CN113634587A - 一种利用菱镁矿脱硫及硫的资源化利用方法 - Google Patents
一种利用菱镁矿脱硫及硫的资源化利用方法 Download PDFInfo
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- CN113634587A CN113634587A CN202110984039.1A CN202110984039A CN113634587A CN 113634587 A CN113634587 A CN 113634587A CN 202110984039 A CN202110984039 A CN 202110984039A CN 113634587 A CN113634587 A CN 113634587A
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- 239000001095 magnesium carbonate Substances 0.000 title claims abstract description 56
- 229910000021 magnesium carbonate Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 55
- 235000014380 magnesium carbonate Nutrition 0.000 title claims abstract description 54
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 21
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 18
- 239000011593 sulfur Substances 0.000 title claims abstract description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 22
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- 239000001301 oxygen Substances 0.000 claims abstract description 7
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 238000005086 pumping Methods 0.000 claims abstract description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
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- 238000001035 drying Methods 0.000 claims description 7
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- 239000000376 reactant Substances 0.000 claims description 4
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- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
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- 229910052748 manganese Inorganic materials 0.000 claims description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
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- 239000002253 acid Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
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- 239000012467 final product Substances 0.000 description 3
- 239000013082 iron-based metal-organic framework Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract
本发明公开一种利用菱镁矿脱硫及硫的资源化利用方法,属于工业固体废弃物资源化处理技术领域;本发明将将菱镁矿尾矿经破碎筛分,得菱镁矿尾矿颗粒;利用半熔法对菱镁矿尾矿颗粒进行焙烧,然后采用水闪蒸干法迅速降温形成Mg(OH)2气溶胶;将Mg(OH)2气溶胶泵入吸收氧化塔内,使其与吸收塔内的催化剂、氧气、含SO2的工业废气接触形成MgSO4浆液;MgSO4浆液经蒸发结晶获得MgSO4•7H2O;本方法在脱硫的同时一步制得MgSO4产品,具有烟气脱硫效率高、设备投资及运用维护费用低、不产生污水、副产品能综合回收等优点,能实现了工业固体废弃物和废气的资源化利用。
Description
技术领域
本发明属于工业固体废弃物资源化处理技术领域,涉及一种利用菱镁矿脱硫及硫的资源化利用的方法。
背景技术
我国是世界上菱镁矿储量最为丰富的国家,总储量位居世界第一,其主要成分为MgCO3, 含有少量Si、Ca、Fe和Al等杂质元素;这些菱镁矿绝大部分用于冶金行业,同时在菱镁矿的开采过程中大约产生30-50%的尾矿,到目前为止,已产生的尾矿据不完全统计已有80.5亿吨,且每年仍以3-4亿吨的速度增长;这些尾矿占用了大量的空间,浪费了宝贵的资源,造成了严重的环境污染。
硫酸镁主要应用在农业、环保工业、建材行业、建筑业中;硫酸镁在农业领域的水产养殖作用是有利于阳性菌的生长,使水产更丰收;环保工业上,其作为污水处理剂直接使用或作为污水处理剂的一种原料用于工业污水处理,对废液污水起到凝结和沉降作用,使其达到排污标准;在建材行业中,其溶于水后与重质轻烧粉(氧化镁)发生反应形成硫氧镁水泥,此水泥具有较好的保温性、耐火性、耐久性及环保性,应用于防火板、外墙保温板、门芯板、硫酸镁板等的生产;在建筑行业中七水硫酸镁可以用作水泥的助凝剂。
因此,利用菱镁矿尾矿制备MgSO4•7H2O是当前菱镁矿尾矿的重要资源化途径。当前,对菱镁矿尾矿制备MgSO4•7H2O的处理方法主要为酸法,即将矿石在700-900℃轻烧得到的轻烧镁粉,然后与一定浓度的硫酸反应,将MgO浸出,再进一步制备MgSO4•7H2O产品。但由于酸具有强腐蚀性,对设备要求高,且酸的用量和中和用碱量都很大,产生大量含酸、碱的废水,因此该方法不易实现工业化生产。申请号201710439295公开了一种低品位菱镁矿镁碳双利用方法,该方法利用浮选后的菱镁矿与硫酸反应来制备MgSO4•7H2O,但整个过程工艺复杂,操作要求高。申请号202010776040公开了一种菱镁矿尾矿制备硫酸镁的方法,该方法中采用破碎、煅烧、硫酸酸化和结晶制备硫酸镁晶体,但整个过程能耗高、有废水产生,造成环境的二次污染。因此,在菱镁矿尾矿资源化利用制备MgSO4•7H2O亟需低成本、无大量废水产生的新工艺技术。
目前,利用菱镁矿一步脱硫同时制备MgSO4•7H2O的方法未见到报道。
发明内容
本发明目的在于提供一种利用菱镁矿脱硫及硫的资源化利用方法,即将菱镁矿尾矿进行破碎筛分后进行半熔法焙烧,焙烧后的菱镁矿外部成分主要为MgO;随后经水闪蒸干法,利用高温条件下MgO与H2O反应生成Mg(OH)2,且利用水的蒸发潜热使焙烧炉迅速降温,形成Mg(OH)2气溶胶;经循环泵将Mg(OH)2气溶胶泵入吸收氧化塔喷淋层,利用SO2气体具有的酸性与Mg(OH)2气溶胶的碱性进行反应生成MgSO3浆液,MgSO3浆液在催化剂与氧气作用下进行催化氧化反应形成MgSO4浆液;生成的MgSO4浆液经过蒸发结晶后形成MgSO4•7H2O。
