CN100457703C - 精制苯酚的方法和催化剂 - Google Patents
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 9
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- 238000001935 peptisation Methods 0.000 claims abstract description 8
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 7
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
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- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- GPKFMIVTEHMOBH-UHFFFAOYSA-N cumene;hydrate Chemical compound O.CC(C)C1=CC=CC=C1 GPKFMIVTEHMOBH-UHFFFAOYSA-N 0.000 description 1
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- 229940001516 sodium nitrate Drugs 0.000 description 1
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
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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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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明的目的是通过转化存在于苯酚原料中的杂质以生成高纯苯酚，该苯酚原料是由过氢氧化异丙苯分解得到的。通过采用铝锆催化剂精制含有脂肪族和芳香族羰基化合物的混合物的苯酚来实现所述目标。该催化剂包含铝和锆的氧化物和硫酸盐的混合物，并且铝和锆的硫酸盐的总含量为5-15%质量(基于SO4离子计算)，和铝的氧化物和硫酸盐的总含量是5-30%质量(基于氧化铝计算)。能够在硫酸盐化和胶溶步骤中，用硫酸两次处理氢氧化锆，和采用由质量比为1∶3至3∶1的勃姆石和假勃姆石的混合物组成的氧化铝制备该催化剂。
Description
本申请是美国非临时申请，基于2002年2月8日申请的俄罗斯申请2002103669，并要求其优先权，该申请在此引入作为参考。
背景技术
本发明涉及化学和石油化学领域，更具体地涉及通过异丙基苯法生产苯酚和丙酮的方法。
通过用酸性催化剂分解过氢氧化异丙苯(cumyl hydroperoxide)而生产的苯酚用作原料，不能满足消费者的要求，因为它含有羟丙酮(HA)、2-甲基苯并呋喃(2-MBF)、α-甲基苯乙烯(AMS)、苯乙酮(AP)、异亚丙基丙酮(MO)和二甲基苯甲醇(DMPC)混合物，而且需要将这些杂质除去。
相对纯净的最终产物苯酚通过过氢氧化异丙苯的分解产物的分馏，分离出较低沸点和较高沸点的组分而获得[美国专利4251325(1978)]。然而，即使小心操作精馏器，分离出来的苯酚还是含有相对少量但仍不希望的杂质如HA和2-甲基苯并呋喃。
用于精制用作原料的苯酚的已知方法包括采用各种多相(heterogeneous)催化剂，其将上列杂质几乎全部转化为高沸点化合物，该高沸点化合物之后能通过蒸馏法从苯酚中分离出来。HA是一个例外，其根据催化剂的效率可以转化为2-甲基苯并呋喃或较高沸点产物。这样，在催化转化期间，仅有的杂质2-甲基苯并呋喃能积累在催化产物中，使得接下来的分离过程复杂化。
