CN112237941A - 芳构化催化剂及其制备方法和低碳烯烃芳构化方法 - Google Patents
芳构化催化剂及其制备方法和低碳烯烃芳构化方法 Download PDFInfo
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- CN112237941A CN112237941A CN201910654576.2A CN201910654576A CN112237941A CN 112237941 A CN112237941 A CN 112237941A CN 201910654576 A CN201910654576 A CN 201910654576A CN 112237941 A CN112237941 A CN 112237941A
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- catalyst
- aromatization
- phosphorus
- alumina
- microporous material
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- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 60
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 69
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 62
- 239000011574 phosphorus Substances 0.000 claims abstract description 62
- 239000012229 microporous material Substances 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 238000010335 hydrothermal treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000571 coke Substances 0.000 abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- -1 carbon hydrocarbon Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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Abstract
本发明涉及将低碳烯烃芳构化为芳烃领域,公开了一种芳构化催化剂及其制备方法和低碳烯烃芳构化方法。该芳构化催化剂包括微孔材料和粘合剂,以及可选的金属活性组分;所述粘合剂为含有铝元素和磷元素的化合物,铝元素与磷元素的摩尔比大于等于1且小于5;所述芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1。该芳构化催化剂可以将低碳烯烃进行芳构化反应生成芳烃,催化剂稳定性高,且芳烃产物的选择性好,还可以有效减少甲烷和焦炭的生成。
Description
技术领域
本发明涉及将低碳烯烃芳构化为芳烃领域,具体涉及芳构化催化剂及其制备方法和低碳烯烃芳构化方法。
背景技术
由于乙烷和乙烯的价格相对便宜且原料容易获得,越来越多的工艺转向烷烃或烯烃芳构化制备轻质芳烃(如BTX)。例如US20090209794A1公开了用于乙烷转化成芳烃的方法,该方法包括:步骤(a)、使乙烷与脱氢芳构化催化剂进行接触,所述催化剂含有0.005~0.1重量%的铂,含量不小于铂量的镓,10~99.9重量%的硅铝酸盐和粘合剂;以及步骤(b)、从步骤(a)的反应产物中分离甲烷、氢和C2~C5烃,得到含有苯的芳族反应产物。首先,该方法中的催化剂必须使用贵金属(铂、嫁),通过将贵金属与ZSM-5分子筛结合使用,成为双功能催化剂;其次,为了活化乙烷,该方法的反应温度高,需要在630℃下进行,然而乙烷的转化率却较低,转化率不大于70%,此外催化剂迅速失活,活性低于40%,即便在优化条件下,BTX收率通常也仅为30%至40%;再次,该方法中大部分乙烷转化为低价值的甲烷,未转化的乙烷和甲烷也增加了轻馏分分离和循环回收的难度。