所述菱镁矿尾矿颗粒粒径小于100目,目的是将菱镁矿尾矿中的MgCO3完全暴露。
所述半熔法焙烧是在600-900℃下焙烧0.5-4h,其目的是在该条件下会完全分解生成MgO。
采用水闪蒸干法形成Mg(OH)2气溶胶是将沸腾的水经雾化器雾化,雾化后的雾滴进入焙烧炉后与高温的MgO接触,吸收MgO表面的温度且与其进行反应,烟气温度迅速降低至200-350℃,形成Mg (OH)2气溶胶;水蒸气量1-8t/h;
在吸收氧化塔喷淋层中Mg (OH)2气溶胶通过化学吸附与体积浓度1%-30%的SO2气体形成MgSO3浆液,催化剂使整个过程脱硫效率更高,SO2流量为5-35万Nm3/h;氧气的来源为空气,空气流速为3-20万Nm3/h,其目的是通过气-固-液反应,在催化剂上发生催化氧化作用,生成MgSO4浆液,可防止因MgSO4晶体堵塞催化剂活性位点造成催化剂中毒的问题,提高催化剂耐久性。
所述催化剂为采用水热法制得双金属催化剂,以MOF材料为载体,金属Ⅰ和金属Ⅱ为活性组分,金属Ⅰ为Ni、Cu、Ca或Mn,金属Ⅱ为Mo、Co、Ce、Cu或Fe具体制备工艺如下:
(1)在去离子水中加入均苯三甲酸、三乙胺、金属Ⅱ的盐,搅拌混匀后,转移到反应釜中,在 180-200℃下反应20-24h,反应物离心获得沉淀物,沉淀物用去离子水洗涤3-4次,得金属Ⅱ-MOF催化剂,其中均苯三甲酸与三乙胺的质量体积比g:mL为1:1.5-2.5,均苯三甲酸与金属Ⅱ的盐的质量比为1:1.2-1.5; (2)将金属Ⅱ-MOF催化剂、金属Ⅰ的盐溶液、硝酸混合后转移到不锈钢高压釜中,在150-170℃下加热8-10h,固液分离,固体用去离子水清洗并干燥,最后在N2气氛下煅烧2h,即得双金属催化剂,其中金属Ⅱ-MOF催化剂、金属Ⅰ的盐、硝酸的质量比为1:1:1~1.1:1:1.4。
所述蒸发结晶是将MgSO4浆液脱去一部分水形成MgSO4•7H2O;蒸发结晶温度为40-100℃,步骤(2)反应过程中尾矿在高温条件下与水进行接触后会生成一些小颗粒物质,存在于Mg(OH)2气溶胶中;在结晶过程中,MgSO4浆液中的这些小颗粒物质为MgSO4结晶提供了晶核,加快MgSO4浆液结晶;结晶后形成的产物MgSO4•7H2O的纯度高达99%以上。
本发明与现有技术相比具有的优点:
(1)本发明提高了菱镁矿行业资源的利用率,极大改善了因抛弃资源的堆存对周边环境的严重影响;
(2)本发明整个过程以废治废,无废水排出,无二次污染,节约成本,尾气资源化高效利用,对环境保护具有重要的意义,提高企业的经济效益,有利于企业实行规模化应用;
(3)整个过程操作简单,可针对不同类型的含硫尾气来进行处理,适用范围广;
(4)本发明方法在脱硫的同时就能直接制得MgSO4产品,且方法简单,整个过程无污水产生,热能消耗低,节约了处理成本,回收了菱镁矿尾矿中的镁资源,菱镁矿中的镁资源利用率达到95%以上,对工业废气中的SO2进行高效利用,产生了社会效益。
附图说明
图1为本发明菱镁矿脱硫及硫的资源化工艺流程图。
具体实施方式
下面通过实施例对本发明做进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:本菱镁矿脱硫及硫的资源化利用方法步骤如下:
1、FeMn双金属催化剂采用水热法制得,具体为在去离子水中加入均苯三甲酸、三乙胺、硝酸铁,搅拌混匀后,转移到反应釜中,在 190℃下反应24h,反应物在6000r/min下离心获得沉淀物,沉淀物用去离子水洗涤3次,得Fe-MOF催化剂,其中均苯三甲酸与三乙胺的质量体积比g:mL为1:2.0,均苯三甲酸与硝酸锰的质量比为1:1.2;将Fe-MOF催化剂、硝酸锰溶液、硝酸混合后转移到不锈钢高压釜中,在160℃下加热9h,固液分离,固体用去离子水清洗并干燥,最后在N2气氛下煅烧2h,即得FeMn双金属催化剂,其中Fe-MOF催化剂、硝酸锰、硝酸的质量比为1:1:1;
