CN103785415B - Hydrogenation of carboxylic acids cobalt bismuth catalysts prepared alcohol - Google Patents

Hydrogenation of carboxylic acids cobalt bismuth catalysts prepared alcohol Download PDF

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CN103785415B
CN103785415B CN201210429785.5A CN201210429785A CN103785415B CN 103785415 B CN103785415 B CN 103785415B CN 201210429785 A CN201210429785 A CN 201210429785A CN 103785415 B CN103785415 B CN 103785415B
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catalyst
acid
metal
hydrogenation
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CN103785415A (en
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黄龙
王国清
田保亮
唐国旗
杨溢
戴伟
彭晖
李宝芹
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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北京化工研究院
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Abstract

本发明涉及一种至少含钴和铋催化剂及其应用于羧酸加氢制备为醇的方法。 The present invention relates to a catalyst containing at least cobalt and bismuth-carboxylic acid and applied to a method of hydrogenation of the alcohol. 在本发明中,使用的催化剂至少含有占催化剂总重的10wt%~40wt%的钴和3wt%~30wt%的铋。 In the present invention, the catalyst used comprises at least accounts for 10wt% ~ 40wt% of the total weight of the cobalt catalyst and 3wt% ~ 30wt% bismuth. 通过该催化剂,在220~300℃和0.5~4.0MPa条件下,羧酸可以以高于90%的选择性转化为相应的醇和酯,使用的催化剂活性高,稳定性好并且成本较低,并且使用的反应条件不苛刻,因此较易实现商业化操作。 Passed over the catalyst at 220 ~ 300 ℃ 0.5 ~ 4.0MPa and conditions, the carboxylic acid may be greater than 90% selectivity into the corresponding alcohols and esters, the use of high catalyst activity, good stability and low cost, and the reaction conditions used are not critical, and therefore easier to achieve commercial operation.

Description

錢酸加氨制备醇的钻祕催化剂 Amino acid addition money ol drill secret catalyst

技术领域 FIELD

[0001] 本发明设及一种能将簇酸高收率加氨转化为醇的钻祕催化剂及其制备和应用方法。 [0001] The present invention is provided, and one of the cluster acid in a high yield can increase ammonia conversion catalyst drill secret preparation and application to alcohols. 技术背景 technical background

[0002] 簇酸加氨制备醇是一类重要的化学反应,如乙酸加氨制备乙醇、乳酸加氨制备丙二醇均存在着迫切地需求。 [0002] Preparation of the cluster acid plus ammonia alcohol is an important chemical reactions, such as ammonium acetate plus ethanol, propylene glycol, lactic acid plus ammonia were prepared there is urgent need. 运是由于多个原因造成的:由于工艺进步,导致簇酸的制造成本降低,如醋酸随着甲醇幾基法的成熟,制造成本降低;或者由于原料变更,使得簇酸的制造具有可持续性,如乳酸、3-径基丙酸等生物质衍生物。 A plurality of transport is due to reasons: Due to advances in technology, the manufacturing cost is reduced cluster acid, such as acetic acid methanol with a few mature group method, manufacturing cost is reduced; or due to material change, such that the cluster acid producing sustainable , such as lactic acid, 3-diameter acid derivatives and other biomass. 阳00引簇酸的加氨制备醇的研究由来已久,如早在1950年,Ford等就申请了使用钉催化剂将簇酸转化为醇的方法,但是由于上世纪石油资源成本较为低廉W及人类的可持续发展重视程度较低,因此醇类的生产多采用締控水合、氧化-水合等技术。 Research cited cluster acid plus ammonia production of alcohols Yang 00 a long time, as early as 1950, Ford and other staples to apply for the use of cluster acid catalyst into alcohol, but due to the cost of the last century, oil resources and relatively low W sustainable development of human low degree of attention, and therefore use more alcohol production associated control hydrous oxide - hydration techniques. 进入21世纪后,人们对可再生体系和石油替代资源(煤炭、天然气、页岩气、煤层气)等的大规模开发,使得簇酸加氨制备醇成为醇类生产的更具经济性和可持续的方法。 In the 21st century, renewable resources, systems and alternatives to oil (coal, natural gas, shale gas, coalbed methane) and other large-scale development, so that the cluster acid plus ammonia ol can be an alcohol and more economical production continuous method.

[0004] 事实上簇酸加氨制备醇具有极高的挑战性,主要的技术难度在于开发出具有高活性和选择性的催化剂,降低所需的反应压力,并且催化剂需要具备有长时间使用的稳定性, 当然催化剂的成本需要在合理的范围内,W保证其商业价值。 [0004] In fact the cluster acid ol Ammonia is highly challenging, the main technical difficulty is to develop a catalyst having high activity and selectivity of the desired reaction pressure is reduced, and the catalyst has a long-term use requires stability, of course, the cost of the catalyst required within a reasonable range, W to ensure its commercial value.

[0005] US4104478公开一种簇酸加氨催化剂及其应用方法,使用的催化剂为M-鍊双金属催化剂,M为钉、锭、销和钮中的一种,在170~250°C和2. 0~14. OMPa的条件下,将相应的簇酸转化为脂肪醇。 [0005] US4104478 discloses an acid catalyst and adding ammonia cluster method of application, the catalyst used is a bimetallic catalyst M- chains, M being nail, lozenges, and one pin of the knob, in and 170 ~ 250 ° C 2 0 ~ 14. OMPa conditions, the cluster acid into the corresponding fatty alcohols. 公开的实施例压力都非常地高07. OMPa)。 Example embodiments disclosed are very high pressure 07. OMPa).

[0006] US4517391公开一种醋酸气相加氨制备乙醇的催化剂,催化剂含有不少于50wt% 的钻,W及铜、儘、钢、铭和憐酸中的一种或者多种。 [0006] US4517391 discloses a catalyst for the gas phase ammonia acetate was added ethanol, the catalyst contains not less than 50wt% of the drill, W, and copper, although, steel, Ming pity and one or more acids. 在唯一的实施例中,钻含量更高达70%, 使用的反应压力为3(K)bar,乙醇收率为97%。 In a single embodiment, up to 70% more content of the drill, the reaction pressure used was 3 (K) bar, the ethanol yield was 97%. 虽然该专利催化剂钻金属含量极高,但是由于不使用贵金属,成本具有一定的优势,不过该催化剂活性较低,乙醇收率仅0. 〇9kg/kg Cat/ h,综合考虑催化剂成本依然较高,并且反应器将会非常庞大,因此并不具有商业化价值。 Although the patent high metal content catalyst drill, but does not use the noble metal, the cost has certain advantages, but the low activity of the catalyst, the ethanol yield was only 0.5 〇9kg / kg Cat / h, still considering the high cost of the catalyst and the reactor will be very large, and therefore does not have commercial value. 同时实施例未公开尾气中不凝性气相的含量而物料收率低于理论值。 While the embodiment is not lower than the theoretical value of the material yield of the off-gas content of the non-condensable gas is disclosed.

