CN108246239B - 金属掺杂kp型分子筛吸附剂脱除羰基硫的方法 - Google Patents
金属掺杂kp型分子筛吸附剂脱除羰基硫的方法 Download PDFInfo
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003463 adsorbent Substances 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910020451 K2SiO3 Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
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- 229910052802 copper Inorganic materials 0.000 claims description 3
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- 150000003839 salts Chemical class 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000003915 liquefied petroleum gas Substances 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Abstract
本发明涉及的是金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法：在吸附温度为20oC‑60 oC，液化气体积空速为0.1 h‑1‑20 h‑1的条件下，金属掺杂KP型分子筛吸附剂脱除羰基硫，羰基硫的脱除率达85%‑99.5%；利用水热合成法制备出粒径均一、形貌规则的金属掺杂KP型分子筛，金属掺杂KP型分子筛为球形的，粒径为0.5μm‑4μm。本发明制备的金属掺杂KP型分子筛吸附剂，较常规的NaP型分子筛具有更强的K+碱性中心，有利于COS的水解，且COS在碱性中心水解后生成H2S被金属氧化物活性中心化学吸附，可进一步提高液化石油气中COS的脱除率。
Description
技术领域
本发明涉及液化石油气净化领域中脱除羰基硫技术，具体涉及金属掺杂KP型分子筛吸附剂脱除羰基硫的方法。
背景技术
液化石油气包括炼油厂液化气、少量裂解液化气和油田气回收液化气等，90 %的液化石油气由炼油厂生产，主要来自催化裂化、加氢裂化、延迟焦化等装置。LPG的主要成分是价值较高的C3、C4烯烃和烷烃，含有微量的硫杂质，主要包括H2S和羰基硫等，LPG可以直接用作燃气，也可以分离后作为化工原料，但硫含量的高低成为制约LPG是否成为高附加值产品的主要瓶颈之一。
随着进口高硫原油加工量的增加和渣油掺炼比的增大，炼油厂催化裂化等装置生产的LPG的总硫含量也随之升高。通常的LPG精制方法对H2S脱除效果较好，但对羰基硫(COS）的脱除效果不理想。目前国内外用于脱除COS的技术主要有两种，即加氢还原法和水解法。其中，加氢还原法反应温度高（一般为350℃-400℃），易引起反应物的裂解，从而使催化剂结碳而失活，同时需要氢气，成本较高。水解法是在水存在的条件下，使含COS与水解催化剂接触，将其转化为硫化氢和二氧化碳，然后再除去硫化氢和二氧化碳。
公告号103506071B的中国专利，该专利公开一种以活性炭为载体、以可溶性锌盐或铜盐为活性组分的同时去除H2S和COS的洁净剂，该洁净剂制备方法简单、成本低廉，但COS脱除效果不够理想。公开号105664659A的中国专利申请公开一种连续吸附脱除醚化后C4中羰基硫和二甲基二硫醚的方法，该法吸附容量较大，但操作繁琐，吸附剂再生过程复杂。公告号105107459的中国专利申请公开发明了一种以处理过的核桃壳制备得到的活性炭为吸附剂，同时脱除H2S、COS和CS2的方法，该法操作简单，成本低廉，但对COS的脱除效果较差。
综上所述，提供一种可以一步脱除液化石油气或其他气体中的羰基硫的方法是本领域亟待解决的问题。
发明内容
本发明的目的是提供金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法用于解决现有的脱除液化石油气中羰基硫工艺流程复杂或脱除效果不够理想的问题。
