CN112403529A - 一种固态脱硫脱硝剂 - Google Patents
一种固态脱硫脱硝剂 Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 49
- 230000023556 desulfurization Effects 0.000 title claims abstract description 49
- 239000007787 solid Substances 0.000 title claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 29
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LUYGICHXYUCIFA-UHFFFAOYSA-H calcium;dimagnesium;hexaacetate Chemical compound [Mg+2].[Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LUYGICHXYUCIFA-UHFFFAOYSA-H 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 239000011802 pulverized particle Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 229910002089 NOx Inorganic materials 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004868 gas analysis Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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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
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Abstract
本发明公开了一种固态脱硫脱硝剂,属于催化剂制备技术领域。包括原料:氧化铁,二氧化锰,尿素,醋酸钙镁,氧化钛,高岭土和碳酸钙。本发明通过进一步优化固态脱硝剂的配方组分,起到在脱硫同时进行脱硝的技术效果,具体通过对碳酸钙进行改性,增强其吸附脱除能力,脱硫脱硝效果好,脱硝率达80%以上,脱硫效果达97%以上。
Description
技术领域
本发明涉及催化剂制备技术领域,更具体地说是涉及一种固态脱硫脱硝剂。
背景技术
NOX和酸性SO2的排放对大气造成严重污染,然而,由于煤炭燃烧、垃圾焚烧和经济发展等,工况企业生产过程排放的污染物短时间内无法明显下降,环境污染问题无法避免,其中,一氧化氮和二氧化氮是形成光化学烟雾和酸雨的一个重要原因,氮氧化物对人类呼吸系统有害,长期吸入氮氧化物可能会导致肺部构造改变,而酸性SO2主要引起不同程度的呼吸道及眼粘膜的刺激症状。
为降低污染,现有技术中已有干法脱硫吸收技术,具有无污水废酸排出、设备腐蚀程度较轻,二次污染少等优点,而脱硝技术中,同样包括干法脱硝技术。
然而,干法脱硝/脱硫技术对烟气温度范围要求较高,此外,最主要的问题在于反应效率偏低,常规脱硝剂脱硝效率低于70%,脱硫效果低于80%,且对设备要求较多。
因此,如何通过优化脱硫脱硝的原料和工艺,提高脱除效率,对干法脱硝具有重要的价值,是本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明提供了一种固态脱硫脱硝剂。
为了实现上述目的,本发明采用如下技术方案:
一种固态脱硫脱硝剂,包括以下重量份数的原料:氧化铁1~15份,二氧化锰2~6份,尿素40~60份,醋酸钙镁10~25份,氧化钛1~10份,高岭土 5~10份和碳酸钙120~150份。
