CN107261844B - 一种含纳米级催化剂的车用尿素的生产工艺 - Google Patents
一种含纳米级催化剂的车用尿素的生产工艺 Download PDFInfo
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004202 carbamide Substances 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01D—SEPARATION
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
本发明公开了一种含纳米级催化剂的车用尿素的生产工艺,本发明的优点是通过加入催化剂A,优化连续提纯工艺及降低氨含量工艺,能有效降低车用尿素重金属环境污染问题,提高车用尿素降解吸收氮氧化物的效率,解决低温结晶问题。本工艺中添加的催化剂A具有催化活性高、温度窗口宽广、起燃快等特点。
Description
技术领域
本发明涉及一种含纳米级催化剂的车用尿素的生产工艺,属于化工技术领域。
背景技术
尿素-SCR(Selective Catalytic Reduction)技术由于具有可以改善燃油消耗、抗硫中毒能力强等优点,作为控制车用柴油机尾气排放的重要手段在欧洲等发达国家和地区已经得到了广泛的应用,对于改善由汽车尾气造成的大气污染发挥了重要作用。目前,虽然国内几家主要车用柴油机企业已经在柴油机领域开展了SCR技术的研究,但基本上以国外技术引进应用为主,核心技术仍主要掌握在国外相关厂家手中,这成为我国该技术推广和应用的主要瓶颈。
车用柴油机运行工况多变,排气流量和温度变化范围较广,废气中氮氧化物、硫氧化物和烟尘等成分含量也各不相同,由于催化剂的反应条件不同,催化剂中有效成分的配比、辅助成分的选择、制备工艺和性能评价条件等也不一样,配比成分和制备方法的改变往往使载体与活性组分之间的相互作用发生改变,最终影响到催化剂的活性。
再次,车用尿素产品的添加剂都是有毒性的,客户使用之后不但对环境危害性很大,而且对自身的健康和安全都具有一定的威胁性。因此研发无毒性,高效率,耐低温的车用尿素,不但能够有效解决车用尿素重金属环境污染问题,提供车用尿素降解氮氧化物的效率,解决低温结晶问题,保证国四商用车SCR系统良好运转,保障车辆在低温天气正常启动和SCR系统正常运转,并减少低温下NOx的排放,而且拥有大于200g/kg的氨的释放潜值,完全匹配现有的SCR设计,解决氨释放潜值匹配问题并有效预防尿素输送管及存储罐因低温体积膨胀而产生的损伤,降低整车使用成本。
发明内容
为解决现有技术存在的技术问题,本发明提供了一种含纳米级催化剂的车用尿素的生产工艺,采用该工艺生产的车用尿素能有效降低车用尿素重金属环境污染问题,提高车用尿素降解吸收氮氧化物的效率,解决低温结晶问题。
本发明公开了一种含纳米级催化剂的车用尿素的生产工艺,包括以下步骤:
a.制取催化剂A,取等质量的50-80g的偏钒酸铵和草酸,溶于1000g去离子水配成溶液,加入30-40g的偏铝酸钠并进行搅拌,在搅拌过程中加入20g的纳米级WO3/TiO2混合物粉末,并连续搅拌2小时,放入温控电炉中在450℃温度下高温焙烧1小时,然后自然冷却到室温,得到催化剂A。
b.催化剂A稳定:将制备好的催化剂A再次放入电炉内,在水蒸气氛围下加热至高温650一680℃加热30分钟后自然冷却到室温。
c.尿素溶液制备:20-25℃下,将尿素与去离子水按1:2重量份数混合,经过四次提纯,使不溶物低于2%,再次加入去离子水使尿素溶液浓度达到32%.
