CN113509950A - 一种以非金属元素修饰的氧化铝为载体的镓基催化剂的制备方法 - Google Patents
一种以非金属元素修饰的氧化铝为载体的镓基催化剂的制备方法 Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000001294 propane Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 45
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 28
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 229940044658 gallium nitrate Drugs 0.000 claims description 14
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
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- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
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- 235000002949 phytic acid Nutrition 0.000 claims description 2
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- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 6
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- 230000000694 effects Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
本发明公开了一种以非金属元素修饰的氧化铝为载体的镓基催化剂的制备方法,其属于催化剂制备技术领域。其具体是采用非金属元素N、B、P修饰氧化铝后,以其为载体制备镓基催化剂。本发明在载体上掺杂非金属元素,可抑制催化过程中积炭的形成,从而提高催化剂的稳定性,解决了镓基催化剂快速失活的问题;同时,本发明可兼顾以氧化铝作载体的催化剂成本低廉的优点,且所得镓基催化剂可在丙烷脱氢催化反应中展现出高催化稳定性、高催化活性,为今后开发出高性能低碳烷烃脱氢催化剂提供了新的参考。
Description
技术领域
本发明属于催化剂制备技术领域,其涉及一种低碳烷烃脱氢催化剂及其制备方法,具体涉及一种以非金属元素N、B、P修饰的氧化铝为载体的镓基催化剂及其制备方法与应用。
背景技术
氧化铝是一种具有大比表面积、多孔性、高分散性等优点的催化剂载体,因其价格低廉且容易获取而大量应用于工业催化反应中。在丙烷直接脱氢反应中,氧化铝由于其本身强酸性的特点,常常会导致丙烯产物的深度脱氢,这一方面会降低丙烯选择性,另一方面深度脱氢导致的积炭会堵塞孔道并覆盖催化剂上的活性中心进而导致其快速失活。因此往往通过添加金属以及非金属助剂来改善这种状况,例如Pt系催化剂常添加Sn助剂,这种Sn金属所带来的几何效应以及电子效应能够极大的提高该催化剂的抗积炭能力。
在众多氧化物中,Ga2O3无论是采用负载或者物理混合的方法,还是仅仅作为一个氧化物固体,均在乙烷和丙烷脱氢中表现出较高的催化活性。研究者将镓负载在ZSM-5、SBA-15和SiO2表面,研究了不同载体以及不同负载量对镓基催化剂在丙烷脱氢催化反应中的影响,表明金属镓负载时催化剂初始活性较高,但是稳定性却非常差。
为解决镓基催化剂快速失活的问题,同时兼顾以氧化铝作载体成本低廉的优点,本发明采用分布广泛、价格低廉的非金属元素通过浸渍法修饰了氧化铝载体,合成了一种以非金属元素修饰的氧化铝为载体的镓基催化剂,其在丙烷脱氢催化反应中展现出高催化稳定性,且具高催化活性。
发明内容
本发明的目的在于提供是一种以非金属元素N、B、P修饰的氧化铝为载体的镓基催化剂的制备方法,将所得催化剂用于低碳烷烃脱氢反应具有较高的烯烃选择性和催化稳定性。
为实现上述目的,本发明采用如下技术方案:
一种以非金属元素修饰的氧化铝为载体的镓基催化剂的制备方法,其包括以下步骤:
(1)将含非金属元素的前驱体与有机溶剂充分混合,得混合溶液A;