[0007] CN1008088公开一种簇酸加氨制备醇的负载型催化剂,催化剂的第一组分为鹤和钢,第二组分为钮、钉和销中的一种,载体为活性炭。 [0007] CN1008088 discloses a supported catalyst the cluster acid plus ammonia ol A crane and a first steel catalyst component, the second component buttons, pins and pin, the carrier is activated carbon. 该催化剂含有1~lOwt%的贵金属,成本高昂;并且反应空速较低(实施例中的LHSV仅为0. 35h 1,意味着时空收率低于0. 26kg/ Hi3CatA),在实施例中的反应压力为1. OMpa 左右。 The catalyst contains 1 ~ lOwt% noble metal, costly; and a lower reaction space velocity (LHSV embodiment only 0. 35h 1, means that the space time yield is less than 0. 26kg / Hi3CatA), in Example the reaction pressure is about 1. OMpa. CN201110104763. 7 和CN201110103802. 1 公开一种醋酸加氨催化剂及其应用方法,催化剂的第一活性组分为鹤和钢,第二组分为钉、锭、销和钮中的一种,载体为活性炭或者石墨,在其公开的实施例中,反应压力为7. 0-10.0 MPao CN201110104763. 7 and CN201110103802. 1 discloses a catalyst and ammonia added acetic acid application methods, the first active component and the crane steel staples one second component, lozenges, buttons and the pin, supported catalyst activated carbon or graphite, in which embodiments of the disclosed embodiment, reaction pressure of 7. 0-10.0 mPao

[0008] Zhang等研究了乳酸水相加氨制备丙二醇,使用负载的钉催化剂和滴流床反应器,其中水含量一般为40~80% 的水(Aqueous-phase hy化Ogenation of lactic acid to p;roP5dene glycol,Applied Catalysis A:General 219(2001)89-98)。 [0008] Zhang et al. Studied the preparation of lactic acid by adding aqueous ammonia, propylene glycol, and the staple trickle bed reactor catalyst use supported, wherein the water content is generally 40 to 80% water (Aqueous-phase hy of Ogenation of lactic acid to p ; roP5dene glycol, Applied Catalysis A: General 219 (2001) 89-98). 在该方法中,较高含量的水运无疑会大幅增加分离时的能耗;使用的催化剂为5wt%的Ru/C,高昂的催化剂成本使得其不适应于商业化操作。 In this method, water levels higher energy consumption will undoubtedly greatly increase the separation; 5wt% of the catalyst used is Ru / C, the high cost of the catalyst such that it is not suited for commercial operations.

[0009] CN102149662公开一种用于醋酸加氨的钻催化剂,钻的负载量低于20wt%,并且催化剂中还含有Iwt%左右的钮和销。 [0009] CN102149662 discloses a drill acetic acid catalyst for adding ammonia, drilling loading below 20wt%, and the catalyst also contains about Iwt% knob and the pin. 在公开的实施例中钻含量均低于lOwt%。 In the disclosed embodiment the drilling were lower than lOwt%.

[0010] US7863489公开一种醋酸加氨催化剂,催化剂活性组分为销,助剂为锡。 [0010] US7863489 discloses an ammonia addition of acetic acid catalyst, the active component pin, adjuvants tin. 催化剂可W将乙酸W较高的收率转化为乙醇,但是销含量较高,在公布的实施例中,销含量超过Iwt%,众所周知,销的价格非常昂贵而且储量非常有限,因此在商业化应用中将会使得催化剂的成本极高。 W W acid catalyst may be converted to ethanol in good yield, but a higher content pin, published in the embodiment, the pin content of more than Iwt%, is well known, is very expensive and the pin reserves are very limited, and therefore commercialization applications will make high cost of the catalyst. 同样的问题也存在于另一专利US7608744中,钻催化剂含量较低(~lOwt%), 同时催化剂需要使用贵金属助剂,如销和钮,助剂含量高于Iwt%。 The same problem also exists in another patent US7608744, the catalyst content lower drill (~ lOwt%), while using a noble metal catalyst needs adjuvants, such as pins and buttons, aid content than Iwt%.

[0011] CN102149662公开一种含钻的醋酸加氨催化剂,制备方法为浸溃法,钻的负载量为0. lwt%~20wt%,在其公开的实施例中,钻负载量在5wt%~10wt%,而使用的助剂使用贵金属助剂,如销和钮,助剂含量高于Iwt%,运将使得催化剂的成本极其高昂,或者为具有较高污染性的铭助剂;并且醋酸的转化率较低,尽管发明者未公开其时空收率,但是通过其提供的实施例数据,可计算出其时空收率较低,如其公开的钻-铭催化剂,乙醇的时空收率仅在82g/ LA~258g/L/h。 [0011] CN102149662 discloses a drill acetate Ammonia-containing catalyst, prepared as dipping method, the loading of the drill 0. lwt% ~ 20wt%, in the disclosed embodiment thereof, the drill loading of 5wt% ~ 10wt%, the cost of noble metals used auxiliary aids, such as pins and buttons, aid content than Iwt%, the operation is extremely high so that the catalyst, or as having a high polluting Ming aid; and acetic acid low conversion rates, although the inventor does not disclose its space-time yield, but the embodiment is provided by which data embodiment, its low space-time yield can be calculated, as is disclosed drilling - Ming catalyst, the space-time yield of only 82g of ethanol / LA ~ 258g / L / h.

[0012] 综上所述,现有簇酸技术方案中,存在一些技术和商业化问题:催化剂成本高昂而且生产催化剂的原料供给量有限、时空收率低、选择性较低、反应压力较高使得操作条件过于苛刻、能耗过高。 [0012] In summary, the cluster acid prior art embodiment, there are some technical and commercial issues: high catalyst cost and the limited amount of supply of raw materials of the catalyst, low space-time yield, low selectivity, high reaction pressure such that operating conditions are too harsh, high power consumption.

[0013] 本发明所述的方法,在较溫和的反应条件下,能够W较高的收率将醋酸转化为乙醇,并且催化剂具有较高的时空收率和低廉的制造成本。 The method of the present invention, [0013], under relatively mild reaction conditions, high yields W can be converted to ethanol to acetic acid, and the catalyst having a high space-time yield and low manufacturing costs.

发明内容 SUMMARY

[0014] 本发明设及一种使用含有祕助剂的钻金属催化剂将一元簇酸加氨为醇催化剂,该催化剂不仅具有活性高、选择性高和稳定性好的特点,而且成本较为低廉,并且组成较为环保。 [0014] The present invention is provided using a drill and a metal-containing catalyst secret aid monohydric alcohols adding ammonia cluster acid catalyst which not only has high activity, high selectivity and good stability, and relatively inexpensive, and the composition is more environmentally friendly.

[0015] 本发明一种簇酸加氨制备醇的催化剂,所述的催化剂包括如下组分: [0015] A cluster acid catalyst Ammonia ol the present invention, the catalyst comprises the following components:

[0016] (1)含有钻和祕,其中钻金属含量占催化剂总重的10wt%~50wt%,祕金属占催化剂总重的0. lwt%~50wt〇/〇; [0016] (1) comprising a drill and a secret, which accounts for drilling metal content 10wt% ~ 50wt% of the total weight of the catalyst, the total weight of the secret metal catalyst 0. lwt% ~ 50wt〇 / square;

[0017] (2 )氧化物,所述的氧化物选自氧化娃、娃藻±、娃酸巧、氧化错、氧化铁、氧化侣的一种或者多种,其含量占催化剂总重的l〇wt%~80wt% ; [0017] (2) an oxide, said oxide selected baby, baby ± alginate, baby acid Qiao, wrong oxide, iron oxide, or an oxidized companion more, the content thereof based on the total weight of the catalyst l 〇wt% ~ 80wt%;

[0018] 所述的加氨催化剂通过浸溃、共沉淀、沉积-沉淀、蒸氨沉淀、溶胶-凝胶、溶化为合金后抽滤和球磨方法中的一种或者多种结合制备。 [0018] The catalyst is prepared by the addition of ammonia dipping, co-precipitation, deposition - precipitation, ammonia evaporation precipitation, sol - gel, melted alloy after suction filtration as a ball mill method and is prepared by combining or more.

