CN114621047A - 一种低碳烷烃脱氢方法 - Google Patents
一种低碳烷烃脱氢方法 Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052593 corundum Inorganic materials 0.000 claims description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- -1 carbon alkane Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000011865 Pt-based catalyst Substances 0.000 description 4
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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Abstract
本发明涉及一种低碳烷烃脱氢方法。该方法中所用的催化剂为富含不饱和配位氧化铝负载的双单原子Pt‑M/Al2O3催化剂。M为Sn、Zn、Ga、Mg等非贵金属。本发明的方法低碳烯烃的选择性和收率较高，且催化剂稳定性优异。
Description
技术领域
本发明涉及一种低碳烷烃脱氢方法，该方法采用富含不饱和配位氧化铝负载的双单原子Pt-M/Al2O3催化剂，本发明的方法低碳烯烃的选择性和收率较高，且催化剂稳定性优异。
背景技术
随着全球石油化工行业的飞速发展，对低碳烯烃的需求也日益增长。目前，世界上各大石油公司下的千吨级炼厂催化裂解附产大量的低碳烷烃。如何合理利用这些低碳烷烃资源，最大限度提高工业过程的经济性，是当前工业领域和学术领域急需解决的重要课题。低碳烷烃脱氢技术也是增产低碳烯烃的有效途径。
铂族催化剂是低碳烷烃脱氢制低碳烯烃的重要一类催化剂，其中Pt为主活性组分，Sn、Zn等非贵金属为活性助剂。USP4914075，USP4353815，USP4420649等专利公开一系列Pt基催化剂，在低碳烷烃脱氢反应中表现出较高的转化率和烯烃选择性。然而，这些催化剂仍存在Pt活性组分利用率低、稳定性较差等问题。因此，针对上述Pt基催化剂缺陷，需要开发一种高效、高稳定性的Pt基催化剂。
发明内容
本发明旨在针对现有Pt基催化剂的不足，提供一种制备方法简单、活性金属组分利用率接近100％的高活性、高稳定性Pt基低碳烷烃脱氢催化剂。
基于上述目的，本发明采用的技术方案为：
一种低碳烷烃脱氢方法，主要步骤如下：
A)将Pt-M/Al2O3催化剂造粒填充于固定床反应器中，在20％H2-N2气中进行预还原；
B)通入低碳烷烃原料气进行反应；
催化剂Pt-M/Al2O3中Pt和M均为单原子分散尺度，Al2O3为富含不饱和位的氧化铝。
步骤A)中预还原温度为500-650℃，优选为550-610℃，预还原时间为0.5-2h；步骤B)中反应温度为500-650℃，优选为550-610℃；反应压力为常压。
催化剂Pt-M/Al2O3中M为Sn、Zn、Ga、Mg中的一种，Pt的质量百分数为0.1-1wt％，M的质量百分数为0.5-2wt％；催化剂中Al2O3上不饱和配位(五配位)含量为15-35％.
催化剂Pt-M/Al2O3的制备方法为：
a)将表面活性剂、非贵金属Sn、Zn、Ga、Mg的硝酸盐或氯化物与醇混合，配制成非贵金属醇溶液；
b)将酸、铝源与醇混合，配制成醇溶液；
c)将步骤a)和步骤b)醇溶液混合，然后继续搅拌2-10小时；
d)将步骤c)中得到的溶液蒸干醇溶剂，然后继续老化36-72h；
e)取步骤d)中固体物质焙烧；得到固体样品；
f)采用等体积浸渍法将Pt贵金属负载到步骤e)中得到的固体样品上；
g)将步骤f)得到的固体样品再进行焙烧；得到双单原子Pt-M/Al2O3催化剂。
a)和b)中原料按质量份数计包括以下组分：表面活性剂15-25份，酸30-40份，铝源40-50份。
其中所述的表面活性剂为非离子型表面活性剂P123、F127、F68中的一种；
酸为质量浓度为65％的浓硝酸、草酸、柠檬酸、羟基丁二酸中的一种；
铝源为硝酸铝、氯化铝、异丙醇铝、仲丁醇铝中的一种；
溶剂醇为甲醇、乙醇、丙醇中的一种或二种以上的组合；
铝在溶剂中的摩尔浓度为1mol/L。
步骤f)中所述的Pt组分前驱体为H2PtCl6·6H2O、Pt(NH3)4Cl2、Pt(NH3)4(NO3)2的一种。
步骤e)和g)焙烧时的升温速率为0.5-2℃/min，从室温升温至焙烧温度，焙烧温度为400℃-600℃，焙烧时间为4-8h。
本发明提供的低碳烷烃脱氢方法，低碳烷烃转化率高(接近平衡转化率)，烯烃选择性高，催化剂寿命长。
具体实施方式
为了进一步说明本发明，列举以下实施例，但它并不限制各附加权利要求所定义的发明范围。
实施例1
催化剂制备：
a.称取2.0g P123溶于20ml无水乙醇中，加入16mgSnCl2，搅拌溶解成醇溶液。
b.在20ml无水乙醇中滴加3ml浓硝酸，剧烈搅拌下加入4.08g异丙醇铝，剧烈搅拌使异丙醇铝完全溶解。
c.将a和b中得到的醇溶液混合，继续剧烈搅拌6h。
d.将c中得到的溶液于60℃烘箱中老化48h。
e.将d中固体于1℃/min速率下升温至400℃焙烧4h得到Sn/Al2O3,Al2O3中不饱和五配位Al含量约为23％.
f.将8.6mgPt(NH3)4Cl2溶于0.7ml水中，将其滴加到1gSn/Al2O3固体上，然后于120℃烘箱中干燥12h，再将其于1℃/min速率下升温至400℃焙烧4h，得Pt-Sn/Al2O3催化剂，其中Pt的负载量为0.5wt％，Zn的负载量为1wt％，通过电镜可以看出Pt和Sn均为单原子尺度分散在富含不包含配位Al2O3上.
