CN108786879B - 一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法 - Google Patents
一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法 Download PDFInfo
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001273 butane Substances 0.000 abstract description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000004949 mass spectrometry Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
本发明公开一种PdAgNi/N‑C催化剂催化1,3‑丁二烯选择性加氢的方法,其特征在于:先将PdAgNi/N‑C催化剂置于管式反应器中,然后将催化剂床层温度升高至30~60℃,再将1,3‑丁二烯与氢气的混合气体导入反应器中,在压力为1.5~3.2MPa,空速为1.0~4.0h‑1的条件下进行反应。本发明以PdAgNi/N‑C为催化剂,使用该催化剂进行1,3‑丁二烯选择性加氢反应,其中产物中1,3‑丁二烯含量低于900ppb,丁烷含量低于2.3%,催化剂连续运行100h后仍保持良好的催化活性。
Description
技术领域
本发明涉及化学化工技术领域,特别是涉及一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法。
背景技术
在石油化工中,石脑油蒸汽裂解产生了丰富的低链C4烯烃,但是在这些C4烯烃中往往含有少量的二烯烃或者炔烃;在下游烯烃聚合过程中,二烯烃或者炔烃往往较单烯烃更容易吸附在聚合催化剂表面而使催化剂中毒失效,因而人们常常利用二烯烃的选择性加氢生成单烯烃来解决这个问题。
开发高效选择性加氢催化剂是当前研究的热点,美国环球油品公司(UOP)的SHP工艺(Oil Gas J,1988,86(49)40-43)采用贵金属催化剂,丁二烯转化率高达99.8%,但正丁烷生成量却达到35.7%。美国专利US4762956公开了一种用于丁二烯选择加氢的钯基催化剂,以催化剂重量计,含有0.025-1.0%Pd及0.04-4%的Sn或Pb,有效提高了丁二烯加氢的选择性,抑制了烯烃的异构化。中国专利CN106582625A公开了一种丁二烯选择性加氢的催化剂,以催化剂重量份数计,包括以下组分:(a)0.05-0.5%份的金属Pd或其氧化物;(b)0.1-2份的IB族金属或其氧化物;(c)97.5-99.7份的载体氧化铝的技术方案,该方案有效解决了现有技术中存在的丁烯-1损耗高、催化剂成本较高及制备过程使用有毒有害原料的技术问题,但在产物丁二烯含量的控制上略显不足。
发明内容
本发明的目的是提供一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,以PdAgNi/N-C为催化剂,其具有的催化活性和稳定性,有效的降低了1,3-丁二烯的含量,解决上述现有技术存在的问题。
为实现上述目的,本发明提供了如下方案:
本发明提供一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:先将PdAgNi/N-C催化剂置于管式反应器中,然后将催化剂床层温度升高至30~60℃,再将1,3-丁二烯与氢气的混合气体导入反应器中,在压力为1.5~3.2MPa,空速为1.0~4.0h-1的条件下进行反应。
优选的,所述1,3-丁二烯与氢气的摩尔比为1:1.2~2.5。
优选的,所述PdAgNi/N-C催化剂由以下步骤制备:
(1)将一定摩尔量的Pd盐、Ag盐、Ni盐和去离子水加入烧杯中,在0℃冰浴中充分搅拌后,加入N-C材料,进行充分搅拌;
(2)在步骤(1)制得的混合溶液中,逐滴滴加0.1mol/L~0.4mol/L的硼氢化钠溶液,并搅拌还原2h;
(3)将步骤(2)的溶液过滤后干燥,即得到PdAgNi/N-C催化剂。
优选的,所述Pd盐为氯化钯,Ag盐为硝酸银,Ni盐为氯化镍。
优选的,所述Pd、Ag、Ni的摩尔比为1:0.2~0.4:0.1~0.3;Pd、N-C材料的摩尔比为1:500~800。
优选的,步骤(1)中,所述N-C材料由三聚氰胺与葡萄糖按一定质量比焙烧制得,所述三聚氰胺与葡萄糖的质量比为30~60:1,焙烧温度为700~900℃,焙烧时间为2~6h。
优选的,步骤(3)中,所述干燥温度为80~140℃,干燥时间为10~20h。
本发明公开了以下技术效果:
本发明以三聚氰胺和葡萄糖为前驱体合成的N-C材料为载体,催化剂的制备使用氯化钯、硝酸银和氯化镍为前驱体,采用浸渍还原法制备PdAgNi/N-C催化剂,该催化剂具有较高的活性和稳定性,使用该催化剂进行1,3-丁二烯选择性加氢反应,其中产物中1,3-丁二烯含量低于900ppb,丁烷含量低于2.3%,催化剂连续运行100h后仍保持良好的催化活性。
具体实施方式
下面将结合本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合具体实施方式对本发明作进一步详细的说明。
实施例1
(1)催化剂的制备
将0.02mmolPdCl2、0.004mmolAgNO3和0.002mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将10mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比30:1在700℃焙烧2h制得;充分搅拌后,滴加0.1mol/L硼氢化钠溶液还原2h,过滤后在80℃的干燥箱中干燥20h,制得催化剂PdAg0.2Ni0.1/N-C500,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至30℃,再将摩尔比为1:1.2的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为1.5MPa,反应空速为1.0h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于880ppb,丁烷含量低于2.1%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物中1,3-丁二烯含量低于895ppb,丁烷含量低于2.2%。
实施例2
(1)催化剂的制备
将0.02mmolPdCl2、0.008mmolAgNO3和0.006mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将16mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比60:1在900℃焙烧6h制得;充分搅拌后,滴加0.4mol/L硼氢化钠溶液还原2h,过滤后在140℃的干燥箱中干燥10h,制得催化剂PdAg0.4Ni0.3/N-C800,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至60℃,再将摩尔比为1:2.5的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为3.2MPa,反应空速为4.0h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于790ppb,丁烷含量低于1.8%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物1,3-中丁二烯含量低于815ppb,丁烷含量低于2.0%。
