CN116947509A - 一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法 - Google Patents
一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法 Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011819 refractory material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- 239000001294 propane Substances 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000002699 waste material Substances 0.000 claims abstract description 28
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000011449 brick Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000004939 coking Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 19
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052863 mullite Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052849 andalusite Inorganic materials 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052851 sillimanite Inorganic materials 0.000 claims description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000002920 hazardous waste Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
本发明公开了一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法。以Catofin工艺废弃铝铬催化剂作为处理对象，废弃铝铬催化剂作为添加物，将废弃催化剂直接加入Catofin丙烷脱氢耐火材料中，制备具有催化功能的耐火材料；通过高温烧成，将结焦失活的催化剂部分激活，使其成为反应器用砖的一部分，其不仅仅作为耐火衬里，起到隔热保温作用，还能够起到一部分催化作用；通过引入废弃催化剂制备具有催化功能的耐火材料，不仅将废弃的铝铬催化剂重新激活利用，还能提高反应器的整体催化处理能力。
Description
技术领域
本发明涉及一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，属于耐火材料领域。
背景技术
根据《国家危险废物名录（2021年版）》，Catofin工艺丙烷脱氢制丙烯所用的铝铬催化剂属于HW50废物，废物代码261-156-50，危险特性为T（Toxicity毒性）。
由于Catofin工艺丙烷脱氢制丙烯所用的铝铬催化剂属于HW50废物，Catofin工艺丙烷脱氢厂家需要给具备相应资质的危废处理厂家很高一批费用来处理使用后的铝铬催化剂。危废处理厂家往往通过复杂的熔炼工艺来无害化处理，既容易造成二次污染，又花费较大，浪费了能源和资源。
文件附录中列出了《危险废物豁免管理清单》最后一条：危险废物或利用过程不满足本《危险废物豁免管理清单》所列豁免条件的危险废物。豁免环节：利用。豁免条件：在环境风险可控的前提下，根据省级生态环境部门确定的方案，实行危险废物“点对点”定向利用，即：一家单位产生的一种危险废物，可作为另外一家单位环境治理或工业原料生产的替代原料进行使用；豁免内容：利用过程不按危险废物管理。
发明内容
为解决上述技术问题，本发明的目的是提出一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法。
本发明为完成上述目的采用如下技术方案：
一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，以Catofin工艺废弃铝铬催化剂作为处理对象，废弃铝铬催化剂作为添加物，将废弃催化剂直接加入Catofin丙烷脱氢耐火材料中，制备具有催化功能的耐火材料；通过高温烧成，将结焦失活的催化剂部分激活，使其成为反应器用砖的一部分，其不仅仅作为耐火衬里，起到隔热保温作用，还能够起到一部分催化作用；通过引入废弃催化剂制备具有催化功能的耐火材料，不仅将废弃的铝铬催化剂重新激活利用，还能提高反应器的整体催化处理能力；用于制备此材料由以下重量百分比的原料构成：
原料颗粒 10~60%，
废弃催化剂颗粒 5~50%，
基质 25~50%，
外加酸性结合剂 3~5%；
废弃铝铬催化剂为直径2.5-3.2mm，长度3-6mm的多孔材料，直接加入作为颗粒使用；所述的酸性结合剂使六价铬在＞900℃的烧成温度下转化为无害的三价铬，且在酸性环境下，有效抑制了六价铬的再次生成。
所述的原料颗粒为红柱石、氧化铝质量比含量为45~75%的烧结莫来石、硅线石等的两种或多种。
所述的基质为氧化铝质量含量为45~75%的烧结莫来石细粉、红柱石细粉、煅烧氧化铝微粉、二氧化硅微粉、结合粘土的三种或多种。
所述的酸性结合剂为磷酸溶液、磷酸二氢铝溶液、硫酸铝溶液、聚合氯化铝溶液中的一种。
本发明的有益效果是通过对现有Catofin丙烷脱氢耐火材料添加废弃催化剂颗粒，再辅以酸性结合剂，可将危险废物“点对点”定向利用，既使废催化剂作为耐火材料原料的一部分，又通过高温热处理使废弃催化剂重新激活。同时，得到的催化功能耐火材料中的危险特性物质——六价铬能够在生产过程中转化为无害的三价铬；这种危废处理的方法既节省了能源和资源，又不会造成二次污染，还提高了反应器催化效率，对Catofin工艺丙烷脱氢厂家和制造厂家是双赢。