例如，一种已知的方法是将用酸性催化剂分解过氢氧化异丙苯得到的苯酚原料与多相催化剂接触来生产高纯苯酚，该催化剂是具有一定的比表面和一定的表面中心(surface centers)酸度的γ氧化铝。在该方法中，存在于原料苯酚(starting phenol)中的脂肪族的和芳香族的羰基化合物转化为高沸点产物，其通过精馏相对容易地从最终产物中除去[美国专利5264636(1992)]。该方法的缺点是催化剂的活性不够高，特别当原料苯酚中的杂质含量相对小(0.1％质量及更小)时，这意味着最终产物中的2-甲基苯并呋喃的含量降低仅仅很小的范围。
还有一种已知的精制苯酚方法是将异丙基苯氧化过程的副产物从中除去。该方法包括通过将其与活性铝硅酸盐(aluminosilicate)催化剂接触来处理原料苯酚，然后用蒸馏法分离生成的高沸点组分[美国专利2910511-原型(prototype)]。
发明简述
本发明的目的是通过转化存在于由过氢氧化异丙基苯分解得到的苯酚原料中的杂质以生产高纯苯酚。所述目标通过用铝锆催化剂精制含有脂肪族和芳香族羰基化合物的混合物的苯酚来实现。
发明详述
原型使用的催化剂是合成的酸性铝硅酸盐催化剂，其为无定形或晶体且从凝胶或通过酸处理皂土型铝硅酸盐粘土而制备。
用于精制过程的有效温度是50-200℃，该温度使得能在液相和气相中进行精制。催化剂的活性越高，工艺温度越高，达到需要的苯酚的精制程度要求的接触时间就越短。然而，当使用催化剂时，由于其沉积在工艺温度下为固态的反应产物的孔中使得催化剂逐渐失活。再生这些催化剂包括用精制的苯酚进行洗涤。
这一精制苯酚方法的缺点也是存在的HA被铝硅酸盐催化剂很大程度上转化为难以从苯酚中除去的2-甲基苯并呋喃。
铝锆催化剂表示铝和锆的氧化物和硫酸盐的混合物，而铝和锆的硫酸盐的总含量为5-15质量％(基于SO4计算)，以及铝的氧化物和硫酸盐的总含量是5-30质量％(基于氧化铝计算)。
在90-200℃的温度下进行精制，保持通过催化剂床的必要的相对原料定容供料速率(relative raw material volumetric feed rate)，以提供1-6h-1的空速(space velocity)。通过与所提出的催化剂接触而生产的苯酚能蒸馏分离出几乎纯净的苯酚。
包含在苯酚原料中的杂质全部转化为易于从苯酚中除去的高沸点化合物；对HA也是如此，至多30％的HA转化为2-甲基苯并呋喃。
用于精制苯酚所提出的方法的本质表现特征是采用铝锆催化剂，其是铝和锆的氧化物和硫酸盐的混合物，和在给定温度和给定相对原料定容供料速率下进行该工艺。
本发明涉及用于精制苯酚的催化剂及其制备方法。
氧化铝催化剂一般通过在PH 8.7-9.5下，用浓硝酸，采用两种方法：所谓在18-25℃下的“冷”沉淀和所谓在100-102℃下的“热”沉淀，从铝酸钠溶液中沉淀出氢氧化铝，并以不同比例混合这些沉淀物而制备，这使其能控制产物的质量。用水洗涤沉淀混合物以除去硝酸钠，通过煮沸和胶溶(peptizing)来增塑，然后将得到的物质在螺杆挤压机中成型为所需尺寸的颗粒[USSR专利1559494(1990)，俄罗斯联邦专利2058189，公布在Biulleten′izobretenii[Russian Patent Office Journal]no.11，4/20/96]。
用于其它用途而非精制苯酚的铝锆催化剂，通过以下方法制备：用氨水溶液从氯氧化锆(ZrOCl2·8H2O)溶液中沉淀出氢氧化锆，然后干燥产生的沉淀物并用1N的硫酸处理。为了成型为颗粒，混合硫酸化的(sulfonated)粉化氢氧化锆和用作粘合剂的氢氧化铝[J.Catal.153：218-223(1995)]。
