CN1221497C - 异丁烯的选择性二聚方法 - Google Patents
异丁烯的选择性二聚方法 Download PDFInfo
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Classifications
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- C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
- C07C9/16—Branched-chain hydrocarbons
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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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
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Abstract
本发明涉及制备包括三甲基戊烯(类)的反应产物的方法,其包括使含有异丁烯和正丁烯(类)的C4烯属原料与包括β沸石的催化剂接触,在允许异丁烯选择性二聚的条件下获得三甲基戊烯(类)。还包括通过这些方法所获得的产品。
Description
本发明涉及由C4烯属的原料制备包括三甲基戊烯(类)反应产物的选择性的方法。本发明还涉及由该方法所获得的产物。
异丁烯低聚物是制备各种有商业需求的产品如具有8、12或16个碳原子的异链烷烃、高级醇、醛类或羧酸等的有用的中间体。在这些产品中,通过三甲基戊烯氢化所获得的高支化的三甲基戊烷特别益于用作汽油辛烷值增强剂。的确,三甲基戊烷具有高的RON(研究辛烷值)和MON(发动机辛烷值):也被称为异辛烷的2,2,4-三甲基戊烷的RON为100和MON为100;2,3,4-三甲基戊烷的RON为109.9和MON为95.9;2,2,3-三甲基戊烷的RON为109.9和MON为99.9。
制备三甲基戊烯的一个途径是使异丁烯二聚。然而,由异丁烯有效制备三甲基戊烯要求该方法能选择性地获得二聚物而不是低聚物。异丁烯的低聚反应可以在使用磷酸、三氟化硼、硅铝酸盐或含沸石的催化剂的各种酸性条件下进行。然而,这些方法通常获得二聚物、三聚物、四聚物和高分子量低聚物的混合物。
异丁烯的选择性二聚而不是三聚反应和高级低聚反应在USP3325465和DE3542171-A1中是已知的。
在USP3325465中,通过在已经被镍或钴离子交换的硅铝酸盐的存在下进行聚合反应,使具有2-6个碳原子的烯烃二聚,基本上排除了三聚物和高级聚合物。所显示出的异丁烯的二聚是在13X分子筛上进行的,该分子筛的95.9%的钠离子被钴离子交换,转化成二聚物的比率是超过90%,甚至接近100%。然而,并没有给出二聚物产品的精确的组成。DE3542171-A1公开了在150℃下使用掺杂了铋和/或铅的沸石催化剂,使异丁烯选择性二聚为2,4,4-三甲基戊-1-烯和2,4,4-三甲基戊-2-烯。形成二聚物而不是三聚物的选择性高达88%。
因此在USP3325465和DE3542171-A1中公开的方法是由异丁烯原料获得异丁烯二聚物的选择性方法。然而,在工业规模上,更加有利的是使用由石油裂解所获得的工业的C4烯属的原料。这些原料是在炼油厂中生产的,通常包括异丁烯、1-丁烯和2-丁烯;它们还包括丁二烯。
使用混合了其它C4烯烃的异丁烯所带来的问题是异丁烯低聚反应条件除了产生所希望的异丁烯均二聚体即三甲基戊烯外,还产生了异丁烯与原料中其它的一般的C4烯烃的共二聚体。因此由混合的C4烯属的原料选择性制备三甲基戊烯要求高选择性的工艺条件。在该方法中所使用的催化剂必须是不但对二聚物而不是高级低聚物具有选择性,而且必须是有利于异丁烯均二聚反应,而不是异丁烯与原料中其它的一般的C4烯烃的共二聚反应。
在USP4454367和USP5091590中公开了在沸石催化剂下由C4烯烃混合物进行异丁烯的低聚反应。
