CN109675610A - 用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂、苯乙烯制备方法 - Google Patents
用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂、苯乙烯制备方法 Download PDFInfo
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 34
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 79
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 54
- 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 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000005342 ion exchange Methods 0.000 claims description 20
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 27
- 230000029936 alkylation Effects 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000006276 transfer reaction Methods 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- -1 styrene Alkene Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 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 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
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Abstract
本发明公开了一种用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂、苯乙烯制备方法,该催化剂包括:碱性分子筛催化剂和负载型硼催化剂。该复合催化剂用于甲苯甲醇侧链烷基化反应时,能够有效控制甲醇的分解和反应过程中苯乙烯与甲醇之间的氢转移反应,抑制产物乙苯的生成,获得了较高的甲苯转化率和苯乙烯选择性。本发明另一方面还提供了使用了该催化剂的苯乙烯制备方法。
Description
技术领域
本发明涉及一种用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂、苯乙烯制备方法,属于化工领域。
背景技术
苯乙烯(ST)作为重要的芳烃化学品,主要用于生产聚苯乙烯(PS)、发泡级聚苯乙烯(EPS)、丙烯腈-丁二烯-苯乙烯树脂(ABS)、苯乙烯-丁二烯橡胶(SBR)等化工产品。
目前工业上生产苯乙烯的主流技术为乙苯脱氢法,包含苯和乙烯烷基化生成乙苯和乙苯脱氢制苯乙烯两个步骤。除工艺流程较长以外,乙苯脱氢法还存在副反应多、能耗大以及过度依赖石油资源等问题,上述问题使得苯乙烯生产新工艺的开发成为化工领域的一个研究热点。
在众多研究中,甲苯甲醇侧链烷基化制苯乙烯技术,体现出很好的工业应用前景,而改性CsX分子筛催化剂因其具有较好的甲苯甲醇侧链烷基化反应活性被多次公开报道。Unland等人(美国专利4140726A)公开了一种B2O3改性的CsX分子筛催化剂,在甲苯、甲醇进料摩尔比为5:1,反应温度为410℃时,苯乙烯选择性最高可达到35.2%。S.钦塔(CN103917504A)公开了CsX分子筛催化剂在添加一定含量的硼后,甲苯甲醇侧链烷基化反应性能,甲苯转化率由改性前的13.2%提高到16.1%,同时苯乙烯选择性由3.9%提高到22.0%。Alabi等人(Catal.Today,2014,226,117)报导了一种经Cs2O和ZrB2O5共改性的CsX分子筛催化剂,在甲苯甲醇进料摩尔比为6:1,反应温度为410℃时,甲苯转化率和苯乙烯选择性分别由改性前的3.1%和10%提高到5.2%和36.4%。
然而,甲苯甲醇侧链烷基化反应过程中甲醇分解严重以及产物中苯乙烯易与甲醇发生氢转移反应生成乙苯等问题阻碍了该工艺技术的进一步发展应用。
发明内容