[0019] 本发明详细说明如下: [0019] The present invention is described in detail as follows:

[0020] 本发明的催化剂主活性组分为钻,其中钻金属含量占催化剂总重的10wt9W50wt%, 更优选的含量占催化剂总重的15wt%~45wt%,进一步优选占催化剂总重的10wt%~40wt% ;所述的钻金属含量是指元素钻的含量。 [0020] The main active component of the catalyst of the present invention into a drill, a drill in which the metal content accounted 10wt9W50wt% of the total weight of the catalyst, more preferably the amount of from 15wt% ~ 45wt% of the total weight of the catalyst, more preferably from 10wt% of the total weight of the catalyst ~ 40wt%; the metal content refers to drill elements of the drill content. 钻催化剂的含量是经过发明人仔细筛选出的:在较低钻含量时催化剂的活性较低,运会使得催化剂的乙醇时空收率处于较低的水平,由于簇酸具有较强的腐蚀性,因此其直接加氨制备醇的反应器一般需要使用较为昂贵的不诱钢材料,因此时空收率较低下时会使得反应器的成本极高;而更高含量的钻不仅使得催化剂的成本上升,而且并不能够提高催化剂的活性,甚至使活性有所下降,在较高含量时有明显的下降。 The catalyst content in the drill is the result of the inventors carefully screened: a lower activity of the catalyst at lower drill content, so space-time yield of ethanol will transport the catalyst at a low level, since the cluster acid has strong corrosive, Thus prepared alcohol directly added ammonia reactor typically requires the use of more expensive steel is not induced, so that the reactor will be lower when the space time yield at high cost; drilled higher levels of such catalyst not only increased the cost of and is not able to improve the catalytic activity, even the activity declined significantly decreased in the higher levels. 运一结果是出乎意料的:因为往往人们认为提高金属含量会提高催化剂的活性的。 Shipped a result is unexpected: because people tend to believe that increasing metal content increases the activity of the catalyst. 并且,发明人发现在钻含量高于50wt%时候催化剂的制备难度增加,如成型过程等,运将会使得催化剂的商业化较为困难。 Further, the inventors have found difficulty in drilling content is more than 50wt% when prepared catalyst increases, such as molding processes, etc., will make the operation more difficult commercial catalyst.

[0021] 钻金属的来源可选自水溶性的金属盐如硝酸盐、硫酸盐、氯盐、醋酸盐、草酸盐和漠盐,或者选自金属钻,如钻金属板等。 [0021] Source drilled metal selected from water soluble metal salts such as nitrate, sulfate, chloride, acetate, oxalate and desert salts, or a metal selected drilling, such as drilling a metal plate. 更具体的水溶性金属盐选自硝酸钻、氯化钻、草酸钻、硫酸钻、醋酸钻中的一种或者多种,更优选为硝酸钻、醋酸钻和草酸钻中的一种或者多种。 More specifically, the water-soluble metal salt is selected drill nitrate, cobalt chloride, oxalate, drill, drilling sulfate A drill or more of acetic acid, more preferably nitric drill, drill drill acetate and oxalate or more .

[0022] 祕是本发明催化剂中另一种重要的组成组分,适量的祕助剂加入极大地提高了催化剂的活性、选择性和稳定性,并且通过特定的制备方法得到的催化剂更加体现本发明方案的优越性。 [0022] The catalyst of the present invention, the secret is another important component of the composition, a suitable amount of additives added secret greatly improved catalyst activity, selectivity and stability, and is obtained by a specific catalyst preparation method to embody the present advantages embodiment of the present invention.

[0023] 祕助剂加入后,催化剂活性和稳定性等代表催化剂反应性能的指标大幅提高,其中的原因可能是多方面的:祕改善了钻的电子形态或者活化了簇酸。 [0023] After the secret aid was added, the catalyst activity and stability indicators representative of a substantial increase in reactivity of the catalyst, which may be due to many reasons: improved secret electronic form or drill the cluster acid activated. 更意外的,本发明人发现,在通过共沉淀、沉积-沉淀和溶化为合金后抽滤制备的钻催化剂,祕助剂改善催化剂反应性能的效果更加明显。 More unexpectedly, the present inventors have found that, by co-precipitation, deposition - precipitation and the more pronounced effect of solubilized drill alloy catalyst was prepared by suction filtration, secret additives to improve catalyst performance.

[0024] 祕金属占催化剂总重的化lwt%~50wt%,进一步优选的含量占催化剂总重的lwt%~40wt%,更优化的含量为3wt%~30wt%。 [0024] The secret of the total weight of the metal catalyst lwt% ~ 50wt%, more preferably the amount of from 40 wt% of the total weight of ~% catalyst lwt, more optimized content of 3wt% ~ 30wt%.

[0025] 对祕的来源没有限制,可W为所知的所有含祕化合物。 [0025] There is no limit on the source of the secret, the secret may be W-containing compound is all known. 进一步优化的祕的来源有金属祕、氧化祕、硝酸祕、硝酸氧祕、碱式碳酸祕、氯化祕、氧氯化祕和有机祕等。 Further optimization of the secret sources secret metal oxide secret, secret nitrate, zirconyl nitrate, secret, secret basic carbonate, chloride secret, secret chloride, and an organic oxygen secret like.

[00%] 本发明所述的催化剂制备方法可W通过现有催化剂制备技术获得,如浸溃法、离子交换法、共混法、捏合法、共沉淀、沉积-沉淀、蒸锭沉淀、烙融-抽滤、球磨和溶胶-凝胶等方法。 [00%] of the catalyst preparation process of the present invention W may be obtained by conventional catalyst preparation techniques, such as dipping method, an ion exchange method, mixing method, kneading method, co-precipitation, deposition - precipitation, the precipitate was evaporated ingot, branded melting - suction filtration, and milling the sol - gel method. 更优选的方法包括共沉淀、沉积-沉淀、蒸锭沉淀、烙融-抽滤、球磨和溶胶-凝胶中的一种或多种的组合,运些制备催化剂方法大多作为现有成熟技术为本领域技术人员所熟知,在本领域书籍中均有详细的介绍,如黄仲涛所著的<工业催化剂设计与开发〉,Gerhard Rrtl教授等所著的〈Preparation of Solid Catalysts〉。 More preferred method comprises coprecipitation, deposition - precipitation, the precipitate was evaporated ingot, melt branded - suction filtration, and milling the sol - a gel or any combination thereof, most of the catalyst preparation some operation as prior art to the mature those skilled in the art, are described in detail in the books in the art, such as the Huang Zhongtao book <industrial catalysts design and development>, written by Professor Gerhard Rrtl <Preparation of Solid catalysts>. 其中本发明所述的蒸锭沉淀方法,简要步骤如下:(一)将钻盐溶解于水中,也可能含有其他金属或者非金属盐; (二)将氨水逐步加入上述盐溶液中,与氨形成钻锭络合物;(=)加入其他组分;(四)升溫逐步将氨蒸发,钻沉淀下来;(五)洗涂、过滤;(六)干燥、赔烧。 Wherein the ingot was distilled precipitation process of the present invention, a brief procedure is as follows :( a) of the drill salt is dissolved in water, and may also contain other metal or non-metal salt thereof; (ii) aqueous ammonia was gradually added to the above salt solution, formed with ammonia complex drilling spindles; (=) added to the other components; (d) gradually heating the ammonia was evaporated, precipitated drilling; (v) wash-coated, filtered; (f) drying, burning lost. 本发明中的烙融-抽滤法的步骤实质是指Raney催化剂的制备过程:(一)通过在烙炉中将具有催化活性的金属钻、祕和侣(或者娃)烙合,得到的烙体进行泽火冷却,然后粉碎成为均匀的细颗粒,溶化步骤中还可能添加其他的助剂;(二)将催化剂细颗粒成型,成型技术可W采用现有所周知的技术,如打片、捏合挤条、滚球等;(=)将所得的上述成型催化剂在碱液中抽滤,即可获得催化剂。 The present invention is branded into - substantial suction filtration step refers to the preparation of Raney catalysts :( a) by drilling a catalytically active metal in a furnace branded, and Lu secret (or child) baked together, the resulting baked Ze fire body is cooled, and then pulverized to a uniform fine particle, melting step may also add other additives; (ii) the catalyst fine particles are molded using conventional molding techniques may be W well known techniques, such as tabletting, extruding kneader, bowls; (=) the above molded catalyst obtained in lye suction filtration, to obtain a catalyst.

[0027] 本发明进一步优选的催化剂制备方法是共沉淀、沉积-沉淀、和溶化为合金后抽滤的一种或者多种组合而成。 The invention further preferred methods of preparation [0027] The present catalyst is a coprecipitated deposition - precipitation, melted alloy and one or more suction combination.