实施方式
结合具体实施例对本发明加以详细说明：
实施例
各组份配比为（质量百分数）：M60烧结莫来石颗粒15%，红柱石颗粒15%，硅线石颗粒10%，废催化剂颗粒25%，M70烧结莫来石粉10%，红柱石细粉10%，煅烧氧化铝微粉10%，结合粘土5%。先将颗粒部分混合均匀，加入4%的磷酸溶液，用轮碾机混合均匀。再将混合粉加入轮碾机，搅拌5~10分钟后出料，机压成型，经过110℃干燥，1000℃保温8h烧成。
实施例
各组份配比为（质量百分数）：M70烧结莫来石颗粒15%，硅线石颗粒10%，废催化剂颗粒45%，M60烧结莫来石粉5%，红柱石细粉10%，煅烧氧化铝微粉10%，二氧化硅微粉2%，结合粘土3%。先将颗粒部分混合均匀，加入3%的磷酸二氢铝溶液，用轮碾机混合均匀。再将混合粉加入轮碾机，搅拌5~10分钟后出料，机压成型，经过110℃干燥，1300℃保温10h烧成。
实施例
各组份配比为（质量百分数）：M45烧结莫来石颗粒60%，废催化剂颗粒10%，M50烧结莫来石粉22%，二氧化硅微粉3%，结合粘土5%。先将颗粒部分混合均匀，加入5%的硫酸铝溶液，用轮碾机混合均匀。再将混合粉加入轮碾机，搅拌5~10分钟后出料，机压成型，经过110℃干燥，1100℃保温5h烧成。
实施例
各组份配比为（质量百分数）：M50烧结莫来石颗粒25%，红柱石颗粒20%，硅线石颗粒15%，废催化剂颗粒5%，M50烧结莫来石粉15%，红柱石细粉15%，结合粘土5%。先将颗粒部分混合均匀，加入4%的磷酸溶液，用轮碾机混合均匀。再将混合粉加入轮碾机，搅拌5~10分钟后出料，机压成型，经过110℃干燥，1300℃保温8h烧成。
实施例
各组份配比为（质量百分数）：M75烧结莫来石颗粒10%，硅线石颗粒15%，废催化剂颗粒50%，M75烧结莫来石粉10%，煅烧氧化铝微粉10%，结合粘土5%。先将颗粒部分混合均匀，加入5%的聚合氯化铝溶液，用轮碾机混合均匀。再将混合粉加入轮碾机，搅拌5~10分钟后出料，机压成型，经过110℃干燥，1400℃保温10h烧成。
Claims (4)
1.一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，其特征在于：以Catofin工艺废弃铝铬催化剂作为处理对象，废弃铝铬催化剂作为添加物，将废弃催化剂直接加入Catofin丙烷脱氢耐火材料中，制备具有催化功能的耐火材料；通过高温烧成，将结焦失活的催化剂部分激活，使其成为反应器用砖的一部分，其不仅仅作为耐火衬里，起到隔热保温作用，还能够起到一部分催化作用；通过引入废弃催化剂制备具有催化功能的耐火材料，不仅将废弃的铝铬催化剂重新激活利用，还能提高反应器的整体催化处理能力；用于制备此材料由以下重量百分比的原料构成：
原料颗粒 10~60%，
废弃催化剂颗粒 5~50%，
基质 25~50%，
外加酸性结合剂 3~5%；
废弃铝铬催化剂为直径2.5-3.2mm，长度3-6mm的多孔材料，直接加入作为颗粒使用；所述的酸性结合剂使六价铬在＞900℃的烧成温度下转化为无害的三价铬，且在酸性环境下，有效抑制了六价铬的再次生成。
2.如权利要求1所述的一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，其特征在于：所述的原料颗粒为红柱石、氧化铝质量比含量为45~75%的烧结莫来石、硅线石等的两种或多种。
3.如权利要求1所述的一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，其特征在于：所述的基质为氧化铝质量含量为45~75%的烧结莫来石细粉、红柱石细粉、煅烧氧化铝微粉、二氧化硅微粉、结合粘土的三种或多种。
4.如权利要求1所述的一种制备Catofin丙烷脱氢反应器催化功能耐火材料的方法，其特征在于：所述的酸性结合剂为磷酸溶液、磷酸二氢铝溶液、硫酸铝溶液、聚合氯化铝溶液中的一种。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105924181A (zh) * | 2016-04-15 | 2016-09-07 | 安庆寰宜环保科技有限公司 | 利用废催化剂制备耐火砖的生产方法 |
| CN108569907A (zh) * | 2018-06-12 | 2018-09-25 | 中钢集团洛阳耐火材料研究院有限公司 | 一种Catofin丙烷脱氢反应器用耐火材料的制备方法 |
| CN109650936A (zh) * | 2019-02-27 | 2019-04-19 | 广东粤能净环保科技有限公司 | 一种耐火材料及其制备方法 |
| WO2022219572A1 (en) * | 2021-04-16 | 2022-10-20 | Sabic Global Technologies B.V. | Utilization of spent chromia/alumina catalyst for cement production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924181A (zh) * | 2016-04-15 | 2016-09-07 | 安庆寰宜环保科技有限公司 | 利用废催化剂制备耐火砖的生产方法 |
| CN108569907A (zh) * | 2018-06-12 | 2018-09-25 | 中钢集团洛阳耐火材料研究院有限公司 | 一种Catofin丙烷脱氢反应器用耐火材料的制备方法 |
| CN109650936A (zh) * | 2019-02-27 | 2019-04-19 | 广东粤能净环保科技有限公司 | 一种耐火材料及其制备方法 |
| WO2022219572A1 (en) * | 2021-04-16 | 2022-10-20 | Sabic Global Technologies B.V. | Utilization of spent chromia/alumina catalyst for cement production |
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