CN1361718A - 基于氧化锌的脱氢催化剂 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
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- 239000012752 auxiliary agent Substances 0.000 claims description 5
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- 238000001354 calcination Methods 0.000 description 7
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- QHGVXILFMXYDRS-UHFFFAOYSA-N pyraclofos Chemical compound C1=C(OP(=O)(OCC)SCCC)C=NN1C1=CC=C(Cl)C=C1 QHGVXILFMXYDRS-UHFFFAOYSA-N 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
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- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
本发明涉及基于氧化锌作活性组分的脱氢催化剂,该催化剂确定的钠和比表面,本发明还涉及其在仲醇类脱氢以转化为相应酮类中的应用。
Description
本发明涉及一种基于氧化锌作为活性组分的脱氢催化剂及其在仲醇类脱氢生成相应酮类方面的应用。
DE-A-19626587报导了通过在以铜作活性组分和以Al2O3作载体的催化剂上脱氢来制备环己酮的方法。这类催化剂的反应温度照例比无铜情况下的反应温度低。
EP-A-0204046叙述了一种制备环己酮的方法，其中采用的脱氢催化剂由铜、氧化锌和碱金属化合物优选碳酸钠组成。这类催化剂的选择性通常是低的，但它可通过适宜的制备方式以及有效物质和载体的适当组合来加以克服。常常向反应混合物补充混入添加剂如水，以得到可以接受的选择性。不能排除较低的转化率，它是由于较低的反应温度下的不利的平衡态产生的。提高反应温度照例会明显加速这类催化剂的老化，其原因与铜的烧结有关，从而使这类催化剂寿命缩短，经济上产生不良后果。
采用无铜催化剂方法可避免这些缺点。
DE-A-1443642描述了环己醇脱氢的催化剂，该催化剂通过锌盐溶液经碱性沉淀剂而制备。但对催化剂的Na-含量未给出任何数据。DE-A-19609954报导了仲醇类在升高的温度下在气相中脱氢的方法。作为催化剂采用氧化锌和碳酸钠的混合物。用碳酸钠沉淀硝酸锌和硝酸钙，经过滤、洗涤至无钠，并将滤饼干燥以得到该催化剂。然后将该产物煅烧并后制成成形体。但是，采用这种方法只有在将流动的气态氢通入反应器的情况下才能获得选择性。这是该方法的一个重大缺点，因为加入氢会由于不利的反应平衡态以及由于气体混合物在反应器中停留时间的减少而使反应的转化率降低。实例证明，这种方式的时空产率为0.46g环己酮/g催化剂·小时。
在目前已知的方法中，二环己酮是一种最不希望的副产物。
因此，本发明的目的在于，提供一种用于方法中的催化剂，它能以高的选择性、高转化率得到仲酮，优选环己酮。此外，该催化剂具有足够的寿命。本发明的方法中，在由含0.1-0.6产量％钠的氧化锌组成的催化剂存在下，在较高的温度时的气相中使仲醇类脱氢。本发明中可采用环脂醇类以及脂族仲醇类，优选环己醇作为醇类。
因此，本发明的申请是一种催化剂，该催化剂由氧化锌作为活性化合物组成。该催化剂优选含0.1-0.6％的钠，特别优选含0.15-0.4％的钠。其BET-比表面宜界于5-30m2/g，特别优选8-20m2/g。
本发明的催化剂通过从水溶性锌化合物中用碱沉淀出难溶的锌化合物，然后将此沉淀物用专业人员熟知的方式加工。例如本发明的制备方法如下：采用碳酸钠水溶液，向该水溶液添加硫酸锌。此沉淀物经过滤、洗涤、干燥、煅烧，温度不超过650℃。所得产品还可研磨并后制成成形体，例如其中混入成片助剂并在压片机上压片。
通常采用锌盐水溶液。作为锌盐可采用如硫酸锌、硝酸锌、氯化锌或醋酸锌，优选硫酸锌和氯化锌。为进行沉淀可使用水溶性钠盐如氢氧化钠，碳酸氢钠或碳酸钠，优选碳酸钠和氢氧化钠。而且将两种盐中的一种，优选碱，作为溶液置于容器中，再将另一种盐加入水溶液中，直至达到预期的pH-值。优选在pH达6-9下沉淀。这种制备方法例如在DE-A-3900243中有所叙述。温度通常选择20-90℃，优选50-80℃。在此法的另一种方案中，将两种盐溶液同时加入容器，而且这样控制加入，即在容器中保持较恒定的pH值。沉淀过程中优选的pH值为6-9。沉淀经过过滤、洗涤和干燥。优选的洗涤方式是这样进行，即使煅烧的催化剂前体中还含有0.1-0.6％的可洗脱的钠，优选含0.15-0.4％可洗脱的钠。在这种情况下通过测定按每公斤催化剂前体用100升蒸馏水洗涤，洗涤前后的催化剂前体的Na-含量得到可洗脱钠的含量。
在催化剂前体洗涤时，要注意使所采用的锌盐的阴离子完全洗去，因为其对本发明的催化剂可能有不利的影响。在另一优选实施方案中，向被加工的粉末添加预期的钠量，比如用碱溶液，例如碳酸钠溶液使所得沉淀产物成糊剂，然后烘干燥。溶液浓度的选择使该催化剂具有本发明规定的钠含量。由此洗涤工序是特别重要的，因为这里会影响催化剂的钠含量，例如通过专业人员熟悉的元素分析容易得到。
