CN105413446A - 一种固态脱硫剂 - Google Patents
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- 239000007787 solid Substances 0.000 title claims abstract description 20
- 230000003009 desulfurizing effect Effects 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000013256 coordination polymer Substances 0.000 claims abstract description 18
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 17
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000292 calcium oxide Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OJJQJUVBWCJFQM-UHFFFAOYSA-N 5-(3-carboxy-4-methoxyphenyl)-2-methoxybenzoic acid Chemical group C1=C(C(O)=O)C(OC)=CC=C1C1=CC=C(OC)C(C(O)=O)=C1 OJJQJUVBWCJFQM-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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Abstract
本发明涉及脱硫剂，具体涉及一种固态脱硫剂。一种固态脱硫剂，由如下重量份数的组分组成：氧化钙3~9份；三氧化二铁5~16份；氟化钙5~10份；氧化铝1~6份；碳酸氢钠2~8份；含钕配位聚合物7~16份。本发明的固态脱硫剂中通过添加新型的含钕配位聚合物，使得所得的脱硫剂和现有市面常见固态脱硫剂相比具有脱硫效果好，硫容量高的特点。
Description
技术领域
本发明涉及脱硫剂，具体涉及一种固态脱硫剂。
背景技术
气化或热解产生的粗煤气中含有粉尘、HCl 和含硫气体 (90％以上为 H2S)
等污染物，在使用之前必须予以净化。煤气作为燃料气使用时，含硫气体会对燃气轮机叶片等设备造成腐蚀；作为原料气则会使催化剂硫中毒，同时其燃烧转化为SO2释放到大气中会引起酸雨，严重危害环境和人体健康，因此在工艺过程中 H2S 等含硫物质的脱除是生活生产中的必要环节。现有的脱硫剂的脱硫率一般较低，脱硫不完全，硫容量低。
发明内容
本发明所要解决的技术问题是提供一种脱硫效果好，硫容量高的固态脱硫剂。
本发明所要解决的技术问题通过以下技术方案予以实现：
一种固态脱硫剂，由如下重量份数的组分组成：
氧化钙3~9份；三氧化二铁5~16份；氟化钙5~10份；氧化铝1~6份；碳酸氢钠2~8份；含钕配位聚合物7~16份。
进一步的，所述含钕配位聚合物的化学式为：C56H48O12N4Nd。
进一步的，所述含钕配位聚合物为单斜晶系，C2/c空间群，晶胞参数为a=
21.573(2) Å，b= 19.739 (9) Å，c= 23.753(3) Å，α=γ =90º，β=101.43(3)º，V=10037.25(5)
Å 3。
本发明具有如下有益效果：
本发明的固态脱硫剂中通过添加新型的含钕配位聚合物，使得所得的脱硫剂和现有市面常见固态脱硫剂相比具有脱硫效果好，硫容量高的特点。
具体实施方式
下面结合实施例对本发明进行详细的说明，实施例仅是本发明的优选实施方式，不是对本发明的限定。
本发明所用的原料均为市面可得产品。
本发明含钕配位聚合物如无特别说明，均按下述方法制备。
将0.2 mmol4,4'-二甲氧基-[1,1'-联苯基]-3,3'-二羧酸（英文为：4,4'-dimethoxy-[1,1'-biphenyl]-3,3'-dicarboxylic
acid，具体结构式如下所示）、0.2 mmol4,4'-二甲基-2,2'-联吡啶和0.1 mmol的硝酸钕溶于5 mL水和10 mL二甲基甲酰胺的混合溶剂当中，在室温下搅拌形成混合液A，用无机碱将混合液A的pH调节为8，然后将上述混合液A在60℃下回流12小时得到混合液B。
然后将所述混合液B置入25 mL水热反应釜中在溶剂热160℃条件下加热反应48小时后以5℃/小时降至室温得到所述的含钕配位聚合物。
然后将上述含钕配位聚合物进行结构表征。
该配位聚合物的X射线衍射数据是在Bruker
Smart Apex CCD面探衍射仪上，用MoKα辐射(λ =
0.71073 Å)，以ω扫描方式收集并进行Lp因子校正，吸收校正使用SADABS程序。用直接法解结构，然后用差值傅立叶法求出全部非氢原子坐标，并用理论加氢法得到氢原子位置(C−H
1.083 Å)，用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。