[0028] 本发明所述的催化剂还含有选自IB族、钮、销、钉、鍊中的一种或多种元素作为助剂,占催化剂总重的0wt°/c^l0wt% ;优选的选自银、铜、钮、钉、鍊中的一种或多种元素作为助剂,进一步优选自银、铜和鍊中的一种或多种元素作为助剂,更优选的选自银和铜中的一种。 [0028] The catalyst of the present invention further contains selected from Group IB, button, pin, nail, one chain or a plurality of elements as an additive, based on the total weight of the catalyst 0wt ° / c ^ l0wt%; preferably selected from silver, copper, buttons, pins, one kind or more elements of the chain as an auxiliary agent, more preferably selected from silver, copper, and one kind or more elements of the chain as an auxiliary agent, more preferably selected from silver and a copper in.

[0029] 银和铜金属含量占催化剂总重的0wt%~10wt%,更优先的范围为0~5wt%。 [0029] Silver and copper metal content accounts 0wt% ~ 10wt% of the total weight of the catalyst, preferentially in the range of 0 ~ 5wt%. 银金属的来源为硝酸银,铜的来源可W是金属铜、硝酸铜、氯化铜、醋酸铜、草酸铜中的一种或多种。 Sources of silver metal is silver nitrate, the copper source may be copper metal is W, copper nitrate, copper chloride, copper acetate, copper oxalate of one or more. 银和铜的添加方式可W是多样的:如在沉淀、沉积-沉淀、蒸锭沉淀法或者溶胶-凝胶过程中与钻盐一起溶解后加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀、蒸锭沉淀法或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者赔烧分解后的材料中;或者在打片或者挤条等成型阶段加入;或者在与钻溶液浸溃时加入,或者与钻盐分步浸溃;在烙融过程中与钻金属一起加入。 Manner of adding silver and copper may be W is varied: as precipitation, deposition - precipitation, steam precipitation or a sol ingot - the gel during drilling dissolved together with added salt; adding a catalyst precursor, such as precipitation, deposition - precipitation, steam precipitation or a sol ingot - drying the gel obtained cake or xerogel, or lose material after burning decomposition; or added in a tabletting or extrusion molding strips stage; or drill was added the solution dipping, or impregnation step drill salt; join together with the drill branded metal melting process.

[0030] 本发明中的催化剂还可W含有碱金属或碱±金属,所述的碱金属或碱±金属含量占催化剂总量的Owt~30wt%。 [0030] The catalyst in the present invention may further contain W ± alkali metal or alkali metal, the alkali metal or alkali metal content accounts ± total catalyst Owt ~ 30wt%. 更具体而言,选自钟、钢、巧、儀、领中的一种或多种,含量占催化剂总量的Owt~15wt%,进一步优选的范围为Owt%~lOwt%。 More specifically, the selected clock, steel, Qiao, scanner, one or more of the collar, the total catalyst amount of from Owt ~ 15wt%, more preferably in the range Owt% ~ lOwt%. 碱金属和碱±金属来源可W 为水溶性的硝酸盐、碳酸盐、氯盐、憐酸盐、硫酸盐、醋酸盐、氣化物、氨氧化物等。 Alkali metal and an alkali metal source may be ± W is a water soluble nitrate, carbonate, chloride, pity, sulfate, acetate, vapor, ammonia, and other oxides. 更具体而言,碱金属和碱±金属来源选自氨氧化钟、硝酸钟、碳酸钟、醋酸钟、氣化钟、憐酸钟、氨氧化钢、硝酸钢、碳酸钢、碳酸氨钢、氯化钢、硫酸钢、醋酸钢、硝酸巧、憐酸二氨巧、硝酸儀、憐酸儀、硝酸领中的一种或多种。 More specifically, alkali metal and an alkali metal source selected from ammonia oxidation ± bell, bell nitric, carbonic clock, clock acetate, gasification bell, bell pity acids, ammoxidation of steel, steel, nitric, carbonic steel, steel carbonate, ammonia, chlorine steels, steel, sulfuric acid, acetic steel, nitric Qiao, Qiao pity amino acid, nitric acid, one or more instrument, instrument pity acid, nitric acid collar.

[0031] 碱金属和碱±金属元素的加入方式可W选自W下方式中的任意一种:在浸溃、捏合、沉淀、沉积-沉淀或者溶胶-凝胶过程中与钻盐一起溶解后加入;在共混、球磨、烙融等方法中与钻盐一起加入或者分步加入;在浸溃、沉淀、沉积-沉淀或者溶胶-凝胶过程中与钻盐分别或者分步加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者赔烧分解后的材料中;或者在打片或者挤条等成型阶段加入。 [0031] manner was added alkali and alkaline metal element ± W may be selected from any one embodiment W is: in the dipping, kneading, precipitation, deposition - precipitation or sol - gel process salts dissolved together with the drill was added; salt was added together with the drill during blending, milling, or the like baked into the stepwise addition; in dipping, precipitation, deposition - precipitation or sol - gel process with a drill or stepwise addition salt thereof, respectively; catalyst precursor is added, such as precipitation, deposition - precipitation or sol - gel after drying the filter cake or dry gel obtained, or lose material after burning decomposition; or added in a tabletting or extrusion molding strips stage.

[0032] 催化剂还含有氧化物组分,尽管不想做任何限制,但发明人认为运些氧化物主要起到载体的作用,所述的氧化物组分选自氧化娃、氧化侣、娃藻±、娃酸巧、氧化错、氧化铁的一种或者多种,其含量占催化剂总重的l〇wt°/c^80wt%。 [0032] The catalyst further comprises an oxide component, although not want to do any limitation, but the inventors believe that these oxides are mainly transported acts as a carrier, the baby oxide component selected from oxides, oxide Lu, Wa alginate ± , baby acid Qiao, wrong oxide, one oxide of iron, or more, an amount of from 80wt% of the total weight of the catalyst l〇wt ° / c ^. 实际上,运些载体不仅仅是起到支撑作用,还能够协助活性组分的分散或簇酸的活化,因此运些载体影响着催化剂的织构性能、产物和原料在其中的扩散、机械强度、活性和稳定性等关键性指标。 Indeed, some transport vehicle just play a supporting role, but also to assist in dispersing the active ingredient, or activating the cluster acid, and thus affect the transport vehicle some texture properties of the catalyst, in which the diffusion of product and starting material, the mechanical strength , activity and stability and other key indicators.

[0033] 载体氧化娃可W选自水玻璃沉淀法、二氧化娃粉末、正娃酸乙醋水解、娃溶胶等。 [0033] The carrier may be oxidized baby W is selected from waterglass precipitation, baby oxide powder, baby acid ethyl ester hydrolysis positive, baby sol. 所述的二氧化娃粉末可W是通过化学沉积法、水玻璃沉淀后干燥后球磨获得、或者是娃溶胶喷雾干燥等方法获得,其尺寸选自IOnm~500 ym ;如青岛海洋化工厂生产的粗孔微球二氧化娃(平均孔径为8. 0-12. Onm,比表面积为300~600m2/g,孔容为0. 8~1. Iml/g),又如广州人民化工厂生产的沉淀二氧化娃(二氧化娃(Si〇2)含量% >95.0,细度(325目筛余物)%《1. 8,比表面积为400~600m7g)或者活性白炭黑,又如德固赛公司的气相二氧化娃AER0SIL200,其比表面为200m 2/g,又如自制喷雾干燥获得的二氧化娃微球,比表面为400~500mVg,尺寸为2~30 ym。 The baby may be W oxide powder by a chemical deposition method, the ball mill and dried to obtain sodium silicate precipitate, a sol or a baby such as spray drying method to obtain a size selected IOnm ~ 500 ym; as Qingdao Ocean Chemical Plant the crude hole Wa dioxide microspheres (average pore diameter of 8. 0-12. Onm, specific surface area of ​​300 ~ 600m2 / g, a pore volume of 0. 8 ~ 1. Iml / g), and if people chemical plant in Guangzhou The precipitate baby dioxide (Wa dioxide (Si〇2) content%> 95.0 fineness (325 mesh sieve residue)% "1.8, specific surface area of ​​400 ~ 600m7g) or active white carbon, Degussa and if baby's game dioxide gas AER0SIL200, a specific surface area of ​​200m 2 / g, and if spray drying baby made dioxide microspheres, specific surface area of ​​400 ~ 500mVg, a size of 2 ~ 30 ym. 二氧化娃粉末可W在沉淀或者沉积-沉淀法中作为载体加入。 Baby dioxide powder may be precipitated or deposited on W - precipitation method was added as a carrier. 所述的水玻璃直接沉淀法是指W水玻璃为原料,在水玻璃中加入酸性沉淀剂或者离子沉淀剂,如硫酸、盐酸、硝酸、醋酸、硝酸巧、硝酸氧错、氧氯化错、硝酸儀、硝酸钻等。 Direct precipitation of the sodium silicate water glass as a raw material refers to W, or the addition of an acidic ion precipitating agent in water glass precipitating agent, such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, Qiao nitrate, zirconyl nitrate, wrong, oxychloride, nitrate meter, drilling and nitric acid. 沉淀剂加入后形成白色胶状物,洗涂数次后使用或者在此基础之上进行其他组分的沉淀法加入。 After precipitation a white gum is added, the use of several wash-coating or by other components precipitated on this basis was added. 正娃酸乙醋是在溶胶-凝胶法制备本发明的催化剂中使用。 Acid ethyl ester n baby is in a sol - gel method using the catalyst of the present invention. 娃溶胶作为液态娃源,可直接使用进入沉淀、沉积-沉淀法的沉淀物系中。 Baby doll sol as a liquid source, can be used directly into the precipitation, deposition - precipitation method based precipitate in.