EP0785178B1公开了一种生产芳烃的方法,该方法包括使含有烯烃和/或链烷烃的低碳烃原料与沸石催化剂在固定床绝热反应器中进行接触,进行催化反应。低碳烃原料的环化反应需要满足如下条件:(1)沸石催化剂的初始催化活性为0.2(sec-1)或更高。初始阶段,沸石催化剂催化的正己烷分解的一级反应速率常数;(2)催化剂床层的温度为450℃至650℃;(3)催化剂床相对于催化剂床入口到出口的距离的温度分布,其中温度分布具有至少一个最高温度值;(4)催化剂床出口的温度相对于催化剂床入口的温度为+/-40℃。此方法同样地由于反应温度高,很容易形成焦炭,导致催化剂较快失活,因此必须每隔几小时对催化剂进行脱焦处理(再生处理)。此外,较高的反应温度和频繁的再生处理导致贵金属从纳米颗粒状态变为烧结状态,为了将贵金属再次分散在催化剂载体上,必须在脱焦后注入含氯物质,在高温和潮湿环境中加入卤素从而对设备提出更高的要求。催化剂快速地失活还迫使采用更为复杂的反应器,例如移动床等反应器,从而增加了操作成本。
此外,现有技术也有以烯烃为原料进行芳构化反应,李昱,张英强等在《低碳烯烃芳构化催化剂与工艺进展》中介绍了ZSM-5分子筛及其改性催化剂用于低碳烯烃C2~C5的芳构化性能,结果表明在ZSM-5分子筛中加入一些金属如Zn、Ga、Pt、Ni、Cd等得到的改性催化剂可直接将烯烃及其混合物转化为芳烃,且芳烃收率、选择性都大有改善。但是该催化剂主要通过引入金属来改善收率和选择性,依然存在焦炭含量大,需要频繁进行再生处理的问题。
综上,在现有技术中存在大量生成甲烷,易形成焦炭,催化剂寿命短,需要频繁进行再生处理等问题,而且催化剂中必须需要使用金属,甚至是价格较高的贵金属。
发明内容
本发明的目的是为了克服现有技术存在的催化剂易失活,频繁再生,催化剂稳定性不高,反应物转化率低,催化剂中必须使用金属等问题,提供一种芳构化催化剂及其制备方法和低碳烯烃芳构化方法,采用该芳构化催化剂可以将低碳烯烃进行芳构化反应生成芳烃,催化剂稳定性高,且芳烃产物的选择性好,可以有效减少甲烷和焦炭的生成,而且所述芳构化催化剂中可以不使用金属。
为了实现上述目的,本发明第一方面提供了一种芳构化催化剂,该芳构化催化剂包括微孔材料和粘合剂,以及可选的金属活性组分;所述粘合剂为含有铝元素和磷元素的化合物,铝元素与磷元素的摩尔比大于等于1且小于5;所述芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1。
本发明第二方面提供了一种上述芳构化催化剂的制备方法,该方法包括以下步骤:
(a)将微孔材料、氧化铝和含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(b1)可选地,将所述催化剂进行水热处理;和/或,
(b2)可选地,将金属活性组分负载在所述催化剂表面。
本发明第三方面提供了另一种上述芳构化催化剂的制备方法,该方法包括以下步骤:
(A)将微孔材料和氧化铝进行混合和挤出,以及可选地进行水热处理,得到挤出物;
(B)将所述挤出物与含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(C)可选地,将金属活性组分负载在所述催化剂表面。
本发明第四方面提供了一种低碳烯烃芳构化方法,包括:在芳构化条件下,将低碳烯烃、氢气和催化剂接触,其中,所述催化剂为上述的芳构化催化剂。
本发明的芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1,优选不大于0.75,而且芳构化催化剂中的粘合剂包括铝和磷元素,铝元素与磷元素的摩尔比大于1且小于5,采用本发明的芳构化催化剂可以在较宽的温度区间内将低碳烯烃进行芳构化反应生成芳烃,同时以最小的焦炭、甲烷生成量实现较高的芳烃收率,并延长了催化剂的寿命。而且,本发明的原料可以直接来自乙烷裂解装置而无需进行净化和分离操作,从而进一步降低了生产成本。
此外,本发明的催化剂可以不使用金属,这不仅降低了催化剂成本,而且还降低了因含有卤素的再生过程从而增加的设备成本。
附图说明
图1本发明催化剂A和对比例催化剂D1的乙烯转化率的对比图;
图2是本发明催化剂A和对比例催化剂D1的BTX选择性的对比图;
图3是本发明的催化剂A、催化剂RA和催化剂D的乙烯转化率对比图;
图4是本发明的催化剂A、催化剂RA和催化剂D的BTX选择性的对比图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明第一方面提供了一种芳构化催化剂,其中,该芳构化催化剂包括微孔材料和粘合剂,以及可选的金属活性组分;所述粘合剂为含有铝元素和磷元素的化合物,铝元素与磷元素的摩尔比大于等于1且小于5;所述芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1。
