CN1094785C - 环己醇脱氢用催化剂及其制备方法和应用 - Google Patents
环己醇脱氢用催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 16
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 32
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- SRANNWMGKIARLD-UHFFFAOYSA-N [Cu].C1(CCCCC1)O Chemical compound [Cu].C1(CCCCC1)O SRANNWMGKIARLD-UHFFFAOYSA-N 0.000 description 1
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种含有α-氧化铝作载体材料,铜作活性组分的催化剂,其中该氧化铝的BET表面积(如DIN 66131所测定的)不小于30m2/g。本发明还涉及一种制备本发明催化剂的方法,和它在环己醇脱氢成环己酮中的用途,以及BET表面积(如DIN 66131所限定的)不小于30m2/g的α-氧化铝在制备催化剂中的用途。
Description
本发明涉及一种改进的含有α-氧化铝作载体材料,铜作活性组分的催化剂,其中氧化铝的BET表面积(根据DIN 66131进行测定)不小于30m2/g。
本发明进一步还涉及一种制备本发明催化剂的方法,和它在环己醇脱氢成环己酮中的用途,以及BET表面积(根据DIN 66131进行测定)不小于30m2/g的α-氧化铝在制备催化剂中的用途。
环己酮是聚酰胺-6和聚酰胺-6,6的一种重要中间产品,在工业生产中,它主要由环己醇的催化脱氢反应生产。有两种类型的环己醇催化脱氢过程。一种是在320-420℃温度下进行的环己醇高温脱氢,另一种是在220-260℃温度下进行的环己醇低温脱氢。
高温脱氢的缺点是低的环己醇的选择性,因为在高温下发生了明显的副反应,如环己醇脱氢成环己烯,或生成环己烯基环己酮的二聚反应。对这些副产物需要昂贵的综合处理,因此影响了该过程的经济性。
环己醇的低温脱氢需要用铜基催化剂催化反应。这些催化剂能够将反应温度降低到大约240-280℃,由此可达较高的环己酮选择性。然而,由于在较低的温度下平衡的移动,通常共转化率不太高。
一种低温催化剂包括铜和陶瓷载体的组合物,该陶瓷载体可以是SiO2或Al2O3或其混合物。在这种催化剂中铜的含量高达50%(重量)。这些催化剂还可包括少量的作助催化剂的碱金属。
例如,对于环己醇的非氧化性脱氢,英国专利GB-A 1081491公开了Cu/Al2O3催化剂,SU-A 465217公开了Cu/Li/SiO2催化剂,SU-A522853公开了Cu/K/Al2O3催化剂。通常上述铜催化剂的制备方法或是在预制载体上通过沉积铜盐或浸渍合适的铜盐溶液以涂敷活化铜组分,或者共沉淀组成催化剂的各组分。另一种可制备铜催化剂的方法是用组分的干混合物,然后进行焙烧。
在Chang等人的,Appl.Catal.A 103(1994)233-42中,已经公开了一种在有配位剂存在的情况下,使用还原剂在载体上无电镀铜或还原沉积铜,以制备环己醇非氧化性脱氢用铜催化剂的方法。所用的载体是表面积为22.6m2/g的α-Al2O3。根据Chang的文章,选择性受载体酸度的影响,酸性载体如Al2O3或SiO2,将会催化如环己醇脱氢或二聚化等副反应。通过加入碱金属或碱土金属离子,可以降低酸性(参见例如Appl.Cat.A:General Vol.83,No.2(1992),201-11),但是这种方法还会降低活性。由于碱金属或碱土金属的添加,也就在一定程度上失去了铜催化剂相比于高温度催化剂所具有的较高活性的优点。
然而,Appl.Catal.A103(1994)233-42所述的催化剂不适用于工业生产,因为它们是粉末状的。由于它们的可压片性能很差,所以很难将它们压成成形制品,如片状制品。此外,成形制品的硬度低,导致了它们在反应器中抗磨性很低,结果增加了反应过程中的压力下降。因此不可能大规模地用于工业生产。