实施例3
(1)催化剂的制备
将0.02mmolPdCl2、0.006mmolAgNO3和0.004mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将14mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比50:1在800℃焙烧4h制得;充分搅拌后,滴加0.3mol/L硼氢化钠溶液还原2h,过滤后在120℃的干燥箱中干燥15h,制得催化剂PdAg0.3Ni0.2/N-C700,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至50℃,再将摩尔比为1:2.0的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为2.8MPa,反应空速为3h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于820ppb,丁烷含量低于2.0%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物中1,3-丁二烯含量低于840ppb,丁烷含量低于2.1%。
实施例4
(1)催化剂的制备
将0.02mmolPdCl2、0.006mmolAgNO3和0.002mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将12mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比40:1在850℃焙烧4h制得;充分搅拌后,滴加0.2mol/L硼氢化钠溶液还原2h,过滤后在100℃的干燥箱中干燥18h,制得催化剂PdAg0.3Ni0.1/N-C600,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至40℃,再将摩尔比为1:1.5的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为2.2MPa,反应空速为2.0h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于830ppb,丁烷含量低于1.9%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物中1,3-丁二烯含量低于850ppb,丁烷含量低于2.2%。
实施例5
(1)催化剂的制备
将0.02mmolPdCl2、0.004mmolAgNO3和0.004mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将11mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比45:1在750℃焙烧3h制得;充分搅拌后,滴加0.3mol/L硼氢化钠溶液还原2h,过滤后在90℃的干燥箱中干燥12h,制得催化剂PdAg0.2Ni0.2/N-C550,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至35℃,再将摩尔比为1:1.8的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为2.6MPa,反应空速为3.2h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于870ppb,丁烷含量低于1.9%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物中1,3-丁二烯含量低于885ppb,丁烷含量低于2.1%。
实施例6
(1)催化剂的制备
将0.02mmolPdCl2、0.008mmolAgNO3和0.004mmolNiCl2溶于10mL蒸馏水中,在0℃冰浴中搅拌均匀后,再将15mmol N-C材料加入到上述溶液中,其中,N-C材料为三聚氰胺与葡萄糖按质量比45:1在850℃焙烧5h制得;充分搅拌后,滴加0.2mol/L硼氢化钠溶液还原2h,过滤后在120℃的干燥箱中干燥16h,制得催化剂PdAg0.4Ni0.2/N-C750,密闭保存。
(2)加氢反应过程
先将1.5mL步骤(1)制得的催化剂装填至内径为8mm的管式反应器中,然后将催化剂床层温度升高至50℃,再将摩尔比为1:2.3的1,3-丁二烯与氢气的混合气体导入反应器中,反应压力为2.5MPa,反应空速为2.8h-1。
采用气相色谱及质谱分析步骤(2)中反应2h后的产物,产物中1,3-丁二烯含量低于830ppb,丁烷含量低于1.9%;催化剂连续运行100h后,气相色谱及质谱分析产物显示,产物中1,3-丁二烯含量低于850ppb,丁烷含量低于2.2%。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (5)
1.一种PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:先将PdAgNi/N-C催化剂置于管式反应器中,然后将催化剂床层温度升高至30~60℃,再将1,3-丁二烯与氢气的混合气体导入反应器中,在压力为1.5~3.2MPa,空速为1.0~4.0h-1的条件下进行反应;
所述PdAgNi/N-C催化剂由以下步骤制备:
(1)将一定摩尔量的Pd盐、Ag盐、Ni盐和去离子水加入烧杯中,在0℃冰浴中充分搅拌后,加入N-C材料,进行充分搅拌;
(2)在步骤(1)制得的混合溶液中,逐滴滴加0.1mol/L~0.4mol/L的硼氢化钠溶液,并搅拌还原2h;
(3)将步骤(2)的溶液过滤后干燥,即得到PdAgNi/N-C催化剂;
步骤(1)中,所述N-C材料由三聚氰胺与葡萄糖按一定质量比焙烧制得,所述三聚氰胺与葡萄糖的质量比为30~60:1,焙烧温度为700~900℃,焙烧时间为2~6h。
2.根据权利要求1所述的PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:所述1,3-丁二烯与氢气的摩尔比为1:1.2~2.5。
3.根据权利要求1所述的PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:所述Pd盐为氯化钯,Ag盐为硝酸银,Ni盐为氯化镍。
4.根据权利要求3所述的PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:所述Pd、Ag、Ni的摩尔比为1:0.2~0.4:0.1~0.3;Pd、N-C材料的摩尔比为1:500~800。
5.根据权利要求1所述的PdAgNi/N-C催化剂催化1,3-丁二烯选择性加氢的方法,其特征在于:步骤(3)中,所述干燥温度为80~140℃,干燥时间为10~20h。
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