在本发明中,弱酸性位点是指最大解吸温度低于300℃的NH3-TPD峰;强酸性位点是指最大解吸温度高于300℃的NH3-TPD峰。具体地,测试方法为本领域常规的程序升温脱附(TPD)表征酸性位方法。通过NH3-TPD仪器内置的热导检测器(TCD)可以检测不同温度下脱附的氨气量来得到酸度的分布。
在本发明中,对催化剂进行酸性位表征的方法和步骤可以为:称取0.2g催化剂装入石英样品管中,在氦气条件下程序升温至450℃,活化1h后,冷却至150℃,吸附氨气30min,然后切换为氦气吹扫,脱除过剩氨气至检测器基线稳定,然后以10℃/min升温速率程序升温至600℃,通过NH3-TPD仪器内置的热导检测器检测样品的氨气脱附量。
在本发明中,芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1,也即强酸性位点的酸度小于弱酸性位点的酸度,优选地,所述强酸性位点的酸度与弱酸性位点的酸度的比值不大于0.85,进一步优选不大于0.75。
在本发明中,所述微孔材料可以为分子筛,优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50,例如ZSM-5的硅铝比为10、15、20、25、30、35、40、45、50,以及这些数值中的任意两个所构成的范围中的任意值。其中,本发明的硅铝比是指SiO2/Al2O3的比值。
在本发明中,优选地,所述粘合剂为磷酸铝和可选的氧化铝。也即,所述粘合剂为磷酸铝,或者所述粘合剂为磷酸铝和氧化铝。
在本发明中,优选地,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种。
在本发明中,优选地,所述微孔材料和粘合剂的重量比为1:0.05~1,其中,粘合剂以粘合剂中的铝元素计。例如,所述微孔材料和粘合剂的重量比为1:0.05、1:0.1、1:0.15、1:0.2、1:0.25、1:0.3、1:0.35、1:0.4、1:0.45、1:0.5、1:0.55、1:0.6、1:0.65、1:0.7、1:0.75、1:0.8、1:0.85、1:0.9、1:0.95、1:1,以及这些数值中的任意两个所构成的范围中的任意值。
在本发明中,优选地,以所述芳构化催化剂的总量为基准,金属活性组分的含量为0重量%~1重量%,优选为0重量%~0.5重量%。例如,以所述芳构化催化剂的总量为基准,金属活性组分的含量为0重量%、0.001重量%、0.01重量%、0.05重量%、0.1重量%、0.5重量%,以及这些数值中的任意两个所构成的范围中的任意值。在本发明中,芳构化催化剂可以不含有金属活性组分,从而不仅降低了催化剂成本,而且还降低了因含有卤素的再生过程从而增加的设备成本。
在本发明中,微孔材料、粘合剂和金属活性组分的含量可以通过测量方法得到,也可以通过投料量进行计算得到。
本发明第二方面提供了一种上述芳构化催化剂的制备方法,该方法包括以下步骤:
(a)将微孔材料、氧化铝和含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(b1)可选地,将所述催化剂进行水热处理;和/或,
(b2)可选地,将金属活性组分负载在所述催化剂表面。
根据本发明的方法,优选地,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05~1。例如,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05、1:0.1、1:0.15、1:0.2、1:0.25、1:0.3、1:0.35、1:0.4、1:0.45、1:0.5、1:0.55、1:0.6、1:0.65、1:0.7、1:0.75、1:0.8、1:0.85、1:0.9、1:0.95、1:1,以及这些数值中的任意两个所构成的范围中的任意值。在本发明优选的实施方式中,通过加入特定量的含磷溶液,同时通过限定微孔材料和氧化铝,以及含磷溶液浓度,使得本发明制备的芳构化催化剂的强酸性位点的酸度小于弱酸性位点的酸度,采用该芳构化催化剂不仅可以高选择性地生成芳烃,且较少量地生成焦炭,同时还可以提高水热稳定性,进一步提高催化剂再生性能并延长使用寿命。
根据本发明的方法,所述含磷溶液中的溶剂可以为水。优选地,所述含磷溶液中的溶质选自磷酸、磷酸铵、膦及其衍生物中的一种或多种。
根据本发明的方法,优选地,所述含磷溶液中的磷元素的含量为0.5重量%~30重量%,优选为5重量%~15重量%。例如5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%,以及这些数值中的任意两个所构成的范围中的任意值。磷含量在优选的范围内时,制备得到的芳构化催化剂性能更优。