根据本发明的一个方面,提供了一种用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,该催化剂用于甲苯甲醇侧链烷基化反应时,能够有效控制甲醇的分解,抑制反应过程中苯乙烯与甲醇之间的氢转移反应,抑制副产物乙苯的生成,从而获得较高的甲苯转化率和苯乙烯选择性。
所述用于甲苯甲醇侧链烷基化反应制苯乙烯的催化剂,其特征在于,包括:碱性分子筛催化剂和负载型硼催化剂。
本领域技术人员,可根据需要选择上述两种催化的用量。现有各类用于甲苯甲醇侧链烷基化反应制苯乙烯的催化剂中,包含二者即可发挥作用。碱性分子筛催化剂和负载型硼催化剂可以为商业渠道购买,也可以为采用现有方法制备。
可选地,所述催化剂由碱性分子筛催化剂和负载型硼催化剂组成。
可选地,所述碱性分子筛催化剂与所述负载型硼催化剂的质量比为0.1~10:1混合;
优选地,所述碱性分子筛催化剂与所述负载型硼催化剂的质量比为0.5~8:1混合;
更优选地,所述碱性分子筛催化剂与所述负载型硼催化剂按质量比为6~7:1混合。进一步优选地,所述碱性分子筛催化剂与所述负载型硼催化剂按质量比还可以为1:1、3:1、5:1、4:1。
混合碱性分子筛催化剂与负载型硼催化剂时,可以先将二者按比例混合后,充分研磨,成型,得到催化剂。本领域技术人员可根据需要,按现有工艺参数进行混合、研磨,成型。
可选地,所述碱性分子筛催化剂是经碱金属离子改性的分子筛,采用离子交换法制备得到。
可选地,所述分子筛选自X型分子筛、Y型分子筛和β型分子筛中的至少一种。
可选地,所述分子筛的硅铝比为1~5;
优选地,所述分子筛的硅铝比为1.12~4.52;
进一步优选地,所述分子筛的硅铝比为2.63~4.52。碱性分子筛催化剂中载体的硅铝比还可以为1.12。
可选地,所述碱性分子筛催化剂采用离子交换法制备。
可选地,所述离子交换法包括以下步骤:
1)将分子筛载体浸入前驱体溶液中,进行离子交换,得到前躯体分子筛;
2)将所述前躯体分子筛,置于空气气氛中,焙烧,得到所述碱性分子筛催化剂。
本领域技术人员可根据需要,采用该方法的常用参数进行制备。可选地,离子交换法包括以下步骤:在80℃下进行离子交换2~4次,抽滤、洗涤至滤出液呈中性后,干燥、焙烧即得所述碱金属离子交换的分子筛。
可选地,所述碱金属离子选自钾离子、铷离子、铯离子中的至少一种。例如所用前驱体溶液为KNO3溶液、RbNO3溶液或CsNO3溶液中的至少一种。
可选地,所述碱性分子筛催化剂中碱金属离子的离子交换度为30~80%。
可选地,所述碱性分子筛催化剂中碱金属离子的离子交换度范围下限选自30%、35%、36.9%、40%、40.1%或43.6%,上限选自52.1%、51.7%、60.2%、71.4%或80%。
优选地,所述碱性分子筛催化剂中碱金属离子的离子交换度为36.9~71.4%。
进一步优选地,所述碱性分子筛催化剂中碱金属离子的离子交换度为43.6~52.1%。
可选地,所述负载型硼催化剂是具有介孔孔道的载体负载的硼催化剂,采用等体积浸渍法制备。
可选地,所用等体积浸渍法包括以下步骤:
1)将体积相等的介孔载体与硼酸水溶液混合后,进行浸渍;
2)浸渍结束后,经烘干、焙烧得到所述负载型硼催化剂;
优选地,包括预处理所述介孔载体的步骤,所述预处理步骤为在空气气氛中焙烧所述介孔载体。
可选地,所述具有介孔孔道的载体选自介孔SiO2、MCM-41和SBA-15中的至少一种。
本领域技术人员可根据需要,采用该方法的常用参数进行制备。可选地,等体积浸渍法,包括以下步骤:将焙烧预处理过的介孔载体,加入等体积硼酸水溶液中浸渍,室温下浸渍过夜,干燥、焙烧即得负载型硼催化剂。
可选地,所述负载型硼催化剂中硼的负载质量为所述负载型硼催化剂总质量的0.5~3%;
优选地,所述负载型硼催化剂中硼的负载质量为所述负载型硼催化剂总质量的1~2.8%。进一步优选地,还可以为2%、1.5%。
本发明的又一方面还提供了一种苯乙烯制备方法,包括以下步骤:
将含有甲苯和甲醇的原料气与如上述催化剂接触,制备苯乙烯;
反应条件为:
原料气中,甲苯和甲醇的摩尔比为甲苯:甲醇=1~7:1,
以甲苯计,所述原料气的质量空速为1~4h-1;
反应温度为380~500℃,反应压力为0.1~10Mpa。
优选地,所述原料气由甲苯和甲醇组成。
反应温度范围的下限可选自380℃、400℃、420℃或440℃,上限可选自450℃、460℃、470℃、480℃、490℃、500℃。
反应压力范围的下限可选自0.1Mpa、0.2Mpa、0.3Mpa或0.4Mpa,上限可选自0.4Mpa、0.5Mpa、0.8Mpa、1.0Mpa。
原料气的质量空速(以甲苯计)范围下限可选自1h-1或2h-1,上限可选自3h-1或4h-1。
原料气中所述甲苯与所述甲醇的摩尔比范围下限可选自1:1、2:1、3:1或4:1,上限可选自5:1、6:1或7:1。
