. 根据权利要求1所述的方法,其特征在于:步骤(3)中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,溴代甲烷体积浓度不小于20%。 The method according to claim 1, wherein: step a mixed gas of vapor and an inert gas containing bromine compound (3) used is brominated, methyl bromide concentration of not less than 20% by volume.
8. 根据权利要求1所述的方法,其特征在于:步骤(3)中具体溴化过程如下:将负载氧化锰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 -400°C,通入气相含溴化合物气体,气体空速为50h ^1000 h S体系压力为0.1 MPa-O. 5MPa,处理时间为0. 5h_8h。 8. The method according to claim 1, wherein: step (3) following the bromination procedure specific: the load manganese oxide sample was placed in a continuous flow fixed bed reactor, under an inert atmosphere was warmed to 150 ° C -400 ° C, a bromine compound containing gas into a gas, the gas space velocity of 50h ^ 1000 h S system pressure of 0.1 MPa-O. 5MPa, processing time is 0. 5h_8h.
9. 根据权利要求8所述的方法,其特征在于:惰性气氛下升温至180°C -350°C,通入气相含溴化合物气体,气体空速为l〇〇h ^50011 %体系压力为0.1 MPa-O. 3MPa,处理时间为lh_4h〇 9. The method according to claim 8, wherein: heating in an inert atmosphere to 180 ° C -350 ° C, a bromine compound containing gas into a gas, the gas space velocity of 50011% ^ l〇〇h pressure of the system 0.1 MPa-O. 3MPa, the processing time is lh_4h〇
10. 权利要求1至9任一方法制备的催化剂,其特征在于:催化剂中氧化锰重量含量为0. 5%-5% ;溴化锰重量含量为5%-40%。 10. A catalyst prepared by a method according to any of claims 1 to 9, wherein: the content by weight of manganese oxide catalyst is 0.5% -5%; manganese bromide content of 5 wt% -40%.
11. 根据权利要求10所述的催化剂,其特征在于:氧化锰重量含量为1%_3% ;溴化锰重量含量为1〇%-3〇%。 11. The catalyst according to claim 10, wherein: the content of manganese oxide is 1% by weight _3%; content by weight of manganese bromide 1〇% -3〇%.
12. 权利要求10-11任一催化剂在制异丁烯中的应用,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%,然后使卤代甲烷与上述氢气还原活化后的催化剂接触,以制备异丁烯。 Application of a catalyst system of any of 10-11 isobutene claimed in claim 12, further comprising: a reduction catalyst for hydrogen activation, the halogen content of the catalyst is from 20% -90% reduction in the total amount of procatalyst halogen, then contacting methyl halide catalyst after reductive activation with hydrogen above, to produce isobutene.
13. 根据权利要求12所述的应用,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优选为还原前催化剂中卤素总含量的30%-80%,优选40%-80%。 13. The use according to claim 12, characterized in that: said activation conditions such that the hydrogen reduction of the halogen content of the catalyst is preferably 30% -80% reduction in the total content of the catalyst precursor is a halogen, preferably 40% -80% .
14. 根据权利要求12所述的应用,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200h ^200011 1的氢气或氢气与惰性气体的混合气体,在o. lMPa-O. 5MPa保持2h-16h,混合气体中氢气体积百分含量为10%-95%〇 14. The use according to claim 12, characterized in that: said means of activation comprises a reduction with hydrogen, the catalyst was heated to 300 ° C _600 ° C under an inert atmosphere; then purged with hydrogen gas space velocity of 200h ^ 200011 1 or a mixed gas of hydrogen and inert gas, at o. lMPa-O. 5MPa holding 2h-16h, the volume percentage of hydrogen in the mixed gas content of 10% to 95% square
15. 根据权利要求14所述的应用,其特征在于:升温至350°C _550°C;然后通入空速为500h LlOOOh 1的氢气或氢气与惰性气体的混合气体,在0.1 MPa-O. 3MPa保持4h-8h,所述混合气体中氢气体积百分含量为30%-90%。 15. Use according to claim 14, wherein: heated to 350 ° C _550 ° C; then a mixed gas into a space velocity of 500h LlOOOh 1 hydrogen or hydrogen and inert gas, 0.1 MPa-O at. 3MPa holding 4h-8h, the mixed gas of hydrogen gas volume percentage of 30% -90%.