根据本发明的方法,优选地,所述微孔材料可以为分子筛,优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50。在优选的情况下,本发明通过限定硅铝比不大于50,从而使得本发明制备的催化剂具有较高的乙烯转化率和芳烃选择性,较少的焦炭产生量。
根据本发明的方法,优选地,所述水热处理的条件包括:温度为250℃~650℃,时间为0.5h~24h。
根据本发明的方法,可以选择性地负载金属活性组分,在优选的情况下,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种。负载的方法可以为本领域常规方法,例如浸渍法。引入上述金属活性组分的方式可以通过加入含有述金属活性组分的化合物而得到,所述含有述金属活性组分的化合物优选地选自主活性金属元素的氯化物、硝酸盐、硫酸盐、醋酸盐和草酸盐中的一种或多种。例如,引入Pt的方式可以为加入Pt(NO3)2溶液。
根据本发明的方法,优选地,所述焙烧的条件包括:温度为300℃~700℃,优选为450℃~600℃;时间为0.5h~24h,优选为2h~8h。
本发明第三方面提供了另一种上述催化剂的制备方法,该方法包括以下步骤:
(A)将微孔材料和氧化铝进行混合和挤出,以及可选地进行水热处理,得到挤出物;
(B)将所述挤出物与含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(C)可选地,将金属活性组分负载在所述催化剂表面。
根据本发明的方法,优选地,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05~1。例如,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05、1:0.1、1:0.15、1:0.2、1:0.25、1:0.3、1:0.35、1:0.4、1:0.45、1:0.5、1:0.55、1:0.6、1:0.65、1:0.7、1:0.75、1:0.8、1:0.85、1:0.9、1:0.95、1:1,以及这些数值中的任意两个所构成的范围中的任意值。在本发明优选的实施方式中,通过加入特定量的含磷溶液,同时通过限定微孔材料和氧化铝,以及含磷溶液浓度,使得本发明制备的芳构化催化剂的强酸性位点的酸度小于弱酸性位点的酸度,采用该芳构化催化剂不仅可以高选择性地生成芳烃,且较少量地生成焦炭,同时还可以提高水热稳定性,进一步提高催化剂再生性能并延长使用寿命。
根据本发明的方法,所述含磷溶液中的溶剂可以为水。优选地,所述含磷溶液中的溶质选自磷酸、磷酸铵、膦及其衍生物中的一种或多种。
根据本发明的方法,优选地,所述含磷溶液中的磷元素的含量为0.5重量%~30重量%,优选为5重量%~15重量%。例如5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%,以及这些数值中的任意两个所构成的范围中的任意值。磷含量在优选的范围内时,制备得到的芳构化催化剂性能更优。
根据本发明的方法,优选地,所述微孔材料可以为分子筛,优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50。在优选的情况下,本发明通过限定硅铝比不大于50,从而使得本发明制备的催化剂具有较高的乙烯转化率和芳烃选择性,较少的焦炭产生量。
根据本发明的方法,优选地,所述水热处理的条件包括:温度为250℃~650℃,时间为0.5h~24h。
根据本发明的方法,可以选择性地负载金属活性组分,在优选的情况下,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种。负载的方法可以为本领域常规方法,例如浸渍法。引入上述金属活性组分的方式可以通过加入含有述金属活性组分的化合物而得到,所述含有述金属活性组分的化合物优选地选自主活性金属元素的氯化物、硝酸盐、硫酸盐、醋酸盐和草酸盐中的一种或多种。例如,引入Pt的方式可以为加入Pt(NO3)2溶液。
根据本发明的方法,优选地,所述焙烧的条件包括:温度为300℃~700℃,优选为450℃~600℃;时间为0.5h~24h,优选为2h~8h。
本发明第四方面提供了一种低碳烯烃芳构化方法,包括:在芳构化条件下,将低碳烯烃、氢气和催化剂接触,其中,所述催化剂为上述的芳构化催化剂。
根据本发明的方法,低碳烯烃可以含有氢气和其他烃(如未转化的乙烷)等,因此,本发明的低碳烯烃原料可以直接来自乙烷裂解装置而无需进行净化和分离操作。