实施例2
除了在步骤a中使用45.8mgZn(NO3)2·6H2O外，以与实施例1中所述相同方法制备，得到双金属催化剂Pt-Zn/Al2O3。
实施例3
除了在步骤a中使用48.3mgGa(NO3)3·4H2O外，以与实施例1中所述相同方法制备，得到双金属催化剂Pt-Ga/Al2O3。
实施例4
除了在步骤a中使用106.8mgMg(NO3)2·6H2O外，以与实施例1中所述相同方法制备，得到双金属催化剂Pt-Mg/Al2O3。
实施例5
将40-60目的实施例1制备的Pt-Sn/Al2O3催化剂置于6mm的反应管中，600℃下预还原1h。然后通入原料气体积比(C3H8：H2：N2＝1:1.25:4)，在600℃、常压、重时空速为10h-1的条件下反应，丙烷的转化率为49％，丙烯的选择性为100％，反应50h后丙烷转化率保持在41％.
对比例1
采用等体积浸渍法将0.5wt％的Pt和1wt％的Sn负载到商业Al2O3上，经过与实施例1中同样的焙烧、还原条件得到RhZn/Al2O3催化剂，活性金属平均粒径为4.6nm。将其应用于丙烷脱氢反应中，在于实施例5相同的反应条件下，丙烷转化率为30％，丙烯选择性为95％，经50h反应丙烷转化率降至10％以下。
实施例6
除了将催化剂改为实施例2制备的Pt-Zn/Al2O3外，以与实施例5中所述相同方法，丙烷转化率为45％，丙烯选择性为100％.
实施例7
除了将催化剂改为实施例3制备的Pt-Ga/Al2O3外，以与实施例5中所述相同方法，丙烷转化率为41％，丙烯选择性为100％.
实施例8
除了将催化剂改为实施例3制备的Pt-Mg/Al2O3外，以与实施例5中所述相同方法，丙烷转化率为39％，丙烯选择性为100％。
Claims (8)
1.一种低碳烷烃脱氢方法，主要步骤如下：
A)将Pt-M/Al2O3催化剂造粒填充于固定床反应器中，在体积浓度5-30％(优选15-20％)H2-N2气中进行预还原；
B)通入C2-C4的低碳烷烃原料气进行反应；
催化剂Pt-M/Al2O3中Pt和M均分别以单原子形式分散于Al2O3上，Al2O3为富含不饱和位的氧化铝。
2.按照权利要求1所述的制备方法，其特征在于：步骤A)中预还原温度为500-650℃，优选为550-610℃，预还原时间为0.5-2h。
3.按照权利要求1所述的制备方法，其特征在于：步骤B)中反应温度为500-650℃，优选为550-610℃；反应压力为常压，重时空速5-20h-1。
4.按照权利要求1所述的制备方法，其特征在于：催化剂Pt-M/Al2O3中M为Sn、Zn、Ga、Mg中的一种或二种以上，Pt的质量百分数为0.1-1wt％，M的质量百分数为0.5-2wt％；催化剂中Al2O3上不饱和配位(1个Al原子与5个O原子的不饱和配位，为五配位)质量含量为15-35％，其余为1个Al原子与4个O原子的饱和配位(为四配位)和1个Al原子与6个O原子的饱和配位(为六配位)。
5.按照权利要求1所述的制备方法，其特征在于：催化剂Pt-M/Al2O3的粒径和反应管管径比为1：20-1:40，固定床反应器反应管管径为6mm-20cm。
6.按照权利要求1所述的制备方法，其特征在于：催化剂Pt-M/Al2O3的制备方法为：
a)将表面活性剂、非贵金属Sn、Zn、Ga、Mg中的一种或二种以上的硝酸盐或氯化物中的一种或二种以上与醇混合，配制成非贵金属醇溶液；
b)将酸、铝源与醇混合，配制成醇溶液；
c)将步骤a)和步骤b)醇溶液混合，然后继续搅拌2-10小时；
d)将步骤c)中得到的溶液蒸干醇溶剂，然后继续老化36-72h；
e)取步骤d)中固体物质焙烧；得到固体样品；
f)采用等体积浸渍法将Pt贵金属负载到步骤e)中得到的固体样品上；
g)将步骤f)得到的固体样品再于空气中进行焙烧；得到双单原子Pt-M/Al2O3催化剂。
7.按照权利要求6所述的制备方法，其特征在于：c)中溶液混合后原料按质量份数计包括以下组分：表面活性剂15-25份，酸30-40份，铝源40-50份；
其中所述的表面活性剂为非离子型表面活性剂P123、F127、F68中的一种或二种以上；
酸为质量浓度为65％的浓硝酸、草酸、柠檬酸、羟基丁二酸中的一种或二种以上；
铝源为硝酸铝、氯化铝、异丙醇铝、仲丁醇铝中的一种或二种以上；
溶剂醇为甲醇、乙醇、丙醇中的一种或二种以上的组合；
c)中铝在溶剂中的摩尔浓度为0.5-3mol/L；
步骤f)中所述的Pt组分前驱体为H2PtCl6·6H2O、Pt(NH3)4Cl2、Pt(NH3)4(NO3)2的一种或二种以上；
步骤e)和g)焙烧时的升温速率为0.5-2℃/min，从室温升温至焙烧温度，焙烧温度为400℃-600℃，焙烧时间为4-8h。
8.按照权利要求1所述的制备方法，其特征在于：
原料气体积比组成为C2-C4的低碳烷烃：H2：N2＝1:1.25:4。
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