[0034] 载体氧化娃或者氧化侣也可能是在作为烙融-抽滤法制备的催化剂中作为粘结剂加入,使得所得的催化剂粉末能够成型为本发明所需的形状。 [0034] wa oxide carrier or Lu oxide may also be branded as a melting - a catalyst prepared is added as a binder Method suction filtration so that the resulting catalyst powder is capable of forming a desired shape of the present invention.

[0035] 本发明所述的催化剂的形状可W是多种多样的,如球状、条状、柱状、环状等等,尺寸在0.3~15mm之间,更优选在1~IOmm之间,运个尺寸的要求主要是根据本发明所述的固定床反应器设计,W便利于安装、降低床层压力等要求。 [0035] The shape of the catalyst according to the present invention may be W is varied, such as spherical, bar-shaped, cylindrical, annular, etc., between the size of 0.3 ~ 15mm, more preferably between 1 ~ IOmm, transport a primary requirement is size fixed bed reactor according to the present invention, the design, W facilitate installation, reducing the bed pressure requirements. 运些知识均为本专业的技术人员所熟知。 Some of this knowledge are shipped professional skill in the art.

[0036] 所述的氧化错材料来源为粉体氧化错材料或者通过错盐的沉淀。 The peroxide source is [0036] oxide powder material is wrong wrong wrong material or by precipitation of the salt. 粉体氧化错尺寸选自IOnm~500 ym,比表面大于20m7g。 Wrong size oxide powder selected from IOnm ~ 500 ym, a specific surface area greater than 20m7g. 错盐的沉淀可按照W下途径实现:首先将氧氯化错溶解在水中,随后加入苛性钢等强碱,最后将沉淀物洗涂过滤得到的凝胶;或者使用硝酸氧错作为错源,加入苛性钢沉淀后洗涂过滤获得的凝胶。 Precipitated complex salt may be implemented in the ways W: first oxygen error chloride was dissolved in water, followed by addition of caustic alkali such as steel, and finally the precipitate obtained was filtered washed gel coat; dislocation or nitrate as oxygen source fault, after adding caustic wash-coated steel precipitate obtained by gel filtration. 将上述的凝胶加入到其他沉淀物中, 或者将上述的凝胶经过干燥后磨成粉体后作为沉积-沉淀的载体加入。 The above gel was added to precipitate the other, or the above-mentioned gel after drying the milled powder is deposited as a - added to the precipitated carrier.

[0037] 本发明中的氧化铁可W是一些符合要求的市售二氧化铁,如德固赛公司的P25,也可W采用液相沉淀的方法制备,如采用四氯化铁或者硫酸铁作为铁源,加入尿素、氨水、碳酸钢或者苛性钢等作为沉淀剂,也可W采用有机铁酸如铁酸下醋水解制备。 [0037] In the present invention, iron oxide can meet the requirements of some W are two commercially available iron oxides, such as Degussa's P25, liquid phase precipitation method was also prepared W may be employed, such as the use of ferric sulfate or ferric tetrachloride as an iron source, addition of urea, ammonia, caustic or carbonate steel steel as a precipitating agent, the hydrolysis of the acetate was also prepared as an organic acid, ferric iron W acid employed.

[0038] 催化剂还可能含有稀±金属元素,其氧化物含量占催化剂总量的Owt~8wt% ;所述的稀±元素选择铜或者姉中的一种,优选其氧化物含量占催化剂总量的Owt~5wt%。 [0038] The catalyst may also contain a dilute ± metals, oxides content accounts for the total amount of Owt ~ 8wt% catalyst; lean ± said element select one percent of copper or, preferably accounting for the total oxide content of the catalyst the Owt ~ 5wt%. 加入微量的稀±元素可W通过降低不凝性气体含量而使得钻催化剂的选择性得到一定程度的提局。 Adding trace elements may dilute ± W by reducing the content of non-condensable gas such that the selectivity of the catalyst to some extent the drill mention bureau.

[0039] 催化剂还含有一种或多种无机非金属元素,含量占催化剂总量的Owt~5wt%。 [0039] The catalyst further comprises one or more inorganic non-metallic elements, the content of the total accounting Owt ~ 5wt% of the catalyst. 更具体而言,所述的无机非金属元素选自憐、棚、氣中的一种,含量占催化剂总量的Owt~2wt%。 More specifically, the inorganic non-metallic element selected from the self-pity, shed a gas, the content of total accounts Owt ~ 2wt% of the catalyst. 运些无机非金属元素的加入,有的伴随着其他助剂的加入而进入催化剂体系,如氣化钟。 Yun added some inorganic non-metallic elements, and some with the addition of other additives into the catalyst system, such as gasification bell. 有的是通过额外的方式加入,如棚的加入可采用将棚酸水溶液加入滤饼中的方式。 By addition of some additional manner, such as can be added shed shed acid solution was added to the filter cake in such a way.

[0040] 本发明中所述的将有机簇酸加氨转化为脂肪醇的方法,其具体原理是是将一元簇酸气化并与氨气混合,或者将一元簇酸在氨气中气化后进入加氨反应器内,并与本发明所述的催化剂接触转化为脂肪醇和水。 [0040] The present invention will cluster acid organic method for converting alcohols adding ammonia, which is a specific principle is one yuan cluster acid vaporized and mixed with ammonia gas, or the cluster acid monohydric vaporized ammonia after the addition of ammonia into the reactor, and conversion catalyst according to the present invention with the aliphatic alcohol and water.

[0041] 催化剂装填的反应器为固定床反应器,更优选为列管式反应器,更具体而言,是将催化剂装填在管内,而管间充填导热介质,如导热油或者水等,运样更利于反应热的移出。 [0041] The packing of the catalyst reactor is a fixed bed reactor, more preferably tubular reactor, and more specifically, the catalyst is packed in the tube, and the tube is filled between the heat transfer medium, such as water or thermal oil, transport comp more conducive to the heat of reaction is removed. 本领域的技术人员均熟知该项技术要领,如每根管装填量需保持一致等。 Those skilled in the art are well known to the technical points, such as the amount of each tube loading must be consistent and the like.

[0042] 本发明的催化剂在应用于簇酸加氨中时,需要将其充分地还原活化使得绝大部分钻在进行加氨反应前都被还原为零价状态,活化的方式可W是在升溫条件下通入氨气、使用还原剂如棚酸钢等、或者采用电离福照的方法。 [0042] The catalyst of the present invention when applied to the cluster acid plus ammonia, need to be sufficiently reductive activation is performed such that the majority of the drill is reduced to increase both the zero valent state prior to reaction with ammonia, it is activated in the manner W ammonia gas at an elevated temperature, using a reducing agent such as steel shelf acid, or ionizing fu as employed. 运些方法都为本领域的技术人员所熟知。 These transportation methods known to those skilled in the art.