USP4454367公开了使异丁烯转化为低聚物即异丁烯二聚物、三聚物和四聚物的混合物的方法,其中异丁烯来自包括异丁烯和正丁烯的C4烯属混合物。该方法使用了作为催化剂的具有SiO2/Al2O3摩尔比为50-200的高硅丝光沸石,并有利于形成异丁烯低聚合物。在该实施例中,将由26.2摩尔%的丁烷、1.3摩尔%的异丁烯、7.5摩尔%的1-丁烯和65摩尔%的2-丁烯组成的C4烃混合物在80℃下进料到装有高硅丝光沸石的反应器中。在这些条件下,异丁烯转化率在低正丁烯损失情况下达到93%。
USP5091590公开了由包括异丁烯、1-丁烯和/或2-丁烯的C4原料制备MTBE(甲基叔丁基醚)的两步方法。在该方法的第一步中,在固体酸酯化催化剂颗粒下用甲醇处理C4原料(第一反应区)。该步产生了含有MTBE和未反应原料的中间体产品,包括10-55%的来自新鲜原料和过量甲醇的未反应的异丁烯。从第一反应区分离出中间体产品,分馏回收MTBE。接着将中间体产品的剩余部分进行该方法的第二步;将其与中孔固体酸催化剂颗粒接触获得含有MTBE、异丁烯低聚物和C5+烷基化物的产物。第二步优选的催化剂选自ZSM-5、ZSM-11、ZSM-50、β沸石、MCM-22及其混合物。根据该文献,第二步反应在70-280℃下进行。
我们现在发现了从工业的C4烯属原料中除去异丁烯的其它工艺条件,并且该条件只对三甲基戊烯具有选择性,对其它C8烯烃和高级低聚物不具有选择性。
因此,本发明提供了一种制备包括三甲基戊烯(类)的反应产物的方法,其包括使含有异丁烯和正丁烯(类)的C4烯属原料与包括β沸石的催化剂接触,在允许异丁烯选择性二聚的条件下获得三甲基戊烯(类)。
除了异丁烯,在该方法中使用的C4烯属原料可以包括正丁烯,即1-丁烯和/或2-丁烯。任选地,这些原料还可以含有丁二烯。适合的C4烯属原料包括在精制、裂解(催化裂解或蒸汽裂解)和/或油类重整中获得的C4烃混合物,从在油类热裂解生产乙烯中形成的C4副产品馏分中除去丁二烯所获得的丁烷-丁烯馏分,或由含有正丁烷和异丁烷的烃混合物的脱氢作用所获得的C4烃混合物。
本方法有利的是在不必预先从进料中分离出异丁烯的情况下使异丁烯进行低聚。本方法的另一个优点是相对于异丁烯/正丁烯共二聚反应的对异丁烯均低聚反应的高度选择性。在原料中存在的不到10重量%、优选不到5重量%的正丁烯进行低聚。使用包括β沸石的催化剂实现该选择性。
就本方法的目的来说,β沸石是质子形式,因此被称为H-β沸石。H-β沸石是具有相对大孔的沸石。其可商购或可以不同的Si/Al原子比范围例如10-150合成制备。参考文献是P.A.Jacobs和J.A.Martens的“Synthesis of High Silica Aluminosilicate Zeolites”(出版在丛书“Studies in Surfuce Science and Catalysis”中的33卷),其综述了β沸石的合成和性质。具有Si/Al原子比高于150的β沸石能通过脱铝作用如水热的(蒸汽)和/或化学处理获得。我们可参见H.VanBekkum等人的“Introduction to Zeolite Science and Practice”,Elsevier 1991,其在脱铝作用方面更加详细。这些脱铝的H-β沸石也可用于本方法。
所述β沸石催化剂可以粉末(包括由完全地或部分地单晶组成的粉末)形式使用。β沸石催化剂代替地是可以具有一定形状的块集岩例如片剂、挤出物或球体的形式被加入,这可以通过使β沸石与在低聚合反应条件下基本上是惰性的粘合剂材料混合来获得。所述沸石催化剂可以基于沸石和粘合剂材料的重量的1-99重量%的量存在。作为粘合剂材料,可以使用任何适合的材料,例如硅石,金属氧化物,或粘土,例如蒙脱土、皂土和高岭土粘土,所述粘土任选在使用前煅烧或化学改性。该适合的基质原料的其它例子包括二氧化硅-氧化铝、二氧化硅-氧化铍、二氧化硅-氧化镁、硅-氧化钍、二氧化硅-二氧化钛、二氧化硅-氧化铝-氧化镁、二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆和二氧化硅-氧化镁-氧化锆。
本发明的方法可以在各种适合异相反应的反应器中进行,可在固化或液化床反应器中进行。所述方法可以在间歇或连续流动的反应器中进行,或根据催化蒸馏技巧(还称为反应蒸馏)进行。由C4烯属原料向异丁烯的转化可在液相、气相或混合相下进行。