可选地,所述碱金属分子筛和负载型硼催化剂混合后用于甲苯甲醇侧链烷基化制苯乙烯时,至少包含以下步骤:
a)向装有催化剂的反应器中通入氦气,并在550℃温度下活化1~2h;
b)步骤a)活化结束后,向反应器中通入甲苯和甲醇的混合原料气后,原料气与催化剂接触反应产生苯乙烯。
本领域技术人员可根据需要,选择所需反应器,例如所述反应器为一个固定床反应器或多个固定床反应器串联;所述反应器包含至少一个甲苯甲醇侧链烷基化催化剂床层。
本发明能产生的有益效果包括:
1)本发明所提供的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,针对目前甲苯甲醇侧链烷基化反应过程中苯乙烯选择性较低的问题,提供了一种高选择性制苯乙烯催化剂,该催化剂可有效控制甲醇的分解和苯乙烯与甲醇之间的氢转移反应,提高产物中苯乙烯选择性。
2)本发明所提供的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,通过将碱金属分子筛催化剂与负载型硼催化剂混合,有效控制了甲醇的分解和苯乙烯与甲醇之间的氢转移反应,抑制了乙苯的生成,提高了产物中的苯乙烯/乙苯比。
3)本发明所提供的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,该催化剂具有甲苯转化率高、产物中苯乙烯选择性高等特点。
4)本发明所提供的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,该催化剂用于甲苯甲醇侧链烷基化制苯乙烯的方法,操作简便,满足工业应用要求,便于进行大规模工业化生产。
5)本发明所提供的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,用于甲苯甲醇制备苯乙烯时,甲苯转化率可达13.97%,甲醇转化率可达92.41%,苯乙烯可达62.41%,乙苯选择性可达28.61%。
具体实施方式
下面结合实施例详述本发明,但本发明并不局限于这些实施例。
如无特别说明,本发明的实施例中的原料和催化剂均通过商业途径购买,仪器设备采用厂家推荐的参数设置。
实施例中所采用的载体均来自商业购买,其中:
NaX(Si/Al=1.12)购自南开催化剂厂;NaY(Si/Al=2.63)购自南开催化剂厂;Naβ(Si/Al=4.52)购自南开催化剂厂;介孔二氧化硅购自青岛裕民源硅胶试剂厂;MCM-41购自南开催化剂厂;SBA-15购自南开催化剂厂。
实施例中,催化剂的元素组成采用PANAbalytical公司的Axios2.4KW型X射线荧光分析仪(XRF)进行测定。
实施例中,采用安捷伦7890A色谱在线分析。烃类组分采用Agilent CP-WAX 25m×32μm×1.2μm毛细管柱分析,FID检测器检测;CO、CO2和H2采用Porapark Q 4m×1/8″填充柱分析,TCD检测器检测。
实施例中,甲苯的转化率X甲苯、甲醇的转化率X甲醇、苯乙烯选择性S苯乙烯和乙苯选择性S乙苯的计算方法如下:
实施例1碱性分子筛催化剂样品B-1#~B-8#的制备
碱性分子筛催化剂样品B-1#~B-8#的制备,包括以下步骤:
分别取NaX(Si/Al=1.12)、NaY(Si/Al=2.63)、Naβ(Si/Al=4.52)分子筛各100g,然后以0.2mol/L的KNO3、RbNO3、CsNO3前驱体溶液250mL,在80℃下离子交换,经抽滤、洗涤后,于110℃烘干,然后在空气气氛中2℃/min升温至550℃焙烧4h,所得固体磨碎后经压片、破碎并筛分为20-40目备用,所得样品编号为B-1#~B-8#。
所得样品编号、离子交换液种类、浓度、交换次数以及离子交换度如表1所示。
采用XRF元素分析对所得样品进行元素分析,分析得到在步骤2)中离子交换步骤前后,样品B-1#~B-8#的钠含量。
按下式计算各样品B-1#~B-8#的离子交换度:
表1
实施例2负载型硼催化剂样品C-1#~C-8#的制备
负载型硼催化剂样品C-1#~C-8#的制备,包括以下步骤:
1)在550℃的空气气氛中,焙烧待浸渍介孔载体6小时后降至室温。称取50g焙烧过的载体,加入与载体等体积的硼酸水溶液进行浸渍。
2)在室温下浸渍过夜,所得混合物在110℃温度下烘干,然后在空气气氛中,以2℃/min升温至550℃焙烧4小时,所得固体磨碎后经压片、破碎并筛分为20-40目备用得到样品C-1#~C-8#。
样品C-1#~C-8#制备中介孔载体和硼的负载量如表2所示,其他参数如前述负载型硼催化剂样品制备步骤。
表2
样品 | 载体 | 硼负载量(质量) |
C-1<sup>#</sup> | 介孔SiO<sub>2</sub> | 0.5% |