本发明解决其技术问题所采用的技术方案是：这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法：在吸附温度为20oC-60 oC，液化气体积空速为0.1 h-1-20 h-1的条件下，金属掺杂KP型分子筛吸附剂脱除羰基硫，羰基硫的脱除率达85%-99.5%；
金属掺杂KP型分子筛制备方法为：配置一定浓度的金属盐溶液，金属盐溶液中金属为M，金属M的质量分数为0.1wt%-15wt%，依次加入硅酸钾、碱类物质并搅拌均匀，逐滴加入偏铝酸钾搅拌3h-6h，得到合成金属掺杂KP型分子筛溶液，合成金属掺杂KP型分子筛溶液中各物质的摩尔比为K2SiO3/KAlO2 = 0.1-20，KAlO2/M= 0.1-10，K2SiO3/H2O = 0.01-0.5；80oC-150 oC下晶化1h-24h，过滤后产物用去离子水和乙醇洗涤3-5次，80oC-120oC下干燥12h-24h，得到金属掺杂KP型分子筛，金属掺杂KP型分子筛为球形的，粒径为0.5μm-4μm。
上述方案中金属盐为金属可溶性氯化物或者硝酸盐，金属盐中金属M为Co、Ni、Cu、Zn、Mn中的一种或两种。
上述方案中碱类物质包括KOH，KHCO3，K2CO3，K2C2O4，KOCH3、KOCH2CH3中的一种或两种。
上述方案中合成金属掺杂KP型分子筛合成溶液的pH为10.0-14.0。
上述方案中K2SiO3的摩尔浓度为0.05 mol/L-2.0 mol/L，KAlO2的摩尔浓度为0.05mol/L-2.0 mol/L。
上述方案中金属掺杂KP型分子筛吸附脱除羰基硫的吸附温度为20oC-50oC，液化气体积空速为0.5 h-1-15 h-1，液化气中羰基硫的脱除率达90-99.5%。
本发明具有以下有益效果：
1、本发明利用水热合成法制备出粒径均一、形貌规则的金属掺杂KP型分子筛，具有较大的比表面积和孔容，对COS的吸附性能较强。
2、本发明制备的金属掺杂KP型分子筛吸附剂，较常规的NaP型分子筛具有更强的K+碱性中心，有利于COS的水解，且COS在碱性中心水解后生成H2S被金属氧化物活性中心化学吸附，可进一步提高液化石油气中COS的脱除率。
3、KP型分子筛合成过程中产率较高，且制备过程简单，成本低廉，具有广阔的应用前景。
具体实施方式
下面对本发明作进一步的说明：
实施例1
依次向25mL去离子水中加入4.652g Cu(NO3)2·2.5H2O、1.795g KOH和1.234gK2SiO3并搅拌均匀形成混合溶液；将7.84g KAlO2溶解于50mL去离子水中并搅拌均匀，然后逐滴加入到上述混合溶液中再搅拌3h，得到合成金属掺杂KP型分子筛溶液；此时合成金属掺杂KP型分子筛溶液pH值为12.2，再将合成金属掺杂KP型分子筛溶液移入反应釜中，置于130oC下晶化12 h。晶化结束后将产物过滤，用去离子水和无水乙醇分别洗涤4次，将所得固体置于120oC烘箱中干燥，可得到Cu负载量为4.6%的Cu-KP型分子筛。
反应温度为45oC，LPG空速为6 h-1，经Cu-KP型分子筛吸附剂吸附作用后，LPG中COS含量由108.7μg/g下降至1.6 μg/g，气体中未检测到H2S，COS总脱除率为98.5%。
实施例2
依次向50mL去离子水中加入1.533g ZnCl2、4.146g K2CO3和2.314g K2SiO3并搅拌均匀形成混合溶液；将14.7g KAlO2溶解于40 mL去离子水中并搅拌均匀，然后逐滴加入到上述混合溶液中，将所得溶液搅拌3h，得到合成金属掺杂KP型分子筛溶液，此时合成金属掺杂KP型分子筛溶液pH值为13.0，再将合成金属掺杂KP型分子筛溶液移入反应釜中，置于130oC下晶化10h。晶化结束后将产物过滤，用去离子水和无水乙醇分别洗涤4次，将所得固体置于100oC烘箱中干燥，得到Zn负载量为10.4%的Zn-KP型分子筛。
反应温度为40oC，LPG空速为10h-1，经Zn-KP型分子筛吸附作用后，LPG中COS含量由108.7μg/g下降至0.6 μg/g，未检测到H2S，COS总脱除率达到99.4%。
实施例3
依次向50mL去离子水中加入1.090g Ni(NO3)2·2.5H2O、4.146g K2CO3和2.314gK2SiO3并搅拌均匀形成混合溶液；将14.7g KAlO2溶解于40mL去离子水中并搅拌均匀，然后逐滴加入到上述混合溶液中，将所得溶液搅拌3h，得到合成金属掺杂KP型分子筛溶液，此时溶液pH值为13.1，再将合成金属掺杂KP型分子筛溶液移入反应釜中，置于130oC下晶化10h。晶化结束后将产物过滤，用去离子水和无水乙醇分别洗涤3次，将所得固体置于100oC烘箱中干燥，得到Ni负载为4.4%的Ni-KP型分子筛。