得到的粉末有时可预煅烧，优选在喷雾干燥器中预煅烧。然后粉末经过成形工序及产品煅烧，其中煅烧条件，特别是温度的选择要使最终的催化剂的BET内比表面最低为5m2/g和最为30m2/g，尤其优选为8-20m2/g。头几次判断试验表明，煅烧温度愈高和/或煅烧时间选得愈长，则其比表面愈小。有时蛮可将成形和煅烧的顺序颠倒过来。
在一个优选实施方案中，首先经预煅烧，将所得产物与0.1-5重量％，优选1-5重量％，特别优选2-5重量％的助剂混合，并将所得产物压制成成形体，例如片、小星片、环、碎块、轮状物、球，优选为片。优选的成片助剂是石墨，而且由于其较高的纯度特别优选合成石墨，这样在加工工序中就完全避免了催化剂的杂质。最通常应注意，不容许这样的金属氧化物进入催化剂，即专业人员所知那些具有酸性的氧化物。例如活性氧化铝属于这类氧化物。经煅烧法以使BET-内比表面达到最低为5m2/g和最高30m2/g，特别优选8-20m2/g，而且尤其优选催化剂的侧抗碎强度为20-500N，尤其优选40-100N。这种抗碎强度可通过常规措施在压片时调节，例如调节冲压力，并在Instron Mini 44，冲头直径为8mm来测定。
在催化剂用于本发明的方法时，使拟脱氢的仲醇类的蒸汽与该催化剂接触。为此可将该醇在蒸发器中汽化，并使其通过含有催化剂床的加热的流管。在环己醇的情况下，选择单位时间加入的醇量为0.5-3，特别优选1-2kg环己醇/升催化剂床/小时，在其它的醇类的情况下，按其相应于对环己醇比例的分子量。尤其优选一种实施方案，其中采用由环己烷-氧化和接着纯化所得的产物，即环己醇和环己酮的混合物。该反应温度优选200-500℃，特别优选300-450℃，这种条件下催化剂寿命未发生不可接受的变化。在一个优选实施方案中，温度选择使仲醇的转化率达到60-90％，尤其优选65％-85％。而且特别优选的反应温度范围为300-450℃。所得产物通常进行冷凝、去除氢并进行蒸馏处理。
本发明的催化剂具有高选择性，同时寿命较长，活性足够高。
本发明制备的环己酮是聚酰胺-6和聚酰胺-6.6的重要前体。
实施例
实施例1(催化剂制备)
将18升蒸馏水和18升18％的碳酸钠溶液放入60升容器中，加热至60℃并在搅拌下在60分钟内加入20升加热至60℃的含100g锌/l的硫酸锌溶液，该溶液是通过硫酸锌水合物(ZnSO4*7H2O)在蒸馏水中的溶解，并用硫酸酸化至pH＝4.1。容器中pH-值达到7.0时停止加；入硫酸锌溶液，再搅拌30分钟然后放置30分钟，吸出上清液，将悬浮液分到三个吸滤器上，经过滤，并用总量为72升的蒸馏水洗涤。滤饼分布在几个金属板上，并在循环空气炉中在125℃干燥一夜。得到3750克产物，然后该产物在静态炉中加热至400℃，并煅烧1小时。所得产品经研磨，并与4重量％(按总固体物计)合成石墨(平均颗粒直径为44μm)混合，并在压片机上压制成5mm直径和3mm厚的片。该片在实验室炉中在500℃下退火4小时。该催化剂的侧抗碎硬度为104N，BET-内比表面为11m2/g，钠含量为0.20％，硫酸盐含量为0.02％。
实施例2
按照DE 3900243，采用一种锌盐溶液，该溶液由克分子比为1∶2的硫酸锌和氯化锌组成。和为碱采用克分子比为40∶60的碳酸钠和氢氧化钠组成。两种溶液同时配量加入容器，而且控制泵入速度以使pH调节到8。所得产物经过滤。接着在吸滤器上洗涤。其余工序同实施例1。制备好的催化剂的Na-含量为0.39％，侧抗碎硬度为45N，BET-内比表面为9m2/g。
实施例3(参比例)
过程同实施例2，但催化剂片在制造结束时不煅烧。由此得出的BET-内比表面为64m2/g。催化剂的钠含量为0.39％，其侧抗碎硬度为48N。
实施例4(参比例)
过程同实施例2，但是0.5kg的过滤产物补充用530升蒸馏水在真空吸滤器上洗涤。成形体的制造同实施例2。所得的催化剂的钠-含量为0.022％，侧抗碎硬度为35N，BET-内比表面为10m2/g。
实施例5(参比例)
将Grillo公司的“Zinkweiβ Pharma 8”型ZnO粉末与水一起制糊，在125℃的实验室烘箱中干燥产物一夜，所得干饼经破碎并用筛筛出大小为1.5-3mm的组分。所得的颗粒很软，BET-内比表面为7.5m2/g，钠含量为12ppm。
实施例6(催化剂试验)
所得的催化剂在内径为55mm、长度为1m的流管中试验。反应管用电加热，催化剂床的体积总为2升。通过汽化器向反应器每小时加入3kg的电94％环己醇和6％环己酮组成的混合物。催化剂操作7-10天，反应温度逐步提高，致使产品中环己酮的含量达73-75％。然后记录用气相色谱测得的产物中的二环己酮含量和对催化剂进行评价所需的反应温度。在实施例3的催化剂的情况下，转化率不超过63％；与实施例1和实施例2的测量值相当。
按照DE1443462的实施例1操作，催化剂含3.67％的钠。
表1：脱氢试验结果
| 催化剂 | Na含量[％] | BET[m2/g] | 取样时间[h] | 反应温度[℃] | 环己酮含量[％] | 产物中的二环己酮[％] |
| 实施例1 | 0.20 | 11 | 97243 | 309327 | 6473 | 0.190.24 |
| 实施例2 | 0.39 | 9 | 93189 | 333347 | 6475 | 0.090.17 |