16. 根据权利要求12所述的应用,其特征在于:所述接触的条件包括反应温度为150°C _350°C ;反应压力为0· lMPa-5MPa ;空速为50h LlOOOh ^ 16. The use according to claim 12, characterized in that: said contacting conditions include a reaction temperature of 150 ° C _350 ° C; reaction pressure is 0 · lMPa-5MPa; a space velocity of 50h LlOOOh ^
17. 根据权利要求16所述的应用,其特征在于:反应温度为180°C -300°C更优选为200-270°C ;反应压力为0· lMPa-3MPa ;空速为200h ^50011 ^ 17. Use according to claim 16, wherein: the reaction temperature is 180 ° C -300 ° C more preferably 200-270 ° C; reaction pressure is 0 · lMPa-3MPa; a space velocity of 200h ^ 50011 ^
18. 根据权利要求12所述的应用,其特征在于:所述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。 18. The use according to claim 12, characterized in that: said methyl halide is a methyl halide, dihalomethane, trihalomethanes one or more.
19. 根据权利要求12所述的应用,其特征在于:所述卤代甲烷为溴甲烷、二溴甲烷、三溴甲烷中的一种或多种。 19. The use according to claim 12, characterized in that: said methyl halide is methyl bromide, dibromomethane, bromoform one or more.
20. 根据权利要求12所述的应用,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200h ^200011 1的氢气与惰性气体的混合气体,在0.1 MPa-O. 5MPa处理2h-16h后,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%。 20. The use according to claim 12, characterized in that: a catalyst under inert atmosphere was warmed to 300 ° C -600 ° C; and then passed into a space velocity of the mixed gas of hydrogen and inert gas to 200h ^ 200011 1, after 0.1 MPa-O. 5MPa processing 2h-16h, the reaction temperature dropped to methyl halide reaction, said mixed gas volume percentage of hydrogen 1〇% _95%.
21. 根据权利要求20所述的应用,其特征在于:包括惰性气氛下将催化剂升温至350 °C -550 °C ;然后通入空速为500h LlOOOh 1的氢气与惰性气体的混合气体,在0.1 MPa-O. 3MPa处理4h-8h后,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30%-90%。 21. Use according to claim 20, wherein: a catalyst under inert atmosphere was warmed to 350 ° C -550 ° C; and then passed into a space velocity of the mixed gas of hydrogen and inert gas 500h LlOOOh 1 in 0.1 MPa-O. 3MPa workup 4h-8h, the reaction temperature dropped to methyl halide reaction, the mixture of hydrogen gas volume percentage of 30% -90%.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026944A (en) * 1989-12-20 1991-06-25 Energy Mines And Resources Canada Synthesis of isobutene from methane and acetylene
EP1227074A1 (en) * 2001-01-29 2002-07-31 Takefumi Hatanaka Method and system for producing heavier hydrocarbons from solid carbon and water
CN1502411A (en) * 2002-11-20 2004-06-09 信越化学工业株式会社 Zinc chloride-loaded support and method for producing the same
CN102910999A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Method for preparing olefins via light alkane dehydrogenation
CN103506158A (en) * 2013-10-25 2014-01-15 凯瑞化工股份有限公司 Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof
CN104292066A (en) * 2014-09-04 2015-01-21 深圳市飞扬实业有限公司 Preparation method for high purity isobutylene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026944A (en) * 1989-12-20 1991-06-25 Energy Mines And Resources Canada Synthesis of isobutene from methane and acetylene
EP1227074A1 (en) * 2001-01-29 2002-07-31 Takefumi Hatanaka Method and system for producing heavier hydrocarbons from solid carbon and water
CN1502411A (en) * 2002-11-20 2004-06-09 信越化学工业株式会社 Zinc chloride-loaded support and method for producing the same
CN102910999A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Method for preparing olefins via light alkane dehydrogenation
CN103506158A (en) * 2013-10-25 2014-01-15 凯瑞化工股份有限公司 Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof
CN104292066A (en) * 2014-09-04 2015-01-21 深圳市飞扬实业有限公司 Preparation method for high purity isobutylene

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