根据本发明的方法,优选地,本发明所述低碳烯烃可以为C2~C6的烯烃,例如,所述低碳烯烃可以为乙烯、丙烯、1-丁烯、2-丁烯、正戊烯、2-戊烯、1-己烯、2-己烯、3-己烯和2-甲基-1-戊烯中的一种或多种。进一步优选地,所述低碳烯烃中的总碳氢化合物的含量不低于60%,其中,乙烯不少于30%。更进一步优选为乙烯。
根据本发明的方法,优选地,所述低碳烯烃芳构化反应的条件可以包括:以表压计,压力为0.01MPa~2MPa;温度为300℃~700℃,优选为500℃~650℃;氢气与烯烃的体积比为0.1~5,优选为0.5~2;空速为500h-1~50000h-1,优选为1000h-1~10000h-1。
根据本发明的方法,优选地,在低碳烯烃、氢气和催化剂接触之前,该方法还包括进行预热。预热的操作可以为:在大气压下,向反应器中通入66.7sccm的H2并以15℃/min的升温速率将反应器加热至630℃,然后在该温度下保持30分钟。
根据本发明的方法,优选地,在通入低碳烯烃和氢气时,还通入N2,其中,N2用作色谱分析的内标物。
根据本发明的方法,优选地,采用固定床反应器进行低碳烯烃芳构化反应。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中,硅铝比为30的分子筛ZSM-5购自Sigma-Aldrich公司;
氧化铝购自Sasol公司,牌号为Catapal B;
气相色谱购自Agilent公司,型号为7890;
乙烯的转化率按照式1计算:
乙烯转化率%=(乙烯总摩尔数-乙烯剩余摩尔数)/乙烯总摩尔数×100% (式1)
BTX的选择性按照式2计算:
BTX选择性%=产物中BTX总碳摩尔数/转化的乙烯碳摩尔数×100% (式2)
BTX的收率按照式3计算:
BTX收率%=乙烯转化率×BTX选择性 (式3)
CH4选择性按照式4计算:
CH4选择性%=产物中甲烷总碳摩尔数/转化的乙烯碳摩尔数×100% (式4)
C2H6选择性按照式5计算:
C2H6选择性%=产物中乙烷总碳摩尔数/转化的乙烯碳摩尔数×100% (式5)
实施例1
将7g的ZSM-5(硅铝比为30)、1.77g的氧化铝和2g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,制备的芳构化催化剂标记为催化剂A。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计。
实施例2
将7g的ZSM-5(硅铝比为30)、1.25g的氧化铝和2.84g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到20目的颗粒,制备的芳构化催化剂标记为催化剂B。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为1;微孔材料和粘合剂的重量比为1:0.05,其中,粘合剂以粘合剂中的铝元素计。
实施例3
将7g的ZSM-5(硅铝比为30)、2g的氧化铝和18.5g的磷酸铵水溶液(磷酸铵的含量为10重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到40目的颗粒,制备的芳构化催化剂标记为催化剂C。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为3.2;微孔材料和粘合剂的重量比为1:0.08,其中,粘合剂以粘合剂中的铝元素计。
实施例4
将7g的ZSM-5(硅铝比为30)、1.77g的氧化铝和2g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后在600℃下,150mL/min的含20重量%水蒸气的空气中水热处理4小时,制备的芳构化催化剂标记为催化剂D。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计。
实施例5
将7g的ZSM-5(硅铝比为30)与1.77g的氧化铝进行混合和挤出,得到挤出物,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后用2g的磷酸水溶液(磷酸浓度为85重量%)浸渍,于550℃焙烧2小时,制备的芳构化催化剂标记为催化剂E。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计。
实施例6
将7g的ZSM-5(硅铝比为30)与1.77g的氧化铝进行混合和挤出,得到挤出物,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后用2g的磷酸水溶液(磷酸浓度为85重量%)浸渍,于550℃焙烧2小时,然后在600℃下,150mL/min的含20重量%水蒸气的空气中水热处理4小时,制备的芳构化催化剂标记为催化剂F。