[0043] 本发明所述的加氨方法,反应溫度为180~350°C,更优选为220~300°C,在该范围内催化剂的选择性变化较小,维持较高的水平。 [0043] The method of adding ammonia to the present invention, the reaction temperature is 180 ~ 350 ° C, more preferably 220 ~ 300 ° C, the catalyst is less selective variation within this range, to maintain a high level. 反应溫度较低时,簇酸转化率较低,运使得循环能耗增大;而反应溫度继续升高时,副产物尤其是不凝性气体产物如乙烧的量大幅增加。 When the reaction temperature is lower, the cluster acid lower conversion rate, so that the operation cycle of increased energy consumption; the reaction temperature continues to rise, especially byproducts products such as non-condensable gases to burn a substantial increase in the amount of acetate.

[0044] 对于一元簇酸加氨制备为醇,理论上氨气消耗量与簇酸的摩尔比为2,但为维持后续反应压力和催化剂寿命,氨气与簇酸的摩尔比例为4:1~40:1,更优比为6:1~25:1,进一步的优化比率为8:1~20:1。 [0044] For the unary preparing the cluster acid plus ammonia as an alcohol, ammonia consumption amount theoretically cluster acid molar ratio of 2, but the subsequent reaction pressure and to maintain catalyst life, the molar ratio of ammonia and the cluster acid is 4: 1 to 40: 1, more preferably ratio of 6: 1 to 25: 1, further optimization ratio of 8: 1 to 20: 1. 从反应器出来的粗产品经过气液分离器后,过量的氨气可W循环使用。 Out of the crude product from the reactor after the gas-liquid separator, excess ammonia may be recycled W.

[0045] 本发明中使用的催化剂选择性较高,因此副产物中不凝性气体的选择性低于15%, 更优的情况下低于10%,进一步优化情况下低于5%。 Under [0045] The high selectivity of the catalyst used in the present invention, therefore by-products selective non-condensable gases is less than 15%, more preferably less than 10% of cases, further optimization is lower than 5%.

[0046] 簇酸的加氨是典型的加压反应,本发明使用的反应压力为0. 3~8. OMPa,更优选的反应压力为0. 5~4. OMPa,进一步优化的反应压力为1. 0~2. 5MPa。 [0046] Ammonia is a typical cluster acid in a pressurized, a reaction pressure of the present invention is 0. 3 ~ 8. OMPa, the reaction pressure is more preferably 0. 5 ~ 4. OMPa, further optimization of reaction pressure 1. 0 ~ 2. 5MPa. 本发明使用的反应压力, 相对于之前许多加氨技术公开的反应压力低许多,运使得反应条件更加溫和,并且降低了成本。 The reaction pressure in the present invention, the reaction pressure relative to many prior art disclosed Ammonia much lower, so that the transport milder reaction conditions, and reduces the cost.

[0047] 在本方法中,簇酸的体积空速为0. 1~5.化1;更优选的体积空速为0. 2~2.化1。 [0047] In the present method, the volume space velocity of the cluster acid is 0.1 to 5 of 1; more preferably a volume space velocity of 0.2 1 ~ 2. 空速实际是根据工厂希望采出产品组成和后续分离能力有关,本发明在实施中不作限制,运是由于:在空速较高时,虽然醋酸转化率较低,但是乙醇和醋酸乙醋的产率和反而会增加, 特别是醋酸乙醋选择性会提高;在空速较低时,醋酸转化率极高,但是乙醇的产率可能会降低,因此对于有分离能力并且希望多产醋酸乙醋的工厂,可W采用高空速操作模式,而对于后续分离能力较小的工厂,可采用低空速操作。 The actual airspeed is desired recovery plant product composition and subsequent separation capabilities related to the present invention is not limited in the embodiment, since the operation is: at higher space velocity, although lower conversion rate of acetic acid, vinyl acetate, and ethanol but vinegar and it will increase the yield, in particular to improve the selectivity of acetic acid ethyl ester; at lower airspeed, a high conversion rate of acetic acid, but the ethanol yield may be reduced, and therefore the ability to have separate desired prolific vinyl acetate vinegar factories, W may be employed high-speed mode of operation, and for the subsequent separation of the smaller capacity of the plant, can be low speed operation. 本发明所述的催化剂,在0. 3~1.化1内可W 保证醋酸的转化率高于50%,更优选的高于75%,进一步优选的高于90%。 The catalyst according to the present invention, in a 0.3 ~ 1. W 1 may guarantee the conversion of acetic acid was higher than 50%, more preferably greater than 75%, more preferably greater than 90%.

[0048] 本发明可广泛应用于一元簇酸的加氨制备醇,具体而言,所述的一元簇酸选自乙酸、丙酸、下酸、乳酸、3-径基丙酸、衣康酸中的一种或者混合物。 [0048] The present invention is widely applicable to the production of alcohols Ammonia one yuan cluster acid, in particular, the monobasic acid is selected from the cluster acetic acid, propionic acid, lactic acid, 3-diameter acid, itaconic acid of one or a mixture thereof. 运些簇酸来源于可再生的生物质资源,如乳酸、3-径基丙酸、苯甲酸、醋酸/丙酸等混合酸液等,也可W来源于其他石油替代资源,如醋酸。 These transport the cluster acid from renewable biomass resources, such as lactic acid, 3-diameter propionic acid, benzoic acid, acetic acid / propionic acid mixture and the like, may be derived from other petroleum W alternative sources, such as acetic acid. 更优选的,所述的有机酸为乙酸和丙酸中的一种或者混合物。 More preferably, the organic acid is one or a mixture of acetic acid and propionic acid. 进一步优选的有机酸为乙酸。 Further preferred organic acid is acetic acid.

[0049] 本发明所述的方法,当簇酸和氨气与催化剂接触后,反应产物除醇外,还有微量其他副产物,主要来源于(1)脱簇/脱幾产物包括一氧化碳、二氧化碳、烧控;(2)酬基化产物; (3)醇酸/醒缩合产物;(4)脱水产物等。 The method of the present invention, [0049], when the cluster acid catalyst and ammonia with the reaction product of an alcohol addition, there are trace amounts of other by-products, mainly from (1) de-cluster / off several products include carbon monoxide, carbon dioxide burn control; (2) pay product group; (3) an alkyd / wake condensation product; (4) dehydration products and the like. 举例而言,对于醋酸加氨制备乙醇,产物除主要由乙醇和醋酸乙醋外,还有乙醒、乙酸、下醇、丙酬、异丙醇、甲缩醒、甲烧、乙烧、丙烷、一氧化碳、二氧化碳等。 For example, for the preparation of acetic acid was added ethanolamine, mainly composed of products other than ethanol and acetic acid ethyl ester, and ethyl awake, acetic acid, an alcohol, propyl paid, isopropanol, A wake reduction, for methane, burning B, propane , carbon monoxide, carbon dioxide, and the like. 本发明描述的催化剂及其方法可W保证簇酸转化为醇和相应的醋的总选择大于70%,更优化情况大于85%,进一步优化的情况大于90%。 The catalyst and process of the invention described herein may be converted to W to ensure that the cluster acid corresponding alcohol vinegar total selectivity greater than 70%, greater than 85% more optimal situation, the situation is further optimized more than 90%.