d.降低游离氨含量:将c所制得的溶液经过精馏塔和闪蒸槽,使游离氨含量低于0.2%。
e.将催化剂A加入尿素溶液,常温,搅拌30min,储存待用。
优选地,去离子水的电阻率低于15MΩ*cm。
优选地,四次提纯分别为袋式过滤器提纯、机械过滤器提纯、精密滤芯提纯、膜过滤提纯。
本发明的优点是通过加入催化剂A,优化连续提纯工艺及降低氨含量工艺,能有效降低车用尿素重金属环境污染问题,提高车用尿素降解吸收氮氧化物的效率,解决低温结晶问题。本工艺中添加的催化剂A具有催化活性高、温度窗口宽广、起燃快等特点。
具体实施方式
为了能更清楚地理解本发明的技术方案。
车用尿素水溶液指标必须符合ISO2241-1规定,并且检测方法采用ISO2241-2的方法施行,具体指标如表1.并采用标准SCR的活性评价测试试验装置测试DeNOx的效果,以NOx的转化率为指标。
表1
实施例1,a.制取催化剂A,取等质量的50-80g的偏钒酸铵和草酸,溶于1000g去离子水配成溶液,加入30-40g的偏铝酸钠并进行搅拌,在搅拌过程中加入20g的纳米级WO3/TiO2混合物粉末,并连续搅拌2小时,放入温控电炉中在450℃温度下高温焙烧1小时,然后自然冷却到室温,得到催化剂A。
b.催化剂A稳定:将制备好的催化剂A再次放入电炉内,在水蒸气氛围下加热至高温650一680℃加热30分钟后自然冷却到室温。
c.尿素溶液制备:20-25℃下,将尿素与去离子水按1:2重量份数混合,经过四次提纯,使不溶物低于2%,再次加入去离子水使尿素溶液浓度达到32%.
d.降低游离氨含量:将c所制得的溶液经过精馏塔和闪蒸槽,使游离氨含量低于0.2%。
e.将催化剂A加入尿素溶液,常温,搅拌30min,储存待用。
优选地,去离子水的电阻率低于15MΩ*cm。
优选地,四次提纯分别为袋式过滤器提纯、机械过滤器提纯、精密滤芯提纯、膜过滤提纯。
如表2所示,经过四级提纯和添加催化剂A后的溶液完全符合ISO22241-1的要求,其降解氮氧化物的能力得到了提高,结晶温度远低于国家标准。
以上所述仅是本发明的较佳实施方式,故凡依本发明专利申请范围所述的构造、特征及原理所做的等效变化或修饰,均包括于本发明专利申请范围内。
Claims (3)
1.一种含纳米级催化剂的车用尿素的生产工艺,包括以下步骤:
a.制取催化剂A:取等质量的50 - 80g的偏钒酸铵和草酸,溶于1000g去离子水配成溶液,加入30 - 40g的偏铝酸钠并进行搅拌,在搅拌过程中加入20g的纳米级WO3/TiO2混合物粉末,并连续搅拌2小时,放入温控电炉中在450℃温度下高温焙烧1小时,然后自然冷却到室温,得到催化剂A;
b.催化剂A稳定:将制备好的催化剂A再次放入电炉内,在水蒸气氛围下加热至高温650- 680℃加热30分钟后自然冷却到室温;
c.尿素溶液制备:20 - 25℃下,将尿素与去离子水按1:2重量份数混合,经过四次提纯,使不溶物低于2%,再次加入去离子水使尿素溶液浓度达到32%;
d.降低游离氨含量:将c所制得的溶液经过精馏塔和闪蒸槽,使游离氨含量低于0.2%;
e.将催化剂A加入尿素溶液,常温,搅拌30min,储存待用。
2.根据权利要求1所述的一种含纳米级催化剂的车用尿素的生产工艺,其特征在于:所述去离子水的电阻率低于15MΩ*cm。
3.根据权利要求1所述的一种含纳米级催化剂的车用尿素的生产工艺,其特征在于:所述四次提纯分别为袋式过滤器提纯、机械过滤器提纯、精密滤芯提纯、膜过滤提纯。
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CN110339866A (zh) * | 2019-07-14 | 2019-10-18 | 茌平县鲁华工贸有限公司 | 一种车用尿素生产用催化剂及其生产工艺 |
CN112090277A (zh) * | 2020-09-30 | 2020-12-18 | 河南弘康环保科技有限公司 | 一种含纳米级催化剂的车用尿素的生产工艺 |
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CN112316723A (zh) * | 2020-11-13 | 2021-02-05 | 河南弘康环保科技有限公司 | 一种高效解决结晶堵塞的车用尿素溶液 |
CN112316722A (zh) * | 2020-11-13 | 2021-02-05 | 河南弘康环保科技有限公司 | 一种添加多种活性剂的防冻保质型汽车尿素液制备方法 |
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DE102010020842A1 (de) * | 2010-05-18 | 2011-11-24 | Continental Automotive Gmbh | Füllstandsensoren, Füllstandserkennungsverfahren sowie Kraftfahrzeug mit einem Füllstandssensor |
CN102806011A (zh) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | 一种车用尿素液还原剂的制备方法 |
GB201322576D0 (en) * | 2013-12-19 | 2014-02-05 | Equigerminal Sa | Urea delivery system for scr system |
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