本方法选择性地使在C4烯属原料中存在的异丁烯转化为包括三甲基戊烯类的反应产物:二聚物可表示为所有形成的低聚物的至少45重量%,优选60重量%,和三甲基戊烯类可表示为所有形成的二聚物的至少80重量%。这种对三甲基戊烯类的选择性可在适合的温度如低于50℃下实现。
因此,本发明还包括使C4烯属原料与包括β沸石的催化剂接触所获得的产品。所述产品可以通过一个或多个转化步骤,例如分馏、氢化作用、接着氧化或氢化的氢甲酰化作用、羰基化作用、酯化作用、环氧化作用或水合作用被转化为具有商业需求的其它产品。本发明还包括通过这些进一步转化所获得的产品,例如烷烃、醇类、醚类、醛类、环氧化物类或羧酸类。
例如,能立即随着氢化作用获得由C4烯属原料使异丁烯选择性二聚成包括至少45重量%三甲基戊烯类的反应产物。其获得的烃组合物包括至少45重量%三甲基戊烷类,它是用于清洁配方、涂层配方、粘合剂配方等的溶剂。
来自C4烯属原料的异丁烯的二聚可以在醇存在下进行。在这一情况下,三甲基戊烯类的醚化作用与异丁烯的二聚同时进行。
下面的非限定性的实施例用于解释本发明。
下面研究在各种H-β沸石催化剂的存在下来自工业的C4烯属原料的异丁烯的选择性二聚。
将沸石催化剂(烯属原料的10重量%)和C4烯属原料(具有下面的组份,用重量%表示:12%异丁烷,19%正丁烷,14%1-丁烯,20.2%异丁烯,20.5%反-2-丁烯和13.1%顺-2-丁烯)装入配置了加热元件和机械搅拌的1升的反应器中。将该反应器用氩加压直到10bars。接着将该混合物加热到40℃,保持该温度2小时。反应之后,将反应器冷却,在加压下取样。
然后通过气相色谱法(GC)使用氢气作为载气测定产品混合物的组份。把注射器衬圈填充氢化催化剂(0.03克的在Al上的0.5%Pt),这样进行原位氢化,确定链属烃的所有组份。通过把产品混合物的气相色谱法分析同相同条件下的原料的气相色谱法分析相比来测定丁烯/异丁烯的转化率。原料含有在反应条件下是惰性的丁烷和异丁烷;因此把丁烷和异丁烷用作计算转化率的内标。
被测试的催化剂是:
-H-β10:具有Si/Al原子比为10.5的H-β沸石,商购自ZeolystInternational;
-H-β30:具有Si/Al原子比为30的H-β沸石,以钠形式从β沸石获得,其已经在空气下在550℃下锻烧了16小时,然后在回流下用0.5N氯化铵水溶液(对1g催化剂来说,100ml溶液)进行交换12小时,接着在空气中在550℃下干燥和锻烧10小时。根据在EP187522中公开的过程来合成制备在该过程所使用的以钠形式的β沸石;
-H-β30蒸汽:将上述H-β在650℃下蒸16小时;
-H-β30蒸汽再生:将上述H-β30蒸汽在使用后通过在空气中在550℃下干燥和锻烧10小时已经再生的;
-硝酸H-β30:将上述的H-β30在回流下用6N硝酸处理2小时,过滤和洗涤直到洗液中没有酸,然后在75℃下真空干燥过夜;
-H-β50:具有Si/Al原子比为50的H-β沸石,商购自Sud Chemie;
-H-β100:具有Si/Al原子比为100的H-β沸石,商购自Sud Chemie;
-H-β150:具有Si/Al原子比为150的H-β沸石,商购自Sud Chemie;
-H-β150蒸汽:将上述H-β150在650℃下蒸16小时;
-硝酸H-β150:将上述的H-β150在回流下用6N硝酸处理2小时,过滤和洗涤直到洗液中没有酸,然后在75℃下真空干燥过夜;
该表给出了这些沸石中的每一个所获得的结果。
在该表中,
-iC4=指异丁烯;
-nC4=指正丁烯;
-C8表示所形成的二聚物的重量%;
-C12表示所形成的三聚物的重量%;
-C16表示所形成的四聚物的重量%;
-NC8表示以辛烯(氢化后的辛烷)的形式所获得的二聚物的重量%;
-MC7表示以甲基庚烯(氢化后的甲基庚烷)的形式所获得的二聚物的重量%;
-DMC6表示以二甲基己烯(氢化后的二甲基己烷)的形式所获得的二聚物的重量%;
-TMC5表示以三甲基戊烯(氢化后的三甲基戊烷)的形式所获得的二聚物的重量%;
-2,2,4-TMP表示以2,2,4-三甲基戊烷(氢化后)的形式以TMC5的重量%计的部分;
-2,3,4-TMP表示以2,3,4-三甲基戊烷(氢化后)的形式以TMC5的重量%计的部分;
催化剂 | 重量(g) | 转化率 重量% | 选择性 重量% | 氢化后C8支化(重量%) | ||||||||