C-2<sup>#</sup> | 介孔SiO<sub>2</sub> | 1% |
C-3<sup>#</sup> | 介孔SiO<sub>2</sub> | 2% |
C-4<sup>#</sup> | MCM-41 | 1.2% |
C-5<sup>#</sup> | MCM-41 | 2.5% |
C-6<sup>#</sup> | MCM-41 | 3% |
C-7<sup>#</sup> | SBA-15 | 1.5% |
C-8<sup>#</sup> | SBA-15 | 2.8% |
实施例3催化剂样品CAT-1#~C AT-16#的制备
在所制备的碱性分子筛催化剂B-1#~B-8#中选取一个样品,同时在所制备的负载型硼催化剂C-1#~C-8#中选取一个样品,然后分别按照表3中的比例装填在小型固定床反应器的恒温区,并在反应器两端装填石英砂。
每次实验的样品组合所选取的碱性分子筛催化剂样品的编号以及负载型硼催化剂样品的编号如表3所示。
表3
装填完反应器后,催化剂床层首先在氦气气氛下(40mL/min)550℃活化1h,然后降温至反应温度,用微量进料泵通入原料甲苯和甲醇,甲苯与甲醇进料摩尔比、空速、反应压力、反应温度见表4。产物通过安捷伦7890A气相色谱仪进行检测,反应结果列于表4中。
表4侧链烷基化催化剂的反应结果
由表4可见,本发明提供的复合催化剂,用于甲苯甲醇侧链烷基化反应制苯乙烯时,能有效提高乙苯选择性、苯乙烯选择性和甲醇转化率。甲苯转化率可达13.97%,甲醇转化率可达92.41%,苯乙烯可达62.41%,乙苯选择性可达28.61%。
以上所述,仅是本发明的几个实施例,并非对本发明做任何形式的限制,虽然本发明以较佳实施例揭示如上,然而并非用以限制本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,包括:碱性分子筛催化剂和负载型硼催化剂。
2.根据权利要求1所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述碱性分子筛催化剂与所述负载型硼催化剂的质量比为0.1~10:1;
优选地,所述碱性分子筛催化剂与所述负载型硼催化剂的质量比为0.5~8:1。
3.根据权利要求1所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述碱性分子筛催化剂是经碱金属离子改性的分子筛,采用离子交换法制备得到。
4.根据权利要求3所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述分子筛选自X型分子筛、Y型分子筛和β型分子筛中的至少一种。
5.根据权利要求3所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述分子筛的硅铝比为1~5;
优选地,所述分子筛的硅铝比为1.12~4.52;
进一步优选地,所述分子筛的硅铝比为2.63~4.52。
6.根据权利要求3所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述碱金属离子选自钾离子、铷离子、铯离子中的至少一种。
7.根据权利要求3所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述碱性分子筛催化剂中碱金属离子的离子交换度为30~80%;
优选地,所述碱性分子筛催化剂中碱金属离子的离子交换度为36.9~71.4%;
更优选地,所述碱性分子筛催化剂中碱金属离子的离子交换度为43.6~52.1%。
8.根据权利要求1所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述负载型硼催化剂是具有介孔孔道的载体负载的硼催化剂,采用等体积浸渍法制备;
优选地,所述具有介孔孔道的载体选自介孔SiO2、MCM-41和SBA-15中的至少一种。
9.根据权利要求1所述的用于甲苯甲醇侧链烷基化反应制苯乙烯的复合催化剂,其特征在于,所述负载型硼催化剂中硼的负载质量为所述负载型硼催化剂总质量的0.5~3%;
优选地,所述负载型硼催化剂中硼的负载质量为所述负载型硼催化剂总质量的1~2.8%。
10.一种苯乙烯制备方法,其特征在于,包括以下步骤:
将含有甲苯和甲醇的原料气与如权利要求1~9中任一项所述的复合催化剂接触,制备苯乙烯;
反应条件为:
原料气中,甲苯和甲醇的摩尔比为甲苯:甲醇=1~7:1,
以甲苯计,所述原料气的质量空速为1~4h-1;
反应温度为380~500℃,反应压力为0.1~10Mpa。
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