(2)将氧化铝与步骤(1)所得混合溶液A充分混合,在常温条件下搅拌一定时间,然后将混合物加热升高至一定温度并进行搅拌,至混合物呈现粘稠状,然后转移至烘箱中干燥;
(3)将步骤(2)干燥后的产物在惰性气体条件下高温焙烧一定时间;
(4)将步骤(3)焙烧后的产物再在空气氛围条件下高温焙烧一定时间,以除去碳前驱体;
(5)将含金属元素镓的前驱体与有机溶剂充分混合,得混合溶液B;
(6)将步骤(4)焙烧后的产物与步骤(5)所得混合溶液B充分混合,在常温下搅拌一定时间,然后将固液混合物在常温下进行超声浸渍,再升温至一定温度并搅拌至干;
(7)将步骤(6)所获得的固液混合物转移至烘箱中,经干燥后获得所述镓基催化剂。
进一步地,步骤(1)和步骤(5)中所述的有机溶剂均为甲醇、乙醇、乙二醇、甘油、甲醛、乙酸中的一种或多种。
进一步地,步骤(1)中所述非金属元素为N、B、P中的一种或多种;
其中,当所用非金属元素为N时,采用的前驱体为氢氧化铵、硝酸铵、氯化铵、三聚氰胺、盐酸多巴胺、尿素中的一种或多种;
当所用非金属元素为B时,采用的前驱体为单质硼、硼酸、无水硼酸、偏硼酸钠、偏硼酸钾、十水硼砂中的一种或多种;
当所用非金属元素为P时,采用的前驱体为植酸、磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三乙酯、磷酸氢二钾、磷酸二氢钾中的一种或多种。
进一步地,步骤(1)中所得混合溶液A中非金属元素的含量为1~8mg/mL。
进一步地,步骤(2)中混合溶液A与氧化铝的用量比为0.1-10mL:0.1-1g;两者混合后在常温条件下搅拌的时间为20~60min;之后加热升高至100~120℃;干燥的温度为100~120℃,时间为10~12h。
进一步地,步骤(3)中所述惰性气体为氩气或氮气;所述高温焙烧的温度为600-1000℃,时间为1~5h。
进一步地,步骤(4)中所述高温焙烧的温度为500~800℃,时间为1~5h。
进一步地,步骤(5)中所述含金属元素镓的前驱体为硝酸镓、硫酸镓、碳酸镓、醋酸镓中的一种或多种;所得混合溶液B中金属元素镓的含量为1~8mg/mL。
进一步地,步骤(6)中焙烧后的产物与混合溶液B的用量比为0.1-1g:0.1-10mL;两者混合后在常温下搅拌的时间为0.1~4h;超声浸渍的时间为1~4h;之后升温至100~120℃
进一步地,步骤(7)所述干燥的温度为80~100℃,时间为10~12h。
本发明所得镓基催化剂具有催化活性高、催化稳定性高的特点,可用于丙烷脱氢催化反应。
本发明显著优点在于:
本发明采用非金属元素N、B、P修饰的氧化铝为载体制备的镓基催化剂,可以解决镓基催化剂快速失活的问题,这是由于掺杂的非金属元素可抑制催化过程中积炭的形成,从而提高催化剂的稳定性。同时,本发明可兼顾以氧化铝作载体的催化剂成本低廉的优点。将所得催化剂应用在丙烷脱氢催化反应中,可展现出高催化稳定性及高催化活性。
附图说明
图1为实施例所制备催化剂A、B、C、E的NH3-TPD图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1:
以三聚氰胺为溶质、甲醛为溶剂配制氮浓度为5mg/mL的三聚氰胺甲醛溶液;然后将1.2mL的三聚氰胺甲醛溶液加入到0.6g氧化铝中,再加入8.8mL甲醛溶液使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至110℃,搅拌至干,再于110℃烘箱中干燥10h。将干燥后的产物在氮气氛围下800℃焙烧1h,然后在空气条件下550℃焙烧1h,得到氮掺杂的氧化铝载体。以硝酸镓为溶质,乙醇为溶剂配制镓浓度为5mg/mL的硝酸镓乙醇溶液;取3mL硝酸镓乙醇溶液加入到0.3g氮掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到氮掺杂的氧化铝负载镓基催化剂。所得催化剂中N的负载量为1wt%,Ga的负载量为5wt%,记为A。
实施例2:
以硼酸为溶质、无水乙醇为溶剂配制硼浓度为5mg/mL的硼酸无水乙醇溶液;然后将6mL的硼酸无水乙醇溶液加入到0.6g氧化铝中,再加入4mL乙醇使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至100℃,搅拌至干,再于100℃烘箱中干燥10h。将干燥后的产物在氮气氛围下800℃焙烧1h,然后在空气条件下650℃焙烧4h,得到硼掺杂的氧化铝载体。以硝酸镓为溶质,乙醇为溶剂配制镓浓度为5mg/mL的硝酸镓乙醇溶液;取3mL硝酸镓乙醇溶液加入到0.3g硼掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到硼掺杂的氧化铝负载镓基催化剂。所得催化剂中B的负载量为5wt%,Ga的负载量为5wt%,记为B。