iC4= nC4= | C8 C12 C16 | NC8 MC7 DMC6 TMC5 | 2,2,4TMP 2,3,4TMP* | |||||||||
H-β10 | 10.0 | 87 | 4 | 60 | 28 | 10 | 0.0 | 0.0 | 11 | 89 | 45 | 5 |
H-β30 | 10.2 | 93 | 6 | 60 | 30 | 8 | 0.0 | 0.0 | 16 | 84 | 49 | 7 |
H-β30蒸汽 | 9.5 | 50 | 0 | 68 | 24 | 6 | 0.0 | 0.0 | 3 | 97 | 90 | 3 |
H-β30蒸汽再生 | 7.5 | 56 | 0 | 71 | 27 | 0 | 0.0 | 0.0 | 3 | 97 | 91 | 1 |
硝酸H-β30 | 9.4 | 44 | 0 | 74 | 18 | 5 | 0.0 | 0.0 | 5 | 95 | 82 | 2 |
H-β50 | 6.4 | 96 | 7 | 58 | 34 | 7 | 0.0 | 0.0 | 16 | 84 | 55 | 7 |
H-β100 | 8.7 | 100 | 9 | 48 | 33 | 18 | 0.0 | 0.0 | 19 | 81 | 45 | 8 |
H-β150 | 9.1 | 96 | 6 | 55 | 44 | 0.0 | 0.0 | 0.0 | 15 | 85 | 55 | 6 |
H-β150蒸汽 | 8.3 | 32 | 0 | 63 | 27 | 7 | 0.0 | 0.0 | 7 | 92 | 79 | 3 |
硝酸H-β150 | 10.0 | 53 | 1 | 63 | 35 | 0.0 | 0.0 | 0.0 | 8 | 92 | 74 | 4 |
以重量%计的组合物;12%iC4 19%nC4 14%nC4=1 20.2%iC4=20.5%反式C4=2 13.1%顺式C4=2原料同催化剂在40℃下反应2小时
*残余TMP是2,2,3-和2,3,3-三甲基戊烷
Claims (8)
1.一种制备包括三甲基戊烯的反应产物的方法,其包括使含有异丁烯和正丁烯的C4烯属原料与包括β沸石的催化剂接触,在允许异丁烯选择性二聚的条件下获得三甲基戊烯,其特征在于所述反应的温度低于50℃并且在使用前使所述β沸石进行脱铝作用。
2.根据权利要求1的方法,其特征在于在C4烯属原料中存在的不到10重量%的正丁烯进行低聚。
3.根据权利要求1或2的方法,其特征在于β沸石的脱铝作用是通过蒸汽和/或化学处理来进行的。
4.根据权利要求1或2的方法,其特征在于该方法是在间歇或连续流动的反应器中进行。
5.根据权利要求1或2的方法,其特征在于根据催化蒸馏技术进行该方法。
6.根据权利要求1的方法,其特征在于异丁烯二聚物表示为所有形成的产物的至少45重量%,和三甲基戊烯类表示为所有形成的二聚物的至少80重量%。
7.根据权利要求6的方法,其特征在于异丁烯二聚物表示为所有形成的产物的至少60重量%。
8.根据权利要求1的方法,其特征在于该方法还包括分馏、氢化作用、接着氧化或氢化的氢甲酰化作用、羰基化作用、酯化作用、环氧化作用或水合作用。
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US5910528A (en) * | 1996-03-27 | 1999-06-08 | Falicoff; Waqidi | Table tennis rubber solvent and adhesive systems |
AU4064997A (en) * | 1996-09-09 | 1998-03-26 | Catalytic Distillation Technologies | Alkylation of organic aromatic compounds using beta zeolite catalyst |
CA2346902C (en) * | 1998-10-16 | 2010-02-09 | Fortum Oil And Gas Oy | Process for dimerizing olefinic hydrocarbon feedstock and producing a fuel component |