使用α-Al2O3作载体的另一个缺点是与活化铜组分的相互作用性差。相互作用性差将会导致活性组分迅速结块,结果降低了催化活性表面的表面积,由此导致活性降低。为了提高转化率,在脱氢过程中就要升高反应器的温度,但是这会加速催化剂的结块,并因此使催化剂进一步去活。
本发明的目的是提供一种没有上述缺点的催化剂。更具体地说,该催化剂将有很长的运行寿命,并在较低的反应温度下能以高产高选择性地将环己醇脱氢成环己酮。而且无需不断地调节反应温度。此外,该催化剂容易加工成成形制品,尤其是片、条、环、圆柱体制品,且其硬度和抗磨性良好。
由此发现一种改进催化剂,它由α-氧化铝作载体材料,铜作活性组分,其氧化铝的BET表面积(根据DIN 66131进行测定)不小于30m2/g。
本发明还提供了一种制备本发明催化剂的方法,和它在环己醇脱氢成环己酮中的用途,以及BET表面积(如DIN 66131所测定的)不小于30m2/g的α-氧化铝在制备催化剂中的用途。
本发明的催化剂是用传统方式,如浸渍、沉淀、干燥混合或无电镀铜,通过在BET表面积不小于30m2/g的α-Al2O3载体材料上覆以活化铜组分而制得。
优选地所用α-Al2O3载体材料的BET表面积在50-300m2/g范围内,尤其优选地是在100-250m2/g范围内。这种高表面积的α-Al2O3市场有售(例如Alcoa公司)。
浸渍过程通常包括用一种铜盐水溶液使载体浸渍,优选地用硝酸铜、硫酸铜、乙酸铜或氯化铜,然后对浸渍后的载体进行干燥和焙烧。
沉淀过程通常包括在有载体存在的情况下,将铜盐(如上所述)水溶液与沉淀剂相混合,这将会生成微溶的铜化合物。优选地用碳酸钠沉淀铜。接下来用传统方式进行干燥和焙烧。
干燥混合通常包括将载体与所需的铜盐相混合,然后进行焙烧。
在本发明的一个优选实施例中,在有本发明使用的高表面积的α-氧化铝载体(参见Appl.Catal.A 103(1994)233-242)存在的情况下,通过无电流沉积制备催化剂。为此,通常首先在载体上孕育贵重金属,如铂、铑、铱、金或钯,优选地是铂,形成触发结晶中心。然后从含还原剂的铜配合物中将铜沉积在载体上。
为了防止在通常所需的高pH条件下铜的过早沉积,优选地加入强配位剂如乙二胺四乙酸盐、其碱金属盐如四钠盐、1,2-乙二胺或菲咯啉。通常使用能够从铜盐溶液如甲醛或甲酸钠中沉积出铜(0)的还原剂进行还原(或者实际上镀铜)。
通过对数据的观察,我们发现无电流沉积能产生非常小的铜颗粒。用X-射线衍射测量,它们的粒径通常在50nm以下,优选地小于20nm。
无论用何种方式在载体上涂覆铜,都要在250-450℃的温度范围内,在空气或惰性气体气氛,优选地是氮气中,焙烧得到的粉末或相应的成形制品1-24小时。可以在焙烧前或后使制品成形。
最好将从无电流沉积或上述其它过程得到的催化剂粉末,通过与压片助剂相混合,压制成成形制品,如片、条、环形、车轮形、星形、块形、球形、粒状或挤出物,优选地是片形。一般的压片助剂都可以使用。压片助剂的例子包括石墨、硬脂酸镁、甲基纤维素(如Walocel)、铜粉或它们的混合物。
通常在催化剂中,铜占催化剂总重量的0.01-50%(重量),优选地在2-30%(重量)范围内,尤其优选地是在5-20%(重量)范围内。
通常催化剂中α-氧化铝的BET表面积(根据DIN 66131进行测定)不小于30m2/g,优选地在50-300m2/g范围内,更优选地在100-250m2/g范围内。
通常都是在气相中,在180-400℃的温度范围进行环己醇到环己酮的脱氢反应,优选地在200-350℃的温度范围内,更优选地是在220-260℃的温度范围内。通常压力在50kPa-5Mpa范围内;特别适宜的压力是大气压。
通常反应原料是环己醇和环己酮的混合物。当然还可以采用纯环己醇。通常所用的混合物中含有50-100%(重量)的环己醇,50-0%(重量)的环己酮;优选地是含有60-99%(重量)的环己醇,40-1%(重量)的环己酮;尤其优选地是96%(重量)的环己醇,4%(重量)的环己酮。通常通过氧化环己烷,随后通过蒸馏分离环己酮和其它低沸化合物,而浓缩环己醇,由此得到环己醇和环己酮。
一般来说,在实际反应之前,要用氢还原催化剂。通常在一定温度下,优选地在120-300℃的温度下,在催化剂上方通入被惰性气体,优选的是氮气稀释的氢气气流,由此对催化剂进行还原。然后连续增加还原气体中氢气的含量,直到温度不再进一步明显地变化为止。
