CN111039742A - 以三甲苯异构化制均三甲苯的催化剂 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011230 binding agent Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- 238000011068 loading method Methods 0.000 abstract description 8
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
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- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 239000003377 acid catalyst Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- -1 mesitylene antioxidant 330 Chemical compound 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7846—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及一种以三甲苯异构化制均三甲苯的催化剂,以催化剂重量百分比计,包括如下组分:1)45~65wt%的氢型EUO结构分子筛;2)30~60%γ‑Al2O3;3)第VIII族元素两种金属;4)第VIB族元素一种金属,催化剂的制备方法包括如下步骤:氢型EUO分子筛和γ‑Al2O3混匀。加入硝酸水溶液混捏挤条成型,阴干、烘干和焙烧。经三种金属负载、烘干、焙烧得催化剂,本发明制备的催化剂在三甲苯异构化制均三甲苯时,抗结焦能力强,稳定性好,寿命长;本发明制备的催化剂中所负载的金属元素协同作用,C8前轻组分少,氢耗小,反应压力低,降低生产成本。
Description
技术领域
本发明涉及一种芳烃异构化的催化剂,尤其涉及一种以三甲苯异构化制均三甲苯的催化剂。
背景技术
均三甲苯是一种宝贵的精细化工原料,其作为有机化工原料制取合成树脂、M 酸、均三甲苯胺抗氧剂330、高效麦田除草剂、聚酯树脂稳定剂、醇酸树脂增塑剂等,还可用于生产活性艳蓝、K-3R 等染料中间体,具有广阔的市场前景。
均三甲苯的生产方法可分为合成法与分离提纯法等。合成法主要包括丙酮与浓硫酸合成法以及二甲苯气相合成法等;分离法包括精馏法、磺化法、深冷结晶法、HF-BF3 抽提法、异构化法和烷基化法等。目前国内工业上的生产方法主要以烷基化法和偏三甲苯异构化法为主。
将三甲苯转化为均三甲苯的异构化催化剂早有报导,其载体多由氧化铝或氧化硅和 一种或多种沸石共同构成,并负载有一种或多种金属组元。
CN1510017A公开了一种同时制备均三甲苯和均四甲苯的催化剂,该催化剂为含β沸石的结晶金属硅酸盐的酸式催化剂,在温度为210 -400℃,压力为1-50巴,重量空速为0.1-20h-1条件下以偏三甲苯为原来可生成均三甲苯和均四甲苯。
CN102746092A公开了一种重芳炷加氢裂解分离生产均三甲苯的方法,以负载质量百分比0. 005 -0. 5%铂或钯的氢型无粘结剂十元环沸石为催化剂,以氢气和重芳烃为原料进行加氢裂解处理,可以増产BTX芳炷和分离生产均三甲苯。
李仲明等将偏三甲苯同氢在浸渍了铝镍的缺铝氢型丝光沸石催化剂上反应生成均三甲苯,已在南京炼油厂实现了工业化生产,但其产量达不到设计能力的200吨/年,规模小,生产成本高,纯度难以达到 98.5%。
南京炼油厂研究所在微反色谱联用装置上研究了用精馏分离制备偏三甲苯过程中的塔底油即混合三甲苯代替纯偏三甲苯作原料,以镍钼丝光沸石为催化剂,得到了接近热力学平衡分布的均三甲苯产物,反应的适宜温度为320℃-380℃,压力0.11-1.15MPa,空速 1.10-2.10h-1。
发明内容
本发明的目的是提供一种以三甲苯异构化制均三甲苯的催化剂,以实现异构化反应高选择性、稳定性好、寿命长和产物中均三甲苯浓度超过化学平衡组成的技术目标,提高均三甲苯收率,降低生产成本。
本发明采用了如下技术方案:
本发明提供的一种以三甲苯异构化制均三甲苯的催化剂,以催化剂重量百分比计,包括如下组分:
1)45~65wt%的氢型EUO结构分子筛;
2)30~60%γ-Al2O3;
3)第VIII族元素两种金属;
4)第VIB族元素一种金属。
以上技术方案中,以催化剂重量百分比计,所述氢型EUO结构分子筛的摩尔硅铝比优选范围为30~50,所述VIII族元素的负载量范围优选0.005~0.05%,所述VIB族元素的负载量优选范围为0.05~0.15%。
优选的技术方案,所述第VIII族元素为铂、钯、铱、钌、钴或镍元素中的两种,优选铂、钯。所述VIB族元素为铬、钼元素中的一种,优选的钼。
所述的以三甲苯异构化制均三甲苯的催化剂的制备方法,包括如下步骤:
(1)将EUO结构分子筛氢型原粉与γ-Al2O3混合、加入无机粘结剂捏合;
所述的无机粘结剂选自硝酸或磷酸,优选的为重量浓度2%的硝酸或重量浓度2%的磷酸,无机粘结剂的重量用量为:
EUO结构分子筛氢型原粉与γ-Al2O3∶无机粘结剂=10:2~5;
(2)然后挤压成条,阴干24小时,120℃烘干3小时,530-540℃下焙烧4小时得到催化剂本体;