[0050] 相对于现有技术,本发明的簇酸加氨催化剂及其方法同时具有W下优点: [0050] with respect to the prior art, the cluster acid catalyst of the present invention, addition of ammonia and the method also has the advantage that W:

[00川(1)催化剂活性较高,目的产物选择性高; [Chuan 00 (1) high catalyst activity, high selectivity of desired product;

[0052] (2)催化剂制造成本较为低廉,使得投资和运行成本降低; [0052] (2) Catalyst for producing relatively inexpensive, so that the investment and operating costs;

[0053] (3 )反应条件较溫和,可W在较宽的反应操作条件下运行,增宽了操作窗口。 [0053] (3) The reaction conditions are relatively mild, W may be run over a wide operating reaction conditions, broadening the operating window. 阳054] 实施例 Male 054] Example

[0055] W下实施例是对本发明更为详细的举例描述,但本发明并不局限于运些实施例。 [0055] Example embodiments of the present invention at W is for example described in more detail, but the present invention is not limited to these examples operation. 阳〇56] 实施例1 Male 〇56] Example 1

[0057] 取1. 5mol/L的硝酸钻水溶液1升,在其中加入五水硝酸祕20g,加入20wt%碳酸钢溶液进行沉淀至PH值为9. 0左右,在加热的条件下揽拌2小时,得到前驱体I。 [0057] Take 1. 5mol / L aqueous solution of nitric acid drill 1 liter of nitric acid was added thereto pentahydrate secret 20g, was added 20wt% carbonate solution was precipitated into steel PH value is about 9.0, hangs under heating for 2 hours, to obtain a precursor I. 阳05引将IOg浓硝酸和6g四水硝酸巧加入300ml水中,缓慢地加入到500g稀释的水玻璃水溶液中(二氧化娃含量约lOwt%)中,形成白色沉淀物,使用大功率揽拌器揽拌沉淀物形成浆态物,将运些浆态物质加入到前驱体I中,在揽拌的条件继续老化1小时。 The anode lead 05 IOg concentrated nitric acid and 6g nitrate tetrahydrate was added 300ml water Qiao, slowly added to 500g of the diluted aqueous solution of water glass (baby dioxide content of about lOwt%), a white precipitate formed, using high-power stirrer embrace the precipitate formed embrace stirred slurry was transported to some substance to a slurry precursor I, continued aging conditions embrace stirred for 1 hour. 洗涂过滤, 并干燥过夜得到干燥滤饼,在该滤饼中喷入含有0.1 wt%的硝酸银溶液15ml后造粒。 Washcoated filtered, and dried overnight to obtain a dry cake, the cake injected containing 0.1 wt% of the silver nitrate solution 15ml granulated. 将粒子赔烧分解后打片成型,得到催化剂C监-71。 After firing the particles to lose an exploded tableting molding, to obtain a catalyst monitoring -71 C.

[0059] 实施例2 [0059] Example 2

[0060] 取1. Omol/L的硝酸钻水溶液1升,在其中加入五水硝酸祕18g克和硝酸铜3. Ig, 溶解后加入50g经过精制了的娃藻± (北京化工研究院自产)并充分揽拌,后加入尿素,升溫至80度缓慢水解至PH值为6. 5左右,将上述浆态物过滤洗涂,并干燥过夜得到干燥滤饼, 并在滤饼上喷淋稀释憐酸液体10ml。 [0060] Take 1. Omol / L nitric acid aqueous solution of 1 liter drill, in which the secret nitrate pentahydrate was added 18g g of copper nitrate and 3. Ig, dissolved after addition of 50g of a purified alginate baby ± (Beijing Research Institute of Chemical production ) and fully embrace the mix, after addition of urea was heated to 80 degrees to the slow hydrolysis of the PH value is about 6.5, the above coating slurry was filtered washed, and dried overnight to obtain a dry cake, and the filter cake is diluted in the spray pity liquid acid 10ml. 将滤饼赔烧分解后打片成型,得到催化剂CHZ-72。 The filter cake was lost after burning decomposition tableting molding, to obtain a catalyst CHZ-72. 阳OW] 对比实施例1 Male OW] Comparative Example 1

[0062] 取30克二氧化娃载体(青岛海洋化工厂,吸水率约为0. 9g/g),将60克硝酸钻和Ig硝酸银溶于水中,通过结合多次浸溃-共浸溃-等体积浸溃的方法制备得到前驱体,并将该前驱体400°C赔烧获得催化剂CHZ-73。 [0062] 30 g of silica baby carrier (Qingdao Ocean Chemical Plant, water absorption of about 0. 9g / g), 60 g of the drill Ig nitrate and silver nitrate was dissolved in water by combining multiple impregnation - Impregnated co - a method of preparing a volume obtained impregnated precursor, and the precursor 400 ° C obtained by burning the catalyst lost CHZ-73. 阳〇6引对比实施例2 Yang cited 〇6 Comparative Example 2

[0064] 按照CN200980134837. 2公开的方法,制备了一个巧改性的二氧化娃负载钻-销催化剂,钻负载量为lOwt%和销负载量0. 85wt%。 . [0064] CN200980134837 2 according to the method disclosed, a clever modified silica supported drilling prepared baby - pin catalyst loading of drilling and the pin lOwt% loading of 0. 85wt%. 该催化剂为CHZ-74。 The catalyst is CHZ-74. W65] 实施例3 W65] Example 3

[0066] 将上述催化剂在固定床反应器中进行评价,用于醋酸加氨制备乙醇,装填量为IOml,采用1 :1的石英砂稀释,在使用前采用纯氨气还原,还原最高溫度为450~500°C,具体反应条件和反应结果如表1中所示。 [0066] The above catalyst was evaluated in a fixed bed reactor for the preparation of acetic acid was added ethanolamine, loading is IOml, 1 adopted: 1 dilution of quartz sand, pure ammonia reduction before use, reducing the maximum temperature of 450 ~ 500 ° C, the specific reaction conditions and reaction results are shown in table 1.

[0067] 在本实施例中,醋酸转化率和乙醇选择性按照各组分的碳摩尔百分含量计算获得。 [0067] In the present embodiment, conversion and selectivity to ethanol acetate obtained by calculation according to carbon molar percentage of each component.

Figure CN103785415BD00101

[0070] 其他产物有:乙醒、乙烧、甲烧、一氧化碳、二氧化碳、乙酸醒、丙酬、丙醇等。 [0070] Other products are: acetate awake, burning B, A burning, carbon monoxide, carbon dioxide, acetic acid wake up, pay propionate, propanol and the like. W71] 实施例4 W71] Example 4

[0072] 将上述催化剂在固定床反应器中进行评价,用于乳酸(20wt%水溶液)加氨制备1,2-丙二醇,装填量为IOml,采用1 :1的石英砂稀释,在使用前采用纯氨气还原,还原最高溫度为450~500°C,具体反应条件和反应结果如表2中所示。 [0072] The above catalyst was evaluated in a fixed bed reactor, a lactic acid (20wt% aqueous solution) was added 1,2-propanediol production of ammonia, loading is IOml, 1 adopted: 1 dilution of quartz sand is used prior to use pure ammonia reduction to reduce the maximum temperature of 450 ~ 500 ° C, specific reaction conditions and reaction results are shown in table 2.

[0073] 在本实施例中,乳酸转化率和1,2-丙二醇选择性按照各组分的碳摩尔百分含量计算获得。 [0073] In the present embodiment, the conversion of lactic acid and 1,2-propanediol obtained by calculation in accordance with the selective carbon molar percentage of each component. 其他副产物包括:正丙醇、异丙醇、2-径基-丙醒、丙烷、乙烧、一氧化碳、二氧化碳、乙醇、戊二酬等。 Other by-products include: n-propanol, isopropanol, 2-diameter-yl - propan-wake, propane, burning acetate, carbon monoxide, carbon dioxide, ethanol, and the like glutaric paid.