在一个优选实施方案中,优选地使原料气体以0.1-100h-1的液时空速(LHSV)从催化剂上方通过,更优选地是以0.1-20h-1的液时空速。可将原料与惰性气体如氮气或蒸气相混合。用传统方式(见DE-A 1,296,625和DE-A 1,443,462)综合加工脱氢反应产物,以便进一步进行处理。
在另一个优选实施方案中,使氢气与离开反应区的反应混合物分离,然后将氢气加到进入反应区的气体混合物中。更有利的是循环该反应混合物,直到达到所需的转化率。
由于本发明的催化剂具有高活性,因此可以在明显低于工业中通常使用的催化剂的运行温度下运行。该催化剂可被快速激活,提供接近于平衡的高选择性和转化率。此外,该催化剂只在明显长于至今为止已知催化剂的使用期后,才会出现显著减活现象。
本发明的催化剂明显具有良好的压片性能、合适的硬度、低运行温度下的高转化率、高环己醇选择性和长运行寿命。
实施例1-催化剂制备
将5克聚乙烯吡咯烷酮(”PVP”,由Merck提供,序号7443,平均分子量25,000g/mol),加到27.27克浓度为11%(重量)的Pd(NO3)2溶液(以Pd计)、495ml二次蒸馏水和495ml乙醇的混合液中,将得到的混合物回流4小时。得到的溶胶(“Pd溶胶”)中钯的含量为0.34%(重量)(基于Pd溶胶的总重量)。
将20.6ml上述制备的Pd溶胶与23ml水和125克α-Al2O3(由Alcoa提供,BET表面积为156m2/g,吸水量为0.35ml/gAl2O3)相混合。然后使饱和后的载体风干。将预处理和干燥后的载体悬浮在3894ml新制备的溶液中,该溶液中含有0.1M Cu(OAc)2、0.2M Na4EDTA、0.2M甲醛和0.0125M吡啶。并剧烈搅拌下用浓度为35%(重量)的NaOH将溶液的pH值调整到12.5,观察溶液从灰黑色变到红棕色。将悬浊液加热到70℃,并进一步用NaOH(NaOH的消耗量大约为400ml)使溶液的pH值维持在12-12.5范围内。在70℃的温度下搅拌悬浊液30分钟,然后冷却到室温。对悬浊液进行过滤,然后用水对滤渣进行洗涤直至水呈中性(滤液稍稍有些蓝色)。然后在110℃的温度下,在氮气气氛中,对冲洗后的固体干燥16小时,随后在300℃的温度下焙烧2小时。
得到的催化剂中铜占灰黑色催化剂总重量的16.5%(重量),钠占0.046%(重量)。
晶体组分的XRD测定结果如下:Al2O3(19nm);CuO(13.0nm);Cu2O(微量)。
压片(长5mm,直径3mm)的制造
将100克上述制得的催化剂粉末,与占催化剂总重量1%(重量)的铜粉“FFL”(Norddeutsche Affinerie #10914)和占催化剂总重量1%(重量)的硬脂酸镁(Riedel de Haen #4162757)一起预挤压成长20mm长、直径1mm的圆片。然后使这些圆片通过筛号为1.6mm的筛网,接着加入2%(重量)的石墨,压模成长为5mm,直径为3mm的片。
该片的旁压力是53N,标准偏差为16N(用Frank公司的型号为81557的仪器进行测量)。
实施例2-催化剂试验
在一个直径为5cm、长为60cm的管状反应器中进行催化剂试验。对每一个试验,都装上200ml的催化剂,并在反应前用氢气激活该催化剂。在引入原料之前,在120℃的温度下,用1501 N2/h和1.51 H2/h激活催化剂。当温度的升高超过10℃时,停止供应氢气气流。然后在保持氢气流速恒定的情况下,以20℃的增量使温度升高到240℃。在240℃的温度下,用150 1 N2/h和7.5 1 H2/h激活催化剂。在活化后,在大约0.7h-1的LHSV下,使催化剂与96%(重量)的环己醇/4%(重量)的环己酮相接触。用气体色谱法分析反应器的流出物。结果如下表所示。
比较实施例:
用市场有售的铜催化剂(由Procatalyse公司提供的催化剂CU940)重复实施例的脱氢试验。
催化剂 | 温度(℃) | 时间(h) | 转化率(%) | 选择性(%) |
实施例2 | 229 | 42 | 57 | 97.7 |
228 | 150 | 56 | 99.2 | |
228 | 246 | 59 | 99.4 | |
