CN106955682A - 低水比乙苯脱氢催化剂 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001868 water Inorganic materials 0.000 title claims abstract description 44
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 230000000694 effects Effects 0.000 abstract description 12
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- 238000012360 testing method Methods 0.000 description 5
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
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- 238000011069 regeneration method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- DXDWSXBIERDUTF-UHFFFAOYSA-N [Mg].[W].[Ce].[K].[Fe] Chemical compound [Mg].[W].[Ce].[K].[Fe] DXDWSXBIERDUTF-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
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- 229910001950 potassium oxide Inorganic materials 0.000 description 1
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- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
本发明公开了一种低水比乙苯脱氢催化剂,按照重量百分比包括以下组分:(a)60~85%的Fe2O3;(b)3~25%的K2O;(c)0.2~5%的WO3;(d)3~20%的CeO2;(e)0.2~10%的Na2O;(f)0.2~5%的CaO;(g)0.1~1%的Al2O3。本发明提供的低水比乙苯脱氢催化剂,在低水比条件下具有高的活性和稳定性。
Description
技术领域
本发明涉及烷基芳烃脱氢催化剂技术领域,特别涉及一种低水比乙苯脱氢催化剂。
背景技术
以氧化铁为主要成分的脱氢催化剂在各种乙苯脱氢反应中的应用已经是现有技术中长期已知的。例如乙苯脱氢制苯乙烯、异丙苯脱氢制a-甲基苯乙烯等。是强吸热、增分子的可逆反应,工业上通常采用水蒸汽作稀释剂以降低乙苯分压,促使反应向产物方向移动。水蒸汽在反应中有如下作用:
(1)加热反应原料到所需温度,避免将乙苯直接加热到更高温度,抑制副反应的发生,提高选择性;
(2)补充热量,以免由于反应吸热而降温;
(3)通过水煤气反应不断排除催化剂上的积炭,使催化剂自动再生。
但是水蒸汽加入量受到反应系统允许压力降和能耗这两个因素的制约,先进的乙苯脱氢工艺均追求以较低的水比(进料中水蒸汽与乙苯的质量之比)获得较高的苯乙烯收率,采用低水比操作是苯乙烯装置节能降耗的重要措施之一。
乙苯脱氢制苯乙烯催化剂是以氧化铁为主要活性组分、氧化钾为主要助催化剂的铁系催化剂,钾可以成数量级地增加氧化铁的活性,而且能促进水煤气反应将积炭排除、使催化剂自动再生,在低水比条件下,由于反应系统中水蒸气量的减少,导致系统还原性增强,催化剂中的多铁酸钾在还原气氛的作用下分解,钾离子从该化合物中流失,从而引起催化剂选择性的下降。一般催化剂如果在水比(水/乙苯)低于2.0(重量)下进行乙苯脱氢反应,催化剂的选择性变差,虽然能耗降低了,但是物耗却大大增加。
对此,根据迄今为止的有关文献报导,科研人员已作过很多尝试,如已公开的欧洲专利0177832报道了在催化剂中加入1.8-5.4%(重量)的氧化镁后,催化剂可以在水比低于2.0(重量)下表现出稳定的优良性能,但该催化剂的钾含量较高;如已公开的美国专利4535067报道了催化剂中一部分钾以钾霞石复盐形式加入,但该催化剂在614±2℃时转化率不到65%,选择性最高93%,单收不到60%,选择性相对较低。
专利CN101279266A公布了一种低水比催化剂,描述了在铁-钾-铈-钨-钙体系中添加铷的技术方案,在低水比条件下具有较好的稳定性,但该催化剂的应用水比为1.5,依旧较高。
专利201010261733公布了一种低水比催化剂,描述了在铁-钾-铈-钨-镁催化体系中添加铯化合物和至少一种稀土氧化物Sm2O3、Eu2O3、Gd2O3或Dy2O3的催化剂在低水比条件下具有较好的稳定性。但该催化剂应用水比为1.5,依旧较高。
发明内容
基于现有技术中乙苯脱氢催化剂在低水比条件下选择性差、活性低的问题,本发明目的是提供一种低水比乙苯脱氢催化剂,将该催化剂用于乙苯脱氢反应制备苯乙烯工程中具有低水比条件下选择性好和活性高的特点,提高生产效率。
为了克服现有技术的不足,本发明提供的技术方案是:
一种低水比乙苯脱氢催化剂,按照重量百分比包括以下组分:
(a)60~85%的Fe2O3;
(b)3~25%的K2O;
(c)0.2~5%的WO3;
(d)3~20%的CeO2;
(e)0.2~10%的Na2O;
(f)0.2~5%的CaO;
(g)0.1~1%的Al2O3。