-
1999
- 1999-12-23 GB GBGB9930402.4A patent/GB9930402D0/en not_active Ceased
-
2000
- 2000-12-20 MX MXPA02006200A patent/MXPA02006200A/es active IP Right Grant
- 2000-12-20 EP EP00988248A patent/EP1242342B1/en not_active Expired - Lifetime
- 2000-12-20 KR KR1020027008135A patent/KR100635314B1/ko not_active IP Right Cessation
- 2000-12-20 CA CA002394030A patent/CA2394030C/en not_active Expired - Fee Related
- 2000-12-20 AU AU24476/01A patent/AU782012B2/en not_active Ceased
- 2000-12-20 AT AT00988248T patent/ATE273259T1/de not_active IP Right Cessation
- 2000-12-20 BR BR0016719-3A patent/BR0016719A/pt not_active Application Discontinuation
- 2000-12-20 DE DE60012979T patent/DE60012979T2/de not_active Expired - Lifetime
- 2000-12-20 WO PCT/US2000/034840 patent/WO2001046095A1/en active IP Right Grant
- 2000-12-20 MY MYPI20006008A patent/MY125097A/en unknown
- 2000-12-20 JP JP2001546609A patent/JP4691303B2/ja not_active Expired - Fee Related
- 2000-12-20 CN CNB008175659A patent/CN1221497C/zh not_active Expired - Fee Related
- 2000-12-22 AR ARP000106888A patent/AR027087A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
CN1433390A (zh) | 2003-07-30 |
MXPA02006200A (es) | 2004-02-26 |
MY125097A (en) | 2006-07-31 |
DE60012979T2 (de) | 2005-07-28 |
CA2394030C (en) | 2009-01-20 |
JP4691303B2 (ja) | 2011-06-01 |
AR027087A1 (es) | 2003-03-12 |
EP1242342A1 (en) | 2002-09-25 |
CA2394030A1 (en) | 2001-06-28 |
KR100635314B1 (ko) | 2006-10-18 |
AU2447601A (en) | 2001-07-03 |
ATE273259T1 (de) | 2004-08-15 |
BR0016719A (pt) | 2002-09-03 |
EP1242342B1 (en) | 2004-08-11 |
WO2001046095A1 (en) | 2001-06-28 |
DE60012979D1 (de) | 2004-09-16 |
GB9930402D0 (en) | 2000-02-16 |
KR20020081231A (ko) | 2002-10-26 |
JP2004505008A (ja) | 2004-02-19 |
AU782012B2 (en) | 2005-06-30 |
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