其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计。
实施例7
将7g的ZSM-5(硅铝比为30)、1.77g的氧化铝和2g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒;
然后将0.25重量%的Pt(NO3)2水溶液浸渍5g颗粒,25℃下浸渍时间为2小时,得到混合物,然后将所得混合物在旋转蒸发器中加热至80℃,旋转蒸发60分钟,获得干燥产物,接着将产物在550℃焙烧2小时,得到Pt含量为500ppm的芳构化催化剂,制备的芳构化催化剂标记为催化剂G。
其中,该芳构化催化剂包括微孔材料、粘合剂和金属活性组分,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计;以芳构化催化剂的总量为基准,金属活性组分的含量为0.05重量%。
实施例8
将7g的ZSM-5(硅铝比为30)、1.77g的氧化铝和2g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后在600℃下,150mL/min的含20重量%水蒸气的空气中水热处理4小时,得到产物,再将0.25重量%的Pt(NO3)2的水溶液浸渍5g产物,25℃下浸渍时间为2小时,然后将所得混合物在旋转蒸发器中加热至80℃,旋转蒸发60分钟,获得干燥产物,接着将产物在550℃焙烧2小时,得到Pt含量为500ppm的芳构化催化剂,制备的芳构化催化剂标记为催化剂H。
其中,该芳构化催化剂包括微孔材料、粘合剂和金属活性组分,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计;以芳构化催化剂的总量为基准,金属活性组分的含量为0.05重量%。
实施例9
将7g的ZSM-5(硅铝比为30)与1.77g的氧化铝进行混合和挤出,得到挤出物,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后用含2g的磷酸水溶液(磷酸浓度为85重量%)进行浸渍,于550℃焙烧2小时后,在600℃下,150mL/min的含20重量%水蒸气的空气中水热处理4小时,得到产物,再将0.25重量%的Pt(NO3)2的水溶液浸渍5g产物,25℃下浸渍时间为2小时,然后将所得混合物在旋转蒸发器中加热至80℃,旋转蒸发60分钟,获得干燥产物,接着将产物在550℃焙烧2小时,得到Pt含量为500ppm的芳构化催化剂,制备的芳构化催化剂标记为催化剂I。
其中,该芳构化催化剂包括微孔材料、粘合剂和金属活性组分,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计;以芳构化催化剂的总量为基准,金属活性组分的含量为0.05重量%。
对比例1
将7g的ZSM-5(硅铝比为30)、3g的氧化铝进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,制备的催化剂标记为催化剂D1。
对比例2
将7g的ZSM-5(硅铝比为30)、2.8g的氧化铝和0.32g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,制备的催化剂标记为催化剂D2。其中,该催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为20。
对比例3
将7g的ZSM-5(硅铝比为30)、2.0g的氧化铝和5g的磷酸水溶液(磷酸浓度为85重量%)进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,制备的催化剂标记为催化剂D3。其中,其中,该催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为0.9。
对比例4
将7g的ZSM-5(硅铝比为30)与3g的氧化铝进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,然后在600℃下水热处理4小时,制备的催化剂标记为催化剂D4。
对比例5
将7g的ZSM-5(硅铝比为30)和0.81g的磷酸水溶液(磷酸浓度为85重量%)进行混合和干燥,然后与2.5g氧化铝进行混合和挤出,于550℃焙烧2小时,将焙烧产物粉碎、筛分,得到30目的颗粒,制备的催化剂标记为催化剂D5。其中,该催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为7。