| 实施例3 | 0.39 | 64 | 92 | 299 | 63 | 0.85 |
| 实施例4 | 0.022 | 10 | 215 | 323 | 74 | 1.65 |
| 实施例5 | 0.0012 | 168 | 340 | 74 | 1.86 |
Claims (7)
1.一种含氧化锌的脱氢催化剂，其特征在于，按总催化剂量计，钠含量界于0.1-3重量％和0.1-0.6重量％，BET-内比表面为5-30m2/g。
2.权利要求1的脱氢催化剂，其特征在于，按总催化剂量计，钠含量为0.1-1重量％，尤其优选0.1-0.6重量％，特别优选0.15-0.4生理％。
3.权利要求1和/或2的脱氢催化剂，其特征在于，BET-内表面界于8-20m2/g。
4.权利要求1-3中至少之一的脱氢催化剂，其特征在于，附加的助剂，优选制片助剂的含量为0.1-5重量％，优选1-5重量％，特别优选2-5重量％，最特别优选是石墨。
5.一种含权利要求1-4之一的脱氢催化剂的成形体，其特征在于，其侧抗碎硬度为20N-500N，优选40N-100N。
6.权利要求5的成形体，其特征在于，它呈片状。
7.一种通过仲醇类脱氢来制备仲酮类的方法，它是在有 1-4中至少一的催化剂和/或权利要求5或6的成形体存在下在气相中于高温，优选200-500℃，特别优选300-450℃下进行。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19933079.4 | 1999-07-19 | ||
| DE19933079A DE19933079A1 (de) | 1999-07-19 | 1999-07-19 | Dehydrierkatalysatoren |
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| Publication Number | Publication Date |
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| CN1361718A true CN1361718A (zh) | 2002-07-31 |
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| CN00810469A Pending CN1361718A (zh) | 1999-07-19 | 2000-07-06 | 基于氧化锌的脱氢催化剂 |
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| Country | Link |
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| EP (1) | EP1202799A1 (zh) |
| JP (1) | JP2003504194A (zh) |
| KR (1) | KR20020013968A (zh) |
| CN (1) | CN1361718A (zh) |
| AU (1) | AU6432100A (zh) |
| DE (1) | DE19933079A1 (zh) |
| HK (1) | HK1048613A1 (zh) |
| WO (1) | WO2001005499A1 (zh) |
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| JP2007022922A (ja) * | 2005-07-12 | 2007-02-01 | Tonen Chem Corp | カルボニル化合物の製造法 |
| MX312760B (es) | 2008-07-18 | 2013-08-29 | Basf Se | Particulas de oxido de zinc modificado. |
| JP6627219B2 (ja) * | 2015-01-05 | 2020-01-08 | 株式会社Ihi | オレフィンの製造方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1211629B (de) * | 1962-08-14 | 1966-03-03 | Basf Ag | Verfahren zum Dehydrieren von Cyclohexanol |
| DE1443462A1 (de) * | 1962-12-18 | 1969-08-14 | Basf Ag | Verfahren zum Dehydrieren von primaeren oder sekundaeren Alkoholen |
| FR1543933A (fr) * | 1966-11-28 | 1968-10-31 | Inst Francais Du Petrole | Procédé et catalyseur de fabrication de cétones cycliques, par déshydrogénationcatalytique d'alcools cycliques |
| DE3200483A1 (de) * | 1982-01-09 | 1983-07-21 | Bayer Ag, 5090 Leverkusen | Kieselsaeurehaltige formkoerper, verfahren zu ihrer herstellung und ihre verwendung |