例如，一种已知的制备用于链烷烃异构化的铝锆催化剂的方法[美国专利6326328(2000)-原型]。所述方法包括加入一种硫酸化剂——硫酸胺盐获取粉化的氢氧化锆和氢氧化铝混合物，将其混合、挤出，并在600℃煅烧所得的颗粒。氢氧化铝或水合氢氧化铝用作粘合剂。然而，由于其活性比用所提出的方法得到的催化剂低，根据该方法制备的催化剂对精制苯酚不适合。尤其是，它不能将最终产物精制到2-甲基苯并呋喃含量要求的范围。
制备用于精制苯酚(其由过氢氧化异丙苯分解得到)的催化剂所提出的组合物的方法的包括下列阶段：沉淀氢氧化铝和氢氧化锆；使氢氧化物硫酸化；使电解质溶液胶溶；螺杆挤出催化物质(catalyzed mass；以及热处理。所用的铝化合物原料是氢氧化铝，其由质量比为1∶3至3∶1(基于氧化铝计算)的勃姆石和假勃姆石组成。硫酸水溶液用作胶溶剂，并在硫酸盐化和胶溶阶段引入到催化物质中。
所提出的方法的本质表现特征是采用所述比例的勃姆石和假勃姆石制备化合物，以及在催化物质的硫酸盐化阶段和胶溶阶段两个步骤中引入硫酸。根据所提出的方法制备的催化剂可将存在于作为原料的苯酚中的几乎所有的杂质转化为易于除去的高沸点化合物。
用于苯酚精制的所提出的催化剂及其制备方法的工业实用性通过下列实施例证实。
实施例
实施例1
a)催化剂的制备
431g的ZrOCl2·8H2O盐溶解在5.2L蒸馏水中。332mL浓度约为25％的NH4OH溶液用20分钟以上滴入上述形成的溶液中。滤出产生的沉淀物并在布氏(Buchner)漏斗上用水洗涤该沉淀物以除去氯化铵。洗涤过的沉淀物在110℃干燥箱中干燥24小时。干燥后的沉淀物在研磨机中研磨，所得的细小粉末通过180μm的筛子进行筛分。粉末的质量是190g或147g，其基于ZrO2计算。
用1.14L 1N的硫酸溶液处理该粉末1个小时使其硫酸化。然后，过滤所得到的混合物以除去过量溶液，产物在110℃下干燥(10h)，再进一步用于成型。
使用3升100g/L的铝酸钠溶液以生产假勃姆石。在温度20-25℃，PH范围9.1-9.5下，通过同时倾入所述铝酸盐溶液和60％的硝酸溶液(流出量(yield)：1.8L)2小时以上进行沉淀。在溶液一起完全倾入之后，在加入铝酸钠溶液以保持PH为9.1-9.3范围不变下通过沸腾(102-105℃)来稳定悬浮液。产物是包含300g Al2O3的假勃姆石玻璃状沉淀的悬浮液。
使用1升100g/L的铝酸钠溶液以生产勃姆石。在温度102-105℃(沸腾时)，PH范围8.5-8.9下，通过同时倾入所述铝酸盐溶液和60％的硝酸溶液(流出量：0.7L)2小时以上进行沉淀。产物是包含100g Al2O3的勃姆石蜂蜜状沉淀的悬浮液。
将所得的假勃姆石和勃姆石的悬浮液合并在一起，并在布氏漏斗上洗涤以除去杂质硝酸钠盐。洗涤的沉淀物在110℃干燥10小时并研磨成细小粉末，所有粉末通过具有0.25mm孔的筛子。当将所得的干燥的混合氢氧化铝粉末在850℃烘烤时，煅烧损失为24.6％质量。氢氧化铝粉末中的勃姆石与假勃姆石的比例是1∶3，基于Al2O3计算。
之后，粉化的硫酸化氢氧化锆与83.6g粉化的氢氧化铝在Werner &Pfleiderer Z页片式搅拌机中进行混合，溶液用硫酸溶液(3.8ml，60％溶液)胶溶化，并加入小份大约250mL的水，使得物质的含湿量(煅烧损失)至55％质量。所得到的物质在螺杆挤压机中通过一个具有2mm直径孔的模头成型。挤出物在110℃下干燥8小时，然后在630℃干燥空气流中烘烤4小时。
最终催化剂的总成分：66.2％质量的ZrO2；30％质量的γ-Al2O3；5.0％质量的S。催化剂中铝和锆的硫酸盐的总含量是15.0％(基于SO4计算)，以及铝的氧化物和硫酸盐的总含量是30％质量(基于Al2O3计算)。
b)苯酚的精制
在温度100℃和原料定容供料速率1.5h-1下，在直流(flow-through)实验装置中，进行用于精制苯酚工艺的所得铝锆催化剂的试验。下表给出了作为原料的苯酚的成分和在所制备的催化剂上催化精制的产物的成分，该苯酚原料由过氢氧化异丙苯分解得到且假定其需要进行精制。