优选的技术方案中,所述Na2O的含量为0.3~5%。
优选的技术方案中,催化剂中不含有MgO。
本发明涉及的催化剂的制备原料为:Fe2O3由氧化铁红(Fe2O3)和氧化铁黄(Fe2O3·H2O)组成,氧化铁红和氧化铁黄的配比为Fe2O3∶Fe203·H2O=0.2~5∶1,优选为1~4.5∶1;所用K以钾盐或氢氧化物形式加入;所用Ce以氧化物、氢氧化物或铈盐形式加入;所用W以其盐或氧化物形式加入;所用Na以氢氧化物或钠盐形式加入,所用Al以氧化物、氢氧化物或盐形式加入。在本发明的制备过程中,除催化剂主体成分外还应加入制孔剂,制孔剂可从石墨、聚苯乙烯微球、羧甲基纤维素中选择,其加入量为催化剂总重量的1-6%。
本发明涉及的催化剂的制备方法为:按照配比称重所需原料以及制孔剂,混合均匀后加入去离子水,制成具有粘性、适合挤条的膏状物,经挤条、切粒成直径为3mm、长为8~10mm的颗粒,然后在60~120℃条件下干燥24h,最后在400~1000℃条件下焙烧4h制得催化剂成品。
与现有技术相比,本发明的优点是:
本发明通过在铁-钾-铈-钨-钙催化体系中添加Na2O和Al2O3的组合,催化剂在水比1.2条件下具有良好的活性,提高了催化剂的活性,当水比从1.2降低到1.0,苯乙烯收率只有少量的损失,提高了低水比条件下的稳定性能。
具体实施方式
以下结合具体实施例对上述方案做进一步说明。应理解,这些实施例是用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以根据具体厂家的条件做进一步调整,未注明的实施条件通常为常规实验中的条件。
制备催化剂采用的原料为氧化铁红、氧化铁铁黄、碳酸钾、碳酸铈、七钨酸铵、氢氧化钙、碳酸钠、铝源(碳酸铝、氢氧化铝、硝酸铝、草酸铝、氧化铝)。
对比例1
将原料氧化铁红、氧化铁铁黄、碳酸钾、碳酸铈、七钨酸铵、氢氧化钙在捏和机中搅拌1小时,加入去离子水,再搅拌0.5小时,取出挤条,挤成直径3毫米、长度8~10毫米的颗粒,放入烘箱,80℃烘干2小时,120℃烘2小时,然后置于马福炉中,在900℃条件下焙烧4小时制得催化剂A。
催化剂A组分按重量百分比包括68.8%的Fe2O3,12.5%的K2O,15.2%的CeO2,2.2%的CaO,1.3%的WO3,催化剂组分参见表1。
制得的催化剂在等温式固定床中进行活性评价,具体过程为:将去离子水和乙苯分别经计量泵输入预热混合器,预热混合成气态后进入反应器,反应器为1寸的不锈钢管,内可装100ml粒径3mm的催化剂,反应器采用电热丝加热至反应所需的温度,由反应器流出的反应物经水冷凝后用气相色谱分析其成分,并采用以下公式计算乙苯的转化率和苯乙烯的选择性:
将100ml催化剂装入反应器,常压、液体空速1.0小时-1、620℃、水比(重量)1.2和1.0条件下进行活性评价,测试结果列于表2-3。
对比例2
其他与对比例1相同,不同之处在于在对比例2中制备催化剂的原料加入了氧化铝,制得催化剂B。催化剂B组分按重量百分比包括68.75%的Fe2O3,12.5%的K2O,15.2%的CeO2,2.2%的CaO,1.3%的WO3,0.05%的Al2O3,催化剂组分参见表1。制得催化剂后按照对比例1的评价方法评价催化剂的活性,测试结果见表2-3。
对比例3
其他与对比例1相同,不同之处在于在对比例3中制备催化剂的原料中加入了氧化铝,制得催化剂C。催化剂C组分按重量百分比包括68.6重量%的Fe2O3,12.5重量%的K2O,15.2重量%的CeO2,2.2重量%的CaO,1.3重量%的WO3,0.2%的Al2O3,催化剂组分参见表1,制得催化剂后按照对比例1的评价方法评价催化剂的活性,测试结果见表2-3。
实施例1-7
添加不同量Na2CO3的情况下制备一系列催化剂DEFGHIJ,其中催化剂D中铝源为碳酸铝,催化剂E中铝源为氢氧化铝,催化剂F中铝源为硝酸铝。催化剂G中铝源为草酸铝,其余催化剂中铝源为氧化铝,各催化剂中按氧化铝含量计算设定为0.5%,其他原料的用量是按照表1所示的实际氧化物的组成而使用。制得催化剂后按照实施例1的评价方法评价催化剂的活性,测试结果见表2-3。
实施例8-13
添加不同量Al2O3和不同量Na2O的情况下,制备一系列催化剂K~S。其他原料的用量是按照表1所示的实际氧化物的组成而使用。
表1催化剂的组成
表2催化剂在水比1.0条件下催化剂的性能
表3是催化剂在水比1.2条件下催化剂的性能,另外表3显示了水比从1.2降低到1.0时(苯乙烯收率△Y 1.2→1.0)苯乙烯收率的降低值△Y。
表3催化剂在水比1.2条件下催化剂的性能
从上述实施例和对比例的测试结果比较可知,催化剂在水比为1.2条件下具有良好的活性,当水比从1.2降低到1.0时候,催化剂的活性损失较少,可见催化剂的稳定性较好。
上述实例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人是能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的保护范围之内。
Claims (3)
1.一种低水比乙苯脱氢催化剂,其特征在于按照重量百分比包括以下组分:
(a)60~85%的Fe2O3;
(b)3~25%的K2O;
(c)0.2~5%的WO3;
(d)3~20%的CeO2;
(e)0.2~10%的Na2O;
(f)0.2~5%的CaO;
(g)0.1~1%的Al2O3。
2.根据权利要求1所述的低水比乙苯脱氢催化剂,其特征在于:所述Na2O的含量为0.3~5%。
3.根据权利要求1或2所述的低水比乙苯脱氢催化剂,其特征在于:催化剂中不含有MgO。
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