经测试解析可知，该含钕配位聚合物化学分子式为C56H48O12N4Nd，单斜晶系，C2/c空间群，晶胞参数为a=
21.573(2) Å，b= 19.739 (9) Å，c= 23.753(3) Å，α=γ =90º，β=101.43(3)º，V=10037.25(5)
Å 3 ，Z=8。
本发明的脱硫剂的制备方法为本技术领域的常用方法，在本发明中不再详细描述。
实施例
1
一种固态脱硫剂，由如下重量份数的组分组成：
氧化钙5份；三氧化二铁14份；氟化钙9份；氧化铝2份；碳酸氢钠5份；含钕配位聚合物10份。
实施例
2
一种固态脱硫剂，由如下重量份数的组分组成：
氧化钙8份；三氧化二铁6份；氟化钙6份；氧化铝6份；碳酸氢钠8份；含钕配位聚合物15份。
实施例
3
一种固态脱硫剂，由如下重量份数的组分组成：
氧化钙3份；三氧化二铁10份；氟化钙7份；氧化铝3份；碳酸氢钠2份；含钕配位聚合物7份。
对比例
一种固态脱硫剂，由如下重量份数的组分组成：
氧化钙5份；三氧化二铁14份；氟化钙9份；氧化铝2份；碳酸氢钠5份。
将上述实施例和对比例所得的固态脱硫剂按照本技术领域的常规性能方法对其检测，性能如表1所示。
表1 固态脱硫剂性能对照表
| 实施例1 | 实施例2 | 实施例3 | 对比例 | |
| 脱硫率 | 87% | 92% | 83% | 68% |
| 硫容量 | 36% | 42% | 33% | 21% |
| 29 次循环后脱硫率 | 81% | 85% | 76% | 40% |
| 29次循环后硫容量 | 25% | 28% | 22% | 7% |
从以上数据可知，本发明通过添加新型的含钕配位聚合物，使得所得的脱硫剂具有脱硫效果好，硫容量高的特点。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应落在本发明的保护范围之内。
Claims (3)
1.一种固态脱硫剂，其特征在于由如下重量份数的组分组成：
氧化钙3~9份；三氧化二铁5~16份；氟化钙5~10份；氧化铝1~6份；碳酸氢钠2~8份；含钕配位聚合物7~16份。
2.根据权利要求1所述的一种固态脱硫剂，其特征在于，所述含钕配位聚合物的化学式为：C56H48O12N4Nd。
3.根据权利要求2所述的一种固态脱硫剂，其特征在于，所述含钕配位聚合物为单斜晶系，C2/c空间群，晶胞参数为a= 21.573(2) Å，b= 19.739 (9) Å，c=
23.753(3) Å，α=γ=90 º，β=101.43(3)º，V=10037.25(5) Å 3。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854521A (zh) * | 2018-06-29 | 2018-11-23 | 浙江钙科机械设备有限公司 | 一种高效活性脱硫剂 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836993A (en) * | 1983-09-27 | 1989-06-06 | Amoco Corporation | Process for removing sulfur oxides from a gas |
| JPH0617067A (ja) * | 1992-06-29 | 1994-01-25 | Kawasaki Steel Corp | 高温ガス用脱硫剤の製造方法 |
| CN102039086A (zh) * | 2009-10-22 | 2011-05-04 | 北京三聚环保新材料股份有限公司 | 一种中温铁锰脱硫剂及其制备方法 |
| CN102899123A (zh) * | 2012-09-25 | 2013-01-30 | 薛华 | 燃煤高效脱硫剂 |
-
2015
- 2015-12-08 CN CN201510898674.2A patent/CN105413446B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836993A (en) * | 1983-09-27 | 1989-06-06 | Amoco Corporation | Process for removing sulfur oxides from a gas |
| JPH0617067A (ja) * | 1992-06-29 | 1994-01-25 | Kawasaki Steel Corp | 高温ガス用脱硫剤の製造方法 |
| CN102039086A (zh) * | 2009-10-22 | 2011-05-04 | 北京三聚环保新材料股份有限公司 | 一种中温铁锰脱硫剂及其制备方法 |
| CN102899123A (zh) * | 2012-09-25 | 2013-01-30 | 薛华 | 燃煤高效脱硫剂 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854521A (zh) * | 2018-06-29 | 2018-11-23 | 浙江钙科机械设备有限公司 | 一种高效活性脱硫剂 |
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