表 原料苯酚和催化精制苯酚的成分
苯酚中杂质的含量在采用OV-I作固定相，配置有25m长的毛细管柱的“Kristall 2000M”色谱仪上由气相色谱法测定。
实施例2
催化剂的制备如实施例1，但在混合的粉化氢氧化铝中，勃姆石和假勃姆石的比例为3∶1(基于Al2O3计算)。氢氧化锆沉淀物用380ml硫酸溶液硫酸化。用于与粉化的硫酸化氢氧化锆进行混合的混合的粉化氢氧化铝为13.9g。余下的参数与实施例1相同。
在得到的烘烤(最终)催化剂样品中铝和锆的硫酸盐的总含量是5.0％质量，基于SO4计算，铝的氧化物和硫酸盐的总含量是5％质量，基于Al2O3计算。
用于精制苯酚工艺的所得的铝锆催化剂的试验在温度110℃和原料定容供料速率6h-1下进行。所得苯酚具有以下成分(ppm)：HA＜1；α-甲基苯乙烯＜1；2-甲基苯并呋喃-50；OM＜5；AP＜1；和DMPC＜1。
实施例3
样品取用铝锆催化剂，其制备和成分描述在实施例1中。根据上述方法，在温度90℃及原料定容供料速率V＝1h-1下进行试验。所得苯酚具有下列成分(ppm)：HA＜1；α-甲基苯乙烯＜1；2-甲基苯并呋喃-58；OM＜5；AP＜1；和DMPC＜1。
实施例4
样品取用铝锆催化剂，其制备和成分描述在实施例2中。根据上述方法，在温度200℃及原料定容供料速率V＝1.5h-1下进行试验。所得苯酚具有下列成分(ppm)：HA＜1；α-甲基苯乙烯＜1；2-甲基苯并呋喃-31；OM＜5；AP＜1；和DMPC＜1。
Claims (2)
1.一种用于精制由过氢氧化异丙苯裂解法得到的苯酚原料的方法，该方法包括：(i)在90-200℃的温度和1-6h-1的原料定容供料速率下，使原料苯酚与酸性氧化铝催化剂接触，和(ii)随后通过蒸馏分离出精制苯酚，其中所述氧化铝催化剂包含铝和锆的氧化物和硫酸盐的混合物，该催化剂中铝和锆的硫酸盐的总含量为5-15％质量，基于SO4离子计算，和铝的氧化物和硫酸盐的总含量是5-30％质量，基于氧化铝计算，
其中所述催化剂由以下方法制备，该方法包括以下步骤：沉淀氢氧化铝和氢氧化锆，硫酸化该混合的氢氧化物，将该硫酸化的氢氧化物胶溶，将该胶溶的氢氧化物挤出和热处理挤出的胶溶的氢氧化物，其中所述氢氧化铝是质量比为1∶3至3∶1的勃姆石和假勃姆石的混合物，基于氧化铝计算。
2.根据权利要求1所述的方法，其中所述催化剂基本上由铝和锆的氧化物和硫酸盐的混合物组成。
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| KR101503072B1 (ko) | 2005-07-20 | 2015-03-16 | 바이엘 헬스케어 엘엘씨 | 게이트형 전류 측정법 |
| KR20130100022A (ko) | 2005-09-30 | 2013-09-06 | 바이엘 헬스케어 엘엘씨 | 게이트형 전압 전류 측정 분석물 결정 방법 |
| WO2008051742A2 (en) | 2006-10-24 | 2008-05-02 | Bayer Healthcare Llc | Transient decay amperometry |
| WO2009076302A1 (en) | 2007-12-10 | 2009-06-18 | Bayer Healthcare Llc | Control markers for auto-detection of control solution and methods of use |
| SA113340468B1 (ar) * | 2012-04-13 | 2015-07-07 | ميتسوي كيميكالز، انك. | عملية لتنقية الفينول |
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