测试例:
酸性位表征
分别称取0.2g催化剂A-I和D1-D5装入石英样品管中,在氦气条件下程序升温至450℃,活化1h后,冷却至150℃,吸附氨气30min,然后切换为氦气吹扫,脱除过剩氨气至检测器基线稳定,然后以10℃/min升温速率程序升温至600℃,通过NH3-TPD仪器(Micromeritics的AutoChem 2920)内置的热导检测器(TCD)检测样品的氨气脱附量。表征结果见表1。
表1
实施例10
采用实施例1制备的催化剂A进行低碳烯烃芳构化反应,具体操作为:
(1)采用固定床反应器,将1克催化剂A装入石英反应器(内径为9毫米)中;
(2)在大气压下,向反应器中通入66.7sccm的H2并以15℃/min的升温速率将反应器加热至630℃,然后在该温度下保持30分钟,进行预热;
(3)以表压计,压力为0.02MPa,空速为0.75h-1,将步骤(2)的66.7sccm的H2替换为10sccm乙烯、10sccm的H2和10sccm的N2(N2用作色谱分析的内标物),反应10分钟后,每隔35分钟通过在线气相色谱分析产物,取12小时的平均值,然后通过上述测试方法(式1-式5)计算得到乙烯转化率、BTX的选择性、BTX收率、甲烷选择性和乙烷选择性,结果见表2。
以上反应器在运行结束后,所得待生催化剂上的焦炭含量通过以下方法测定:秤取10毫克待生催化剂置于氧化铝样品盘中,置于岛津DTG-60H热重分析仪中,在空气气氛下以5℃/min的升温速度升至800℃。取400℃~650℃之间的失重来定量焦炭含量,结果如表2所示。
实施例11
将实施例10的反应12小时的催化剂A进行再生处理,具体操作为:空气气氛下以2℃/min的升温速度加热至550℃,保持4个小时。得到的芳构化催化剂标记为催化剂RA。其中,该芳构化催化剂包括微孔材料和粘合剂,粘合剂中铝元素与磷元素的摩尔比为2;微孔材料和粘合剂的重量比为1:0.07,其中,粘合剂以粘合剂中的铝元素计。
并按照上述测试例的酸性位表征方法测试RA,结果见表1。
实施例12至20
按照实施例10的方法,不同的是,将催化剂A替换为催化剂B-I和RA,结果见表2。
对比例11至15
按照实施例10的方法,不同的是,将催化剂A替换为催化剂D1-D5,结果见表2。
表2
实施例21
本发明催化剂A在不同温度下进行低碳烯烃芳构化反应:
(1)采用固定床反应器,将1克催化剂A样品装入石英反应器(内径为9毫米)中;
(2)在大气压下,向反应器中通入66.7sccm的H2并以15℃/min的升温速率将反应器分别加热至630℃,保持30分钟后,将温度降至400℃保持30分钟;
(3)以表压计,压力为0.02MPa,空速为0.75h-1,将步骤(2)的66.7sccm的H2替换为10sccm乙烯、10sccm的H2和10sccm的N2(N2用作色谱分析的内标物),在400℃下反应60分钟后,然后依次升温至450℃、500℃、550℃、600℃、630℃,并分别在450℃、500℃、550℃、600℃、630℃下反应一个小时,每次升温前将气体切换至66.7sccm的H2吹扫30分钟,升至所需温度后,再将氢气切换至反应气体(10sccm乙烯、10sccm的H2和10sccm的N2,其中,N2用作色谱分析的内标物)。
分别在400℃、450℃、500℃、550℃、600℃、630℃下,每隔30分钟通过在线气相色谱分析产物,取60分钟的平均值,然后通过上述测试方法(式1-式5)计算得到乙烯转化率、BTX的选择性、BTX收率、甲烷选择性和乙烷选择性。结果见表3。
表3
通过表1的结果可以看出,采用本发明的方法可以有效调节催化剂的强/弱酸性位点的酸度,制备的芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值可以小于1,优选比值不大于0.75。
通过表2的结果可以看出,采用本发明的芳构化催化剂可以将低碳烯烃进行芳构化反应生成芳烃,且反应温度低,相比于对比例(对比例1不加入含磷溶液、对比例2和3的粘合剂中铝磷摩尔比不在本发明范围内、对比例4为成型后仅水热处理、对比例5为先将ZSM-5与磷酸水溶液反应,再加入氧化铝),在400℃下依然具有较高的乙烯转化率、BTX选择性和BTX收率,以及较低的甲烷和焦炭的生成量。
此外,将本发明的催化剂A与对比例的催化剂D1进行乙烯转化率和BTX选择性比较,结果如表2、图1和图2所示,从表2中可以看出,催化剂A显示出更好的稳定性,12小时仅形成1.86重量%的焦炭,而催化剂D1的焦炭超过20重量%。而且催化剂A也保持更好的BTX选择性。