2、如图1所示,本实施例采用的菱镁矿尾矿来自于云南省某采矿企业的尾矿(Mg元素平均含量为23.1%),将该尾矿在破碎机中破碎筛分后得到100目以下的菱镁矿尾矿颗粒;取5t的菱镁矿尾矿颗粒置于焙烧炉中,在600℃下焙烧4h,焙烧结束后,气化的水(5t/h)通过焙烧炉顶部的雾化器进入焙烧炉,焙烧炉内温度迅速降低至340℃,随后产生的气体经循环泵进入吸收氧化塔,吸收氧化塔中通过固定床将FeMn双金属催化剂进行固定,吸收氧化塔同时通入某铜冶炼厂艾萨炉的制酸尾气(10.2%SO2,15万Nm3/h)以及空气,检测到吸收氧化塔出口处的SO2浓度为0.1%,吸收塔的脱硫效率为99.0%,形成的MgSO3浆液在FeMn双金属催化剂、氧气(空气流速为15万Nm3/h)作用下进行催化氧化反应形成MgSO4浆液;MgSO4浆液在55℃条件下蒸发结晶,得到最终产物MgSO4•7H2O;经测定,MgSO4•7H2O的纯度为99.2%,且产量为11.6t,则计算所得菱镁矿尾矿中的镁的利用率为98.0%,催化剂的催化效率达96.4%。上述所有的操作属于一个流程,当该流程完成后,重复操作该工艺流程,当催化效率低于95%时,催化剂失活,发现该工艺持续时间为785h。
实施例2:本菱镁矿脱硫及硫的资源化利用方法步骤如下:
1、CeNi双金属催化剂采用水热法制得,具体为在去离子水中加入均苯三甲酸、三乙胺、硝酸铈,搅拌混匀后,转移到反应釜中,在200℃下反应20h,反应物在6000r/min下离心获得沉淀物,沉淀物用去离子水洗涤4次,得Ce-MOF催化剂,其中均苯三甲酸与三乙胺的质量体积比g:mL为1:1.8,均苯三甲酸与硝酸铈的盐的质量比为1:1.4;将Ce-MOF催化剂、硝酸镍溶液、硝酸混合后转移到不锈钢高压釜中,在150℃下加热10h,固液分离,固体用去离子水清洗并干燥,最后在N2气氛下煅烧2h,即得CeNi双金属催化剂,其中Ni-MOF催化剂、硝酸镍、硝酸的质量比为1:1:1.2;
2、采用的菱镁矿(MgCO3)来自于江西省某采矿企业的尾矿(Mg元素平均含量为24.8%),将该尾矿在破碎机中破碎筛分后得到100目以下的菱镁矿尾矿颗粒;取4t的菱镁矿尾矿颗粒置于焙烧炉中,焙烧温度为850℃,焙烧时间为1h;焙烧结束后,气化的水(水蒸气量7t/h)通过焙烧炉顶部的雾化器进入焙烧炉,焙烧炉内温度迅速降低至280℃,随后产生的气体经循环泵进入吸收氧化塔,吸收氧化塔中通过固定床将CeNi双金属催化剂进行固定,吸收氧化塔同时通入某锌冶炼厂的制酸尾气(2.4% SO2,流量为10万Nm3/h)以及空气,检测到吸收塔出口处的SO2浓度为0.01%,吸收塔的脱硫效率为99.6%,MgSO3浆液在催化剂、氧气(空气流速为8万Nm3/h)作用下进行催化氧化反应形成MgSO4浆液,MgSO4浆液在85℃下蒸发结晶,得到最终产物MgSO4•7H2O;经测定,MgSO4•7H2O的纯度为99.7%,且产量为10.06t,则计算所得菱镁矿尾矿中的镁的利用率为98.9%,催化剂的催化效率达97.2%;上述所有的操作属于一个流程,当该流程完成后,重复操作该工艺流程,当催化效率低于95%时,催化剂失活,发现该工艺持续时间为805h。
实施例3:本菱镁矿脱硫及硫的资源化利用方法步骤如下:
1、CoCa双金属催化剂采用水热法制得,具体为在去离子水中加入均苯三甲酸、三乙胺、硝酸钴,搅拌混匀后,转移到反应釜中,在180℃下反应24h,反应物在6000r/min下离心获得沉淀物,沉淀物用去离子水洗涤3次,得Co-MOF催化剂,其中均苯三甲酸与三乙胺的质量体积比g:mL为1:2.2,均苯三甲酸与硝酸钴的盐的质量比为1:1.5;将Co-MOF催化剂、硝酸钙溶液、硝酸混合后转移到不锈钢高压釜中,在170℃下加热8h,固液分离,固体用去离子水清洗并干燥,最后在N2气氛下煅烧2h,即得CoCa双金属催化剂,其中Co-MOF催化剂、硝酸钙、硝酸的质量比为1:1:1.4;