反应温度为40oC，LPG空速为8h-1，经Ni-KP型分子筛吸附作用后，LPG中COS含量由108.7μg/g下降至2.4μg/g，H2S含量低于0.1μg/g，COS总脱除率达到97.8%。
实施例4
依次向25mL去离子水中加入7.03g Mn(NO3)2·4H2O、1.795g KOH和1.234g K2SiO3并搅拌均匀形成混合溶液；将7.84g KAlO2溶解于50mL去离子水中并搅拌均匀，然后逐滴加入到上述混合溶液中再搅拌3h，得到合成金属掺杂KP型分子筛溶液；此时溶液pH值为13.0，再将合成金属掺杂KP型分子筛溶液移入反应釜中，置于130oC下晶化12h。晶化结束后将产物过滤，用去离子水和无水乙醇分别洗涤4次，将所得固体置于110oC烘箱中干燥，可得到Mn负载量为6.8%的Mn-KP型分子筛。
反应温度为40oC，LPG空速为7h-1，经Mn-KP型分子筛吸附剂吸附作用后，LPG中COS含量108.7μg/g下降至1.8 μg/g，未检测到H2S，COS总脱除率达到98.3%。
表1 LPG原料组成
| 组成 | 含量 |
| 丙烷，%（v/v） | 10.3 |
| 丙烯，%（v/v） | 33.5 |
| 正丁烷，%（v/v） | 4.9 |
| 异丁烷，%（v/v） | 32.8 |
| 1-丁烯，%（v/v） | 5.1 |
| 异丁烯，%（v/v） | 5.7 |
| 顺-2-丁烯，%（v/v） | 3.4 |
| 反-2-丁烯，%（v/v） | 2.9 |
| 1,3-丁二烯，%（v/v） | 0.8 |
| COS，μg/g | 108.7 |
Claims (5)
1.一种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，其特征在于：这种金属掺杂KP型分子筛吸附剂脱除羰基硫的方法：在吸附温度为20oC-60 oC，液化气体积空速为0.1 h-1-20 h-1的条件下，金属掺杂KP型分子筛吸附剂脱除羰基硫，羰基硫的脱除率达85%-99.5%；
金属掺杂KP型分子筛制备方法为：配置一定浓度的金属盐溶液，金属盐溶液中金属为M，金属M的质量分数为0.1wt%-15wt%，依次加入硅酸钾、碱类物质并搅拌均匀，逐滴加入偏铝酸钾搅拌3h-6h，得到合成金属掺杂KP型分子筛溶液，合成金属掺杂KP型分子筛溶液中各物质的摩尔比为K2SiO3/KAlO2 = 0.1-20，KAlO2/M= 0.1-10，K2SiO3/H2O = 0.01-0.5；80 oC-150 oC下晶化1h-24h，过滤后产物用去离子水和乙醇洗涤3-5次，80oC-120oC下干燥12h-24h，得到金属掺杂KP型分子筛，金属掺杂KP型分子筛为球形的，粒径为0.5μm-4μm；
金属M为Co、Ni、Cu、Zn、Mn中的一种或两种；碱类物质包括KOH，KHCO3，K2CO3，K2C2O4，KOCH3、KOCH2CH3中的一种或两种。
2.根据权利要求1所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，其特征在于：所述的金属盐为金属可溶性氯化物或者硝酸盐。
3.根据权利要求2所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，其特征在于：所述的合成金属掺杂KP型分子筛合成溶液的pH为10.0-14.0。
4.根据权利要求3所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，其特征在于：所述的K2SiO3的摩尔浓度为0.05 mol/L-2.0 mol/L，KAlO2的摩尔浓度为0.05 mol/L-2.0mol/L。
5.根据权利要求4所述的金属掺杂KP型分子筛吸附剂脱除羰基硫的方法，其特征在于：所述的金属掺杂KP型分子筛吸附脱除羰基硫的吸附温度为20oC-50oC，液化气体积空速为0.5h-1-15h-1，液化气中羰基硫的脱除率达90-99.5%。
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