实施例3:
以磷酸氢二胺为溶质、水为溶剂配制磷浓度为5mg/mL的磷酸氢二胺溶液;然后将6mL的磷酸氢二铵溶液加入到0.6g氧化铝中,再加入4mL乙醇使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至110℃,搅拌至干,再于110℃烘箱中干燥10h。将干燥后的产物在氮气氛围下600℃焙烧2h,然后在空气条件下650℃焙烧4h,得到磷掺杂的氧化铝载体。以硝酸镓为溶质,乙醇为溶剂配制镓浓度为5mg/mL的硝酸镓乙醇溶液;取3mL硝酸镓乙醇溶液加入到0.3g磷掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到磷掺杂的氧化铝负载镓基催化剂。所得催化剂中P的负载量为5wt%,Ga的负载量为5wt%,记为C。
对比例1:
将0.6g氧化铝在110℃烘箱中干燥10h,然后将干燥后的产物在氮气氛围下800℃焙烧1h,再在空气条件下550℃焙烧1h,得到未掺杂非金属元素、未负载镓的氧化铝,记为D。
对比例2:
将0.6g氧化铝在110℃烘箱中干燥10h,然后将干燥后的产物在氮气氛围下800℃焙烧1h,再在空气条件下550℃焙烧1h,得到氧化铝载体。以硝酸镓为溶质,乙醇为溶剂配制镓浓度为5mg/mL的硝酸镓乙醇溶液;取3mL硝酸镓乙醇溶液加入到0.3g氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到氧化铝负载的镓基催化剂。所得催化剂中Ga的负载量为5wt%,未掺杂非金属元素,记为E。
对比例3:
以三聚氰胺为溶质、甲醛为溶剂配制氮浓度为5mg/mL的三聚氰胺甲醛溶液;然后将1.2mL的三聚氰胺甲醛溶液加入到0.6g氧化铝中,再加入8.8mL甲醛溶液使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至110℃,搅拌至干,再于110℃烘箱中干燥10h。将干燥后的产物在氮气氛围下800℃焙烧1h,然后在空气条件下550℃焙烧1h,得到氮掺杂的氧化铝载体。取3mL无水乙醇加入到0.3g氮掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到氮掺杂的氧化铝。所得催化剂中N的负载量为1wt%,Ga的负载量为0wt%,记为F。
对比例4:
以硼酸为溶质、无水乙醇为溶剂配制硼浓度为5mg/mL的硼酸无水乙醇溶液;然后将6mL的硼酸无水乙醇溶液加入到0.6g氧化铝中,再加入4mL乙醇使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至100℃,搅拌至干,再于100℃烘箱中干燥10h。将干燥后的产物在氮气氛围下800℃焙烧1h,然后在空气条件下650℃焙烧4h,得到硼掺杂的氧化铝载体。取3mL无水乙醇加入到0.3g硼掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到硼掺杂的氧化铝。所得催化剂中B的负载量为5wt%,Ga的负载量为0wt%,记为G。
对比例5:
以磷酸氢二胺为溶质、水为溶剂配制磷浓度为5mg/mL的磷酸氢二胺溶液;然后将6mL的磷酸氢二铵溶液加入到0.6g氧化铝中,再加入4mL乙醇使其达到过量浸渍,保证总体积为10mL。在常温下搅拌30min,然后将温度加热至110℃,搅拌至干,再于110℃烘箱中干燥10h。将干燥后的产物在氮气氛围下600℃焙烧2h,然后在空气条件下650℃焙烧4h,得到磷掺杂的氧化铝载体。取3mL无水乙醇加入到0.3g磷掺杂的氧化铝载体中,在常温下搅拌30min,然后将搅拌后的固液混合物常温超声浸渍3h,再室温搅拌3h,之后将温度升至100℃搅拌至干,再于80℃烘箱中干燥10h,得到磷掺杂的氧化铝。所得催化剂中P的负载量为5wt%,Ga的负载量为0wt%,记为H。
催化剂评价:
取200mg催化剂,装填于固定床反应器中,氮气氛围下程序升温至580℃,然后通20mL/min的氢气对催化剂还原1h。还原后关闭氢气,通入20mL/min氮气,再次程序升温至600℃,然后控制氮气流量为57mL/min、丙烷流量为3 mL/min进行反应。反应尾气经过滤后通入色谱检测丙烯产量。催化剂A、B、C、D、E、F、G、H的催化性能列于表1。催化剂C经不同反应时间的催化性能列于表2。图1为催化剂A、B、C、E的NH3-TPD图。
表1 不同催化剂的催化性能
表2 催化剂C在不同反应时间下的催化性能表
比较实施例所得催化剂A、B、C和对比例所得催化剂D、E、F、G、H的丙烷直接脱氢制丙烯的催化性能可以发现,采用非金属元素氮、磷、硼修饰的氧化铝为载体的镓基催化剂比未修饰非金属元素未负载镓的氧化铝、未修饰非金属元素的氧化铝负载的镓基催化剂、非金属元素修饰未负载镓的氧化铝载体催化活性要好,而且稳定性得到大幅度提高。
从图1的NH3-TPD图可以看出,掺杂非金属元素之后,催化剂中高于420℃左右的强酸峰面积有所减少,证明非金属元素的掺杂可抑制催化过程中积炭的形成,从而提高催化剂的稳定性。比较而言,催化剂C催化活性和稳定性最好,催化剂B次之,催化剂A的酸性仅有微弱的减小,因此催化剂提升效果不如催化剂B和催化剂C。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种以非金属元素修饰的氧化铝为载体的镓基催化剂的制备方法,其特征在于:包括以下步骤:
(1)将含非金属元素的前驱体与有机溶剂充分混合,得混合溶液A;
(2)将一定量氧化铝与步骤(1)所得混合溶液A充分混合,在常温条件下搅拌一定时间,然后将混合物加热升高至一定温度并进行搅拌,至混合物呈现粘稠状,然后转移至烘箱中干燥;
(3)将步骤(2)干燥后的产物在惰性气体条件下高温焙烧一定时间;
(4)将步骤(3)焙烧后的产物再在空气氛围条件下高温焙烧一定时间;
(5)将含金属元素镓的前驱体与有机溶剂充分混合,得混合溶液B;
(6)将步骤(4)焙烧后的产物与步骤(5)所得混合溶液B充分混合,在常温下搅拌一定时间,然后将固液混合物在常温下进行超声浸渍,再升温至一定温度并搅拌至干;
(7)将步骤(6)所获得的固液混合物经干燥后获得所述镓基催化剂。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)和步骤(5)中所述的有机溶剂均为甲醇、乙醇、乙二醇、甘油、甲醛、乙酸中的一种或多种。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述非金属元素为N、B、P中的一种或多种;
其中,当所用非金属元素为N时,采用的前驱体为氢氧化铵、硝酸铵、氯化铵、三聚氰胺、盐酸多巴胺、尿素中的一种或多种;
当所用非金属元素为B时,采用的前驱体为单质硼、硼酸、无水硼酸、偏硼酸钠、偏硼酸钾、十水硼砂中的一种或多种;
当所用非金属元素为P时,采用的前驱体为植酸、磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三乙酯、磷酸氢二钾、磷酸二氢钾中的一种或多种。
4.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所得混合溶液A中非金属元素的含量为1~8mg/mL。
5.根据权利要求1所述的制备方法,其特征在于:步骤(2)中混合溶液A与氧化铝的用量比为0.1-10mL:0.1-1g;两者混合后在常温条件下搅拌的时间为20~60min;之后加热升高至100~120℃继续进行搅拌。
6.根据权利要求1中所述的制备方法,其特征在于:步骤(3)中所述惰性气体为氩气或氮气;所述高温焙烧的温度为600-1000℃,时间为1~5h。
7.根据权利要求1中所述的制备方法,其特征在于:步骤(4)中所述高温焙烧的温度为500~800℃,时间为1~5h。
8.根据权利要求1中所述的制备方法,其特征在于:步骤(5)中所述含金属元素镓的前驱体为硝酸镓、硫酸镓、碳酸镓、醋酸镓中的一种或多种;所得混合溶液B中金属元素镓的含量为1~8mg/mL。
9.根据权利要求1中所述的制备方法,其特征在于:步骤(6)中焙烧后的产物与混合溶液B的用量比为0.1-1g:0.1-10mL;两者混合后在常温下搅拌的时间为0.1~4h;超声浸渍的时间为1~4h;之后升温至100~120℃继续进行搅拌。
10.一种如权利要求1所述方法制备的镓基催化剂在丙烷脱氢催化反应中的应用。
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