| JPS59204145A (ja) * | 1983-05-02 | 1984-11-19 | Toa Nenryo Kogyo Kk | カルボニル化合物の製造方法 |
| DE3513568A1 (de) * | 1985-04-16 | 1986-10-16 | Basf Ag, 6700 Ludwigshafen | Verfahren zur aufarbeitung von cyclohexanol, cyclohexanon sowie cyclohexylhydroperoxid enthaltenden reaktionsgemischen |
| US4670605A (en) * | 1985-05-31 | 1987-06-02 | Industrial Technology Research Institute | Process and catalyst for the conversion of cyclohexanol to cyclohexanone |
| US4918239A (en) * | 1988-12-27 | 1990-04-17 | National Science Council | Method of producing cyclohexanone from cyclohexanol through oxidative dehydrogenation |
| JPH04164816A (ja) * | 1990-10-30 | 1992-06-10 | Mitsubishi Materials Corp | 液中合成法による針状酸化亜鉛粉末の製造方法 |
| JPH04164813A (ja) * | 1990-10-30 | 1992-06-10 | Mitsubishi Materials Corp | 酸化亜鉛粉末の製造方法 |
| US5254516A (en) * | 1992-03-26 | 1993-10-19 | Research Triangle Institute | Fluidizable zinc titanate materials with high chemical reactivity and attrition resistance |
| DE19609954A1 (de) * | 1996-03-14 | 1997-09-18 | Basf Ag | Verfahren zur Dehydrierung von sekundären cyclischen Alkoholen |
-
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- 1999-07-19 DE DE19933079A patent/DE19933079A1/de not_active Withdrawn
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2000
- 2000-07-06 WO PCT/EP2000/006376 patent/WO2001005499A1/de not_active Application Discontinuation
- 2000-07-06 KR KR1020027000762A patent/KR20020013968A/ko not_active Application Discontinuation
- 2000-07-06 CN CN00810469A patent/CN1361718A/zh active Pending
- 2000-07-06 JP JP2001510578A patent/JP2003504194A/ja active Pending
- 2000-07-06 AU AU64321/00A patent/AU6432100A/en not_active Abandoned
- 2000-07-06 EP EP00951346A patent/EP1202799A1/de not_active Withdrawn
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| Publication number | Publication date |
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| HK1048613A1 (zh) | 2003-04-11 |
| JP2003504194A (ja) | 2003-02-04 |
| WO2001005499A1 (de) | 2001-01-25 |
| EP1202799A1 (de) | 2002-05-08 |
| ZA200200015B (en) | 2003-01-02 |
| DE19933079A1 (de) | 2001-01-25 |
| AU6432100A (en) | 2001-02-05 |
| KR20020013968A (ko) | 2002-02-21 |
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