[0074] 表1 阳0巧] [0074] Table 1 male Qiao 0]

Figure CN103785415BD00111

Claims (16)

1. 一种羧酸加氢制备醇的催化剂,其特征在于,所述的催化剂包括如下组分: (1) 含有钴和祕,其中钴金属含量占催化剂总重的l〇wt%~50wt%,铋金属占催化剂总重的〇·lwt%~50wt% ; (2) 氧化物,所述的氧化物选自氧化硅、硅藻土、硅酸钙、氧化锆、氧化钛、氧化铝的一种或者多种,其含量占催化剂总重的l〇wt%~80wt% ; 所述的加氢催化剂通过浸渍、共沉淀、沉积-沉淀、蒸氨沉淀、溶胶-凝胶、熔化为合金后抽滤和球磨方法中的一种或者多种结合制备; 所述的催化剂中还含有碱金属或碱土金属、稀土金属元素和无机非金属元素中的至少一种,其中,所述碱金属或碱土金属的含量占催化剂总量的〇wt~30wt%,所述稀土金属元素的氧化物含量占催化剂总量的〇wt~8wt%,所述无机非金属元素的含量占催化剂总量的Owt~5wt%。 A catalyst for producing alcohols hydrogenation of carboxylic acids, characterized in that said catalyst comprises the following components: (1) containing cobalt and secret, wherein the cobalt metal content accounted for ~ 50 wt% of the total l〇wt weight% catalyst bismuth metal based on the total weight of the catalyst square · lwt% ~ 50wt%; (2) an oxide, said oxide selected from silicon oxide, diatomaceous earth, calcium silicate, zirconium oxide, titanium oxide, an aluminum oxide or two or more, the content thereof based on the total weight of the catalyst l〇wt% ~ 80wt%; the hydrogenation catalyst by impregnation, coprecipitation, deposition - precipitation, ammonia evaporation precipitation, sol - gel after melting an alloy pumping one kind of filter in the ball mill method and is prepared by combining or more; the catalyst further contains at least one alkali metal or alkaline earth metals, rare earth metals and inorganic non-metallic elements, wherein the alkali metal or alkaline earth metal the content of total accounts 〇wt ~ 30wt% of the catalyst, the rare earth metal element oxide content of 8 wt% of the total accounts 〇wt catalyst ~, content of the inorganic non-metal element accounts Owt ~ 5wt% of the total catalyst .
2. 根据权利要求1所述的催化剂,其特征在于,所述的催化剂中钴金属含量占催化剂总重的15wt%~45wt%,祕金属占催化剂总重的lwt%~40wt% ;所述的催化剂通过共沉淀、沉积-沉淀、蒸氨沉淀和熔化为合金后抽滤方法中的一种或者多种结合制备。 2. The catalyst according to claim 1, wherein said metal catalyst is a cobalt content accounted for 15wt% ~ 45wt% of the total weight of the catalyst, the metal secret accounting total lwt% ~ 40wt% of catalyst weight; the catalyst is prepared by co-precipitation, deposition - precipitation, the ammonia evaporated and the precipitate filtered off with suction as a method of melting the alloy is prepared by combining or more.
3. 根据权利要求1所述的催化剂,其特征在于,所述的催化剂中钴金属含量占催化剂总重的l〇wt%~40wt%,祕金属占催化剂总重的3wt%~30wt%。 3. The catalyst according to claim 1, wherein said metal catalyst is a cobalt content of ~ 40 wt% accounting for the total weight% of the catalyst l〇wt, secret metal constitutes 3wt% ~ 30wt% of the total weight of the catalyst.
4. 根据权利要求1所述的催化剂,其特征在于,所述的氧化物选自氧化娃、娃藻土和娃酸钙中的一种。 4. A catalyst according to claim 1, wherein said oxide is selected from an oxidized baby, baby diatomaceous earth and calcium in the baby.
5. 根据权利要求1所述的催化剂,其特征在于,所述的催化剂还任选地含有选自IB族、 钯、铂、钌、铼中的一种或多种元素作为助剂,其含量占催化剂总重的Owt%~10wt%。 The catalyst according to claim 1, wherein said catalyst also optionally contain a Group IB is selected from palladium, platinum, ruthenium, rhenium and one or more elements as additives, the content thereof based on the total weight of the catalyst Owt% ~ 10wt%.
6. 根据权利要求5所述的催化剂,其特征在于,所述的助剂选自银、铜、钯、钌、铼中的一种或多种元素。 6. The catalyst according to claim 5, wherein said adjuvant is selected from silver, copper, palladium, ruthenium, rhenium and one or more elements.
7. 根据权利要求6所述的催化剂,其特征在于,所述的助剂选自银、铜、铼中的一种或多种元素。 7. The catalyst according to claim 6, wherein said adjuvant is selected from silver, copper, rhenium and one or more elements.
8. 根据权利要求7所述的催化剂,其特征在于,所述的催化剂助剂为银和/或铜。 8. The catalyst according to claim 7, wherein said catalyst promoter is silver and / or copper.
9. 根据权利要求1所述的催化剂,其特征在于,所述的碱金属或碱土金属选自钾、钠、 钙、镁、钡中的一种或多种,其含量占催化剂总量的〇wt~15wt%。 9. The catalyst according to claim 1, wherein said alkali metal or alkaline earth metal selected from one or more of potassium, sodium, calcium, magnesium, barium in an amount of from billion total catalyst wt ~ 15wt%.
10. 根据权利要求1所述的催化剂,其特征在于,所述的稀土金属元素为镧或铈,其氧化物含量占催化剂总量的〇wt~5wt%。 10. The catalyst according to claim 1, wherein said rare earth element is lanthanum or cerium, oxides 〇wt amount of from 5 wt% of the total catalyst ~.
11. 根据权利要求1所述的催化剂,其特征在于,所述的无机非金属元素选自磷、硼、氟中的一种,其含量占催化剂总量的〇wt-2wt%。 11. The catalyst according to claim 1, wherein said inorganic non-metallic element selected from one of phosphorus, boron, fluorine in an amount of from 2 wt% of the total 〇wt catalyst-.
12. -种羧酸气相加氢制备醇的方法,其特征在于,在固定床反应器中,羧酸蒸汽与含氢气体混合与加氢催化剂接触反应后转化为醇和水,氢气与羧酸的摩尔比为4:1~40:1, 反应温度为180~350°C,反应压力为0. 3~8.OMPa,羧酸的体积空速为0. 1~5.OhS 所述的加氢催化剂为权利要求1~11任意一项所述的催化剂,所述的用于加氢的羧酸为一元羧酸。 12. - gas phase process for preparing carboxylic acids alcohols hydrogenation, characterized in that, in a fixed bed reactor, the carboxylic acid vapor and hydrogen-containing gas is contacted with the mixed hydrogenation catalyst is converted to alcohol and water, hydrogen with a carboxylic acid molar ratio of 4: 1 to 40: 1, reaction temperature of 180 ~ 350 ° C, reaction pressure of 0. 3 ~ 8.OMPa, volume space velocity of the carboxylic acid is hydrogenated 0. 1 ~ 5.OhS the catalyst was the catalyst of claim any one of claims 1 to 11, for the hydrogenation of carboxylic acids are monocarboxylic acids.
13. 根据权利要求12所述的羧酸气相加氢制备醇的方法,其特征在于,氢气与羧酸的摩尔比为8:1~20:1,反应温度为220~300°C,反应压力为0. 5~4.OMPa,羧酸的体积空速为0· 2~2.Oh^ 13. The gas phase hydrogenation of carboxylic alcohols as claimed in claim 12, wherein the molar ratio of hydrogen to carboxylic acid is 8: 1 to 20: 1, reaction temperature of 220 ~ 300 ° C, the reaction pressure is 0. 5 ~ 4.OMPa, volume space velocity of the carboxylic acid 0 · 2 ~ 2.Oh ^
14. 根据权利要求12所述的羧酸气相加氢制备醇的方法,其特征在于,所述的用于加氢的羧酸为乙酸、丙酸、丁酸、乳酸、3-羟基丙酸、苯甲酸中的一种或者混合物。 14. The method of vapor phase hydrogenation of carboxylic acids alcohols as claimed in claim 12, wherein, for the hydrogenation of carboxylic acid is acetic acid, propionic acid, butyric acid, lactic acid, 3-hydroxypropionic acid, benzoic acid or a mixture thereof.
15. 根据权利要求14所述的羧酸气相加氢制备醇的方法,其特征在于,所述的羧酸为乙酸、丙酸中的一种或者混合物。 15. The gas phase hydrogenation of carboxylic acids to alcohols according to claim 14, wherein said carboxylic acid is acetic acid, propionic acid or a mixture thereof.
16. 根据权利要求15所述的羧酸气相加氢制备醇的方法,其特征在于,所述的羧酸为乙酸。 16. The gas phase hydrogenation of carboxylic acids to alcohols according to claim 15, wherein said carboxylic acid is acetic acid.
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