226 | 438 | 55 | 99.9 | |
229 | 558 | 55 | 99.7 | |
237 | 630 | 61 | 99.6 | |
242 | 774 | 60 | 99.5 | |
比较例 | 277 | 0 | 68 | 98.3 |
275 | 12 | 63 | 98.4 | |
275 | 24 | 62 | 98.5 | |
275 | 36 | 61 | 98.6 | |
276 | 48 | 61 | 98.5 | |
280 | 168 | 60 | 98.1 |
在>230℃的这样低温度下,本发明催化剂的选择性>99%(重量),转化率接近平衡。在该温度下没有出现明显的催化剂减活。通过稍微升高反应温度至大约240℃,就可以在不损失选择性的条件下,将转化率增加到大约60%(重量)。此外在该温度下,减活也非常平稳。
由此可以看出,比较例的试验需要在168h后调节温度,以便维持转化率,而采用本发明的催化剂,在大约600小时后都无需进行这种调节。此外,比较例的温度比该实施例的温度高出大约40℃。最后,本发明实施例中的选择性是最佳的。对于BET表面积不小于30m2/g的氧化铝来说,这是料想不到的。
Claims (7)
1、一种含有α-氧化铝作载体材料、铜作活性组分的催化剂,其中该氧化铝的BET表面积按DIN 66131测定不小于30m2/g。
2、一种含有α-氧化铝作载体材料、铜作活性组分的催化剂,其中该氧化铝的BET表面积按DIN 66131测定不小于30m2/g,该催化剂是通过浸渍、沉积、干燥混合或无电镀铜,在α-氧化铝载体材料上涂覆铜而制得。
3、一种制备如权利要求1或2所述的催化剂的方法,改方法通过浸渍、沉积、干燥混合或无电镀铜,在α-氧化铝载体材料上涂覆铜,其特征在于包括使用BET表面积按DIN 66131测定不小于30m2/g的α-氧化铝。
4、权利要求3的方法,其特征在于进一步将该催化剂制成成形制品。
5.权利要求4的方法,其中所述的成形制品是片状、条状、环形或圆柱状制品。
6、权利要求1或2的催化剂在使环己醇脱氢以制备环己酮中的应用。
7、BET表面积按DIN 66131测定不小于30m2/g的α-氧化铝在制备催化剂中的应用。
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CN102500420B (zh) * | 2011-11-30 | 2014-03-05 | 大丰海嘉诺药业有限公司 | 一种醇气相脱氢催化剂及其制备方法和应用 |
RU2546122C1 (ru) * | 2013-10-10 | 2015-04-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования (Российский химико-технологический университет им. Д.И. Менделеева) | Катализатор для дегидрирования циклогексанола в циклогексанон |
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US4310703A (en) * | 1979-07-30 | 1982-01-12 | Mitsubishi Chemical Industries Limited | Process for the preparation of cyclohexanone |
CN1056067A (zh) * | 1990-04-29 | 1991-11-13 | 王炳炎 | 多组分环己醇脱氢催化剂 |
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US4310703A (en) * | 1979-07-30 | 1982-01-12 | Mitsubishi Chemical Industries Limited | Process for the preparation of cyclohexanone |
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