此外,将催化剂A(催化剂为新剂),催化剂RA(催化剂A再生后)和催化剂D(催化剂A水热处理后)的乙烯转化率和BTX选择性进行比较,结果如图3和图4所示,可以看出,本发明的催化剂再生后的活性和选择性可恢复,说明本发明的芳构化催化剂具有优异的水热稳定性,可以多次循环再生使用。
通过表3的结果可以看出,在温度低至400℃时也可以实现超过95%的乙烯转化率。较低温度下的BTX选择性相对较低,大部分产品是C3~C6,甲烷生成量低。
综上所述,本发明的芳构化催化剂在将低碳烯烃进行芳构化反应生成芳烃中,表现出优异的稳定性且芳烃产物的选择性好,同时可以有效减少甲烷和焦炭的生成。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
1.一种芳构化催化剂,其特征在于,该芳构化催化剂包括微孔材料和粘合剂,以及可选的金属活性组分;所述粘合剂为含有铝元素和磷元素的化合物,铝元素与磷元素的摩尔比大于等于1且小于5;所述芳构化催化剂的强酸性位点的酸度与弱酸性位点的酸度的比值小于1。
2.根据权利要求1所述的芳构化催化剂,其中,所述强酸性位点的酸度与弱酸性位点的酸度的比值不大于0.85,优选不大于0.75。
3.根据权利要求1或2所述的芳构化催化剂,其中,所述微孔材料为分子筛,优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50。
4.根据权利要求1或2所述的芳构化催化剂,其中,所述粘合剂为磷酸铝和可选的氧化铝;
优选地,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种;
优选地,所述微孔材料和粘合剂的重量比为1:0.05~1,其中,粘合剂以粘合剂中的铝元素计;
优选地,以所述芳构化催化剂的总量为基准,金属活性组分的含量为0重量%~1重量%。
5.权利要求1-4中任意一项所述芳构化催化剂的制备方法,该方法包括以下步骤:
(a)将微孔材料、氧化铝和含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(b1)可选地,将所述催化剂进行水热处理;和/或,
(b2)可选地,将金属活性组分负载在所述催化剂表面。
6.根据权利要求5所述的方法,其中,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05~1;
优选地,所述含磷溶液中的溶质选自磷酸、磷酸铵、膦及其衍生物中的一种或多种;
优选地,所述含磷溶液中的磷元素的含量为0.5重量%~30重量%,更优选为5重量%~15重量%;
优选地,所述微孔材料为分子筛,更优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50;
优选地,所述水热处理的条件包括:温度为250℃~650℃,时间为0.5h~24h。
7.根据权利要求5或6所述的方法,其中,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种。
8.权利要求1-4中任意一项所述催化剂的制备方法,该方法包括以下步骤:
(A)将微孔材料和氧化铝进行混合和挤出,以及可选地进行水热处理,得到挤出物;
(B)将所述挤出物与含磷溶液进行混合、挤出和焙烧,得到催化剂,其中,氧化铝中的铝元素与含磷溶液中的磷元素的摩尔比大于1且小于5;
(C)可选地,将金属活性组分负载在所述催化剂表面。
9.根据权利要求8所述的方法,其中,所述微孔材料和以铝元素计的氧化铝的重量比为1:0.05~1;
优选地,所述含磷溶液中的溶质选自磷酸、磷酸铵、膦及其衍生物中的一种或多种;
优选地,所述含磷溶液中的磷元素的含量为0.5重量%~30重量%,更优选为5重量%~15重量%;
优选地,所述微孔材料为分子筛,更优选为ZSM-5,进一步优选地,ZSM-5的硅铝比不大于50;
优选地,所述金属活性组分为Pt、Ni、Co、Cu、Zn、Fe、Pd、Rh、Ru、Re、Mo、W、Au和Ga中的一种或多种。
10.一种低碳烯烃芳构化方法,包括:在芳构化条件下,将低碳烯烃、氢气和催化剂接触,其中,所述催化剂为权利要求1-4中任意一项所述的芳构化催化剂;
优选地,所述低碳烯烃为C2~C6的烯烃,优选为乙烯;
优选地,所述芳构化条件包括:以表压计,压力为0.01MPa~2MPa;温度为300℃~700℃,优选为500℃~650℃;氢气与烯烃的体积比为0.1~5,优选为0.5~2;空速为500h-1~50000h-1,优选为1000h-1~10000h-1。
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