有益效果在于:为了增强脱硫效果,优化了配方原料,通过加入碳酸钙,起到强化脱硫脱硝效果的作用。同时,以氧化铁为原料,可以促进反应温度降低,并表现出更好的催化活性。以尿素为原料,可与NOx反应,生成氮气和水,可较好的脱除NOx;氧化钛具有较好的在煤灰气体中脱除NOx的能力,作为配方的一部分,可以促进脱除NOx;高岭土具有优良的比表面积,可以促进对NOx的吸附;醋酸钙镁具有优良的中空多孔,且比表面积大,利于对 NOx的脱除。同时醋酸钙镁高温下分解生成多种强还原气体,与NOx进行还原反应,可以脱除NOx。
优选的:氧化铁10份,二氧化锰4份,尿素50份,醋酸钙镁15份,氧化钛5份,高岭土10份和碳酸钙130份。
优选的:碳酸钙由碳酸钙和改性碳酸钙构成,质量比为1:(2~3)。
有益效果在于,通过对碳酸钙进行改性处理,并与普通碳酸钙混配,既能提高碳酸钙脱除硫的效果,同时兼顾成本。
优选的:改性碳酸钙的制备方法为在70~80℃下,将重质碳酸钙、聚氧乙烯脂肪醇醚、水按质量比100:(3~4):(4~5)混合反应2~3h即得。
有益效果在于:提供了一种易工业操作处理的改性碳酸钙的加工工艺,同时将其应用于脱硫剂中。
本发明提供了一种固态脱硫脱硝剂的制备方法,其特征在于,包括下列步骤:
(1)将氧化铁、二氧化锰、氧化钛、高岭土、碳酸钙混合粉碎,得还原基料;
(2)将步骤(1)制备的还原基料与尿素和醋酸钙镁混合均匀,即得固态脱硫脱硝剂。
优选的:步骤(1)粉碎粒径为30~70nm。
经由上述的技术方案可知,与现有技术相比,本发明公开提供了一种固态脱硫脱硝剂,取得的技术效果为通过优化组分配比,使热解过程产生多种强还原性气体,提高干法脱除反应效率,并适当降低了干法脱硝脱硫的温度范围要求,不必使用复杂的脱除设备,脱硝率达80%以上,脱硫效果达97%以上废气温度范围在750~1200℃间。
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。
本发明实施例公开了一种固态脱硫脱硝剂。实施例所需单一化学品均为市售渠道采购,对其品牌不做限定;实施例中涉及的(实验)设备、仪器,对其品牌不做限定,均为常规设备,例如,采用宜兴禄洪环保科技有限公司提供的成套工业生产脱硝/硫设备(主要包括存储单元包括下料系统及料仓;定量给料单元包括料斗、称重模块、给料螺旋、阀门;气力输送单元包括罗茨风机、气力输送管道、文丘里加速室、喷枪;电控单元包括电气系统和控制系统);采用尾部烟道烟气分析设备(芬兰GASMET公司FT-IR CX-4000傅里叶变换红外光谱分析仪)对烟气进行取样分析;采用美国麦克公司生产的比表面积及孔径分析仪对脱硫脱硝剂原料、成品进行分析鉴定;烟气温度测量元件采用K型热电偶(安徽天康仪表有限公司,量程范围0~1300℃);未提及的方法,均为实验室常规实验方法,在此不在一一赘述。
实施例1
一种固态脱硫脱硝剂,包括以下原料:氧化铁1g,二氧化锰6g,尿素 40g,醋酸钙镁25g,氧化钛10g,高岭土5g和碳酸钙120g。
实施例2
一种固态脱硫脱硝剂,包括以下原料:氧化铁10g,二氧化锰4g,尿素 50g,醋酸钙镁15g,氧化钛5g,高岭土10g和碳酸钙130g。
实施例3
一种固态脱硫脱硝剂,包括以下原料:氧化铁15g,二氧化锰2g,尿素 60g,醋酸钙镁10g,氧化钛1g,高岭土10g和碳酸钙150g。
实施例4
实施例1~3的固态脱硫脱硝剂的制备方法:
(1)将氧化铁、二氧化锰、氧化钛、高岭土、碳酸钙混合粉碎,得还原基料;
(2)将步骤(1)制备的还原基料与尿素和醋酸钙镁混合均匀,即得固态脱硫脱硝剂。
为进一步优化技术方案:步骤(1)粉碎粒径为30~70nm。
改性碳酸钙的制备方法:
在70~80℃下,将重质碳酸钙、聚氧乙烯脂肪醇醚、水按质量比100:(3~4): (4~5)混合反应2~3h即得。
对比例1
与实施例2的区别仅在于,不包含氧化铁、醋酸钙镁组分。
对比例2
与实施例2的区别仅在于,不包含二氧化锰、氧化钛成分。
对比例3
与实施例2的区别在于,碳酸钙未改性,仅为普通碳酸钙。
对比试验
将实施例2、对比例1~3制备的脱硝剂在某小型煤粉电厂锅炉中实施。
实验条件:
1.锅炉参数参见表1:
表1
2.干法脱硝/硫成套设备:
采用宜兴禄洪环保科技有限公司成套设备,主要包括:
存储单元(包括下料系统及料仓)
定量给料单元(包括料斗、称重模块、给料螺旋、阀门)
气力输送单元(罗茨风机、气力输送管道、文丘里加速室、喷枪)
电控单元(包括电气系统和控制系统)
3.烟气分析设备:
尾部烟道烟气分析设备采用芬兰GASMET公司FT-IR CX-4000傅里叶变换红外光谱分析仪,对烟气进行取样分析,样气加热温度180℃
4.测温元件:
烟气温度测量元件采用K型热电偶(安徽天康仪表有限公司),量程范围0~1300℃
步骤如下:
脱除设备安装于0米层,喷枪安装在21.2米层炉膛位置,属于高温区域,在炉膛两侧布置,使脱硫脱硝剂喷入后与烟气混合更充分。人工上料到成套设备料仓高料位。
保持锅炉稳定运行,通过调整干法脱硝成套设备定量给料螺旋转速逐步增加干法脱硫脱硝剂喷入量,调整炉膛烟气温度,每个温度阶段保持3小时 (580℃、1280℃因对锅炉安全运行有影响,保持1.5小时),在每个阶段调整干法脱硫脱硝给料量,达到该温度段最佳脱除效果,通过NOx值计算脱硝效率;通过1-脱出后烟气中SO2浓度/原烟气SO2浓度计算脱硫率,为计算准确性,在每个温度阶段前20分钟暂停脱除,通过烟气分析仪测量出NOx、SO2原始浓度。
实验数据参见表2:
表2
600℃ | 700℃ | 750℃ | 800℃ | 900℃ | 1000℃ | 1100 | 1200 | |
实施例1脱硝效率 | 69 | 77 | 81 | 85 | 87 | 89 | 88 | 85 |
实施例2脱硝效率 | 70 | 79 | 82 | 84 | 88 | 91 | 90 | 86 |
实施例3脱硝效率 | 67 | 76 | 80 | 84 | 87 | 90 | 87 | 83 |
实施例1脱硫效率 | 97 | 98 | 98 | 97 | 99 | 97 | 98 | 98 |
实施例2脱硫效率 | 97 | 96 | 97 | 97 | 98 | 97 | 97 | 98 |
实施例3脱硫效率 | 98 | 98 | 97 | 98 | 99 | 97 | 98 | 97 |
对比例1脱硝效率 | 64 | 63 | 69 | 72 | 84 | 87 | 84 | 79 |
对比例2脱硝效率 | 61 | 66 | 71 | 74 | 85 | 89 | 80 | 72 |
对比例3脱硝效率 | 66 | 74 | 78 | 81 | 84 | 87 | 83 | 80 |
对比例1脱硫效率 | 97 | 96 | 97 | 97 | 96 | 97 | 97 | 97 |
对比例2脱硫效率 | 96 | 97 | 98 | 97 | 96 | 96 | 97 | 97 |
对比例3脱硫效率 | 74 | 76 | 75 | 76 | 74 | 76 | 75 | 74 |
实验结果表明,实施例制备的脱硫脱硝剂在脱硝效果方面:
在750℃已使脱硝效果达到80%以上,750~1200℃脱硝效果最佳,相较于单纯脱硝剂而言,对废气的温度要求略高,但均显著优于对比例,其中,实施例2脱硝效果最优。
在脱硫效果方面:
实验发现,对于脱硫效果,温度影响较低,脱除剂碳酸钙外其他成分的调整对整体的影响较低,但改性碳酸钙的脱硫效果显著优于普通碳酸钙。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (6)
1.一种固态脱硫脱硝剂,其特征在于,包括以下重量份数的原料:氧化铁1~15份,二氧化锰2~6份,尿素40~60份,醋酸钙镁10~25份,氧化钛1~10份,高岭土5~10份和碳酸钙120~150份。
2.如权利要求1所述的一种固态脱硫脱硝剂,其特征在于,氧化铁10份,二氧化锰4份,尿素50份,醋酸钙镁15份,氧化钛5份,高岭土10份和碳酸钙130份。
3.如权利要求1或2所述的一种固态脱硫脱硝剂,其特征在于,所述碳酸钙由碳酸钙和改性碳酸钙构成,质量比为1:(2~3)。
4.如权利要求3所述的一种固态脱硫脱硝剂,其特征在于,所述改性碳酸钙的制备方法为在70~80℃下,将重质碳酸钙、聚氧乙烯脂肪醇醚、水按质量比100:(3~4):(4~5)混合反应2~3h即得。
5.一种固态脱硫脱硝剂的制备方法,其特征在于,包括下列步骤:
(1)将氧化铁、二氧化锰、氧化钛、高岭土、碳酸钙混合粉碎,得还原基料;
(2)将步骤(1)制备的还原基料与尿素和醋酸钙镁混合均匀,即得固态脱硫脱硝剂。
6.如权利要求5所述的一种固态脱硫脱硝剂的制备方法,其特征在于,步骤(1)粉碎粒径为30~70nm。
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