(3)将催化剂本体与第VIII族元素两种金属或其他金属盐的混合溶液进行等体积浸渍24小时,90~110℃烘干5小时;
(4)步骤(3)中烘干后的催化剂本体与第VIB族元素一种金属或其他金属盐溶液等体积浸渍12小时,60℃静置4小时;
(5)步骤(4)中静置后的催化剂本体再90~110℃烘干5小时,550℃焙烧4小时;得到以三甲苯异构化制均三甲苯的催化剂。
本发明的有益效果是:
(1)均三甲苯平衡达成率高,即产物中的均三甲苯含量已超过平衡组成,均三甲苯在产物中含量可达24%;异构性能好,烷基转移等副反应少,三甲苯收率高可达89%;
(2)本发明制备的催化剂在三甲苯异构化制均三甲苯时,抗结焦能力强,稳定性好,寿命长;
(3)本发明制备的催化剂中所负载的金属元素协同作用,C8前轻组分少,氢耗小,反应压力低,降低生产成本。
具体实施方式
对本发明的技术方案做进一步详细说明。
取SiO2/Al2O3摩尔比为30的EUO分子筛和γ-Al2O3粉料按65:35的干基质量比混匀。加入浓度为2%的硝酸水溶液混捏挤条成型,
硝酸的加入重量为:EUO结构分子筛氢型原粉与γ-Al2O3∶硝酸=10:3;
阴干24小时,120℃烘干3小时,530-540℃下焙烧4小时。用氯铂酸和氯化钯的混合溶液进行等体积浸渍24小时,氯铂酸溶液浓度为0.008%,氯化钯溶液浓度为0.05%,90~110℃烘干5小时后用钼酸铵溶液等体积浸渍12小时,钼酸铵溶液浓度为0.1%,60℃静置4小时后再90~110℃烘干5小时,550℃焙烧4小时得催化剂A,其组成见表1。
实例2
按实例1的方法制备催化剂,不同的是将SiO2/Al2O3摩尔比为35的EUO分子筛和γ-Al2O3粉料按60:40的干基质量比混匀成型,经三种金属负载、烘干、焙烧得催化剂B,其组成见表1。
实例3
按实例1的方法制备催化剂,不同的是将SiO2/Al2O3摩尔比为40的EUO分子筛和γ-Al2O3粉料按55:45的干基质量比混匀成型,经三种金属负载、烘干、焙烧得催化剂C,其组成见表1。
实例4
按实例1的方法制备催化剂,不同的是将SiO2/Al2O3摩尔比为45的EUO分子筛和γ-Al2O3粉料按50:50的干基质量比混匀成型,经三种金属负载、烘干、焙烧得催化剂D,其组成见表1。
实例5
按实例1的方法制备催化剂,不同的是将SiO2/Al2O3摩尔比为50的EUO分子筛和γ-Al2O3粉料按45:55的干基质量比混匀成型,经三种金属负载、烘干、焙烧得催化剂E,其组成见表1。
实例6-10,评价实施例
用上述实例1-5制备出的催化剂A、B、C、D、E在氢气气氛中于500℃还原4小时。在固定床反应器中以偏三甲苯为原料进行异构化反应评价。反应器内径20毫米,催化剂装量25克。反应条件为:温度360℃,压力0.5MPa,氢烃比600v/v,质量空速3.0h-1。各实例所用催化剂、原料油组成和反应结果见表2。
表1
表2
注:
均三甲苯/Σ三甲苯=产物中均三甲苯/产物中Σ三甲苯×100%
综上所述,仅为本发明的较佳实施例而已,并非用来限定本发明实施的范围,凡依本发明权利要求范围所述的形状、构造、特征及精神所为的均等变化与修饰,均应包括于本发明的权利要求范围内。
Claims (8)
1.以三甲苯异构化制均三甲苯的催化剂,其特征在于,以催化剂重量百分比计,包括如下组分:1)45~65wt%的氢型EUO结构分子筛;2)30~60%γ-Al2O3;3)第VIII族元素两种金属;4)第VIB族元素一种金属,所述第VIII族元素为铂、钯、铱、钌、钴或镍元素,所述VIB族元素为铬、钼元素中的一种。
2.根据权利要求1所述的以三甲苯异构化制均三甲苯的催化剂,其特征在于,以催化剂重量百分比计,所述氢型EUO结构分子筛的摩尔硅铝比优选范围为30~50。
3.根据权利要求1所述的以三甲苯异构化制均三甲苯的催化剂,其特征在于,以催化剂重量百分比计,所述VIII族元素的负载量范围优选0.005~0.05%。
4.根据权利要求1所述的以三甲苯异构化制均三甲苯的催化剂,其特征在于,以催化剂重量百分比计,所述VIB族元素的负载量优选范围为0.05~0.15%。
5.根据权利要求1所述的以三甲苯异构化制均三甲苯的催化剂,其特征在于,所述第VIII族元素优选铂、钯。
6.根据权利要求1所述的以三甲苯异构化制均三甲苯的催化剂,其特征在于,所述VIB族元素优选钼。
7.根据权利要求1-6任一项所述的以三甲苯异构化制均三甲苯的催化剂的制备方法,包括如下步骤:
(1)将EUO结构分子筛氢型原粉与γ-Al2O3混合、加入无机粘结剂捏合;
(2)然后挤压成条,阴干24小时,120℃烘干3小时,530-540℃下焙烧4小时得到催化剂本体;
(3)将催化剂本体与第VIII族元素两种金属或其他金属盐的混合溶液进行等体积浸渍24小时,90~110℃烘干5小时;
(4)步骤(3)中烘干后的催化剂本体与第VIB族元素一种金属或其他金属盐溶液等体积浸渍12小时,60℃静置4小时;
(5)步骤(4)中静置后的催化剂本体再90~110℃烘干5小时,550℃焙烧4小时;得到以三甲苯异构化制均三甲苯的催化剂。
8.根据权利要求7所述的以三甲苯异构化制均三甲苯的催化剂的制备方法,其特征在于,所述的无机粘结剂选自硝酸或磷酸,优选的为重量浓度2%的硝酸或重量浓度2%的磷酸,无机粘结剂的重量用量为:
EUO结构分子筛氢型原粉与γ-Al2O3∶无机粘结剂=10:2~5。
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