2、采用的菱镁矿(MgCO3)来自于贵州省某采矿企业的尾矿(Mg元素平均含量为25.2%),将该尾矿在破碎机中破碎筛分后得到100目以下的菱镁矿尾矿颗粒;取5t的菱镁矿尾矿颗粒置于焙烧炉中,焙烧温度为750℃,焙烧时间为2h;焙烧结束后,气化的水(气量2t/h)通过焙烧炉顶部的雾化器进入焙烧炉,焙烧炉内温度迅速降低至300℃,随后产生的气体经循环泵进入吸收氧化塔,吸收氧化塔中通过固定床将CoCa双金属催化剂进行固定,塔中同时通入某铜冶炼厂熔炉的制酸尾气(8.6% SO2,流量为10万Nm3/h)以及空气,检测到吸收塔出口处的SO2浓度为0.06%,吸收塔的脱硫效率为99.3%,MgSO3浆液在催化剂、氧气(空气流速为5万Nm3/h)作用下进行催化氧化反应形成MgSO4浆液,MgSO4浆液在65℃条件下蒸发结晶,得到最终产物MgSO4•7H2O;经测定,MgSO4•7H2O的纯度为99.7%,且产量为12.73t,则计算所得菱镁矿尾矿中的镁的利用率为98.5%,催化剂的催化效率达97.2%;上述所有的操作属于一个流程,当该流程完成后,重复操作该工艺流程,当催化效率低于95%时,催化剂失活,发现该工艺持续时间为792h。
Claims (8)
1.一种利用菱镁矿脱硫及硫的资源化利用方法,其特征在于,步骤如下:
(1)将菱镁矿尾矿经破碎筛分,得菱镁矿尾矿颗粒;
(2)利用半熔法对菱镁矿尾矿颗粒进行焙烧,然后采用水闪蒸干法迅速降温形成Mg(OH)2气溶胶;
(3)将Mg(OH)2气溶胶泵入吸收氧化塔内,使其与吸收塔内的催化剂、氧气、含SO2的工业废气接触形成MgSO4浆液;MgSO4浆液经蒸发结晶获得MgSO4•7H2O。
2.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:菱镁矿尾矿颗粒粒径小于100目。
3.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:半熔法焙烧是在600-900℃下焙烧0.5-4h。
4.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:采用水闪蒸干法形成Mg(OH)2气溶胶是在焙烧结束后将气化的水通过雾化器雾化后通入焙烧炉中,烟气温度迅速降低至200-350℃,产生的气体即为Mg(OH)2气溶胶。
5.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:催化剂为采用水热法制得双金属催化剂,以MOF材料为载体,金属Ⅰ和金属Ⅱ为活性组分,金属Ⅰ为Ni、Cu、Ca或Mn,金属Ⅱ为Mo、Co、Ce、Cu或Fe。
6.根据权利要求5所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于,双金属催化剂的制备如下:
(1)在去离子水中加入均苯三甲酸、三乙胺、金属Ⅱ的盐,搅拌混匀后,转移到反应釜中,在 180-200℃下反应20-24h,反应物离心获得沉淀物,沉淀物用去离子水洗涤3-4次,得金属Ⅱ-MOF催化剂,其中均苯三甲酸与三乙胺的质量体积比g:mL为1:1.5-2.5,均苯三甲酸与金属Ⅱ的盐的质量比为1:1.2-1.5; (2)将金属Ⅱ-MOF催化剂、金属Ⅰ的盐溶液、硝酸混合后转移到不锈钢高压釜中,在150-170℃下加热8-10h,固液分离,固体用去离子水清洗并干燥,最后在N2气氛下煅烧2h,即得双金属催化剂,其中金属Ⅱ-MOF催化剂、金属Ⅰ的盐、硝酸的质量比为1:1:1~1.1:1:1.4。
7.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:工业废气中的SO2体积浓度为1%-30%。
8.根据权利要求1所述的利用菱镁矿脱硫及硫的资源化利用方法,其特征在于:蒸发结晶温度为40-100℃。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115026107A (zh) * | 2022-06-09 | 2022-09-09 | 北京科技大学 | 一种利用高碳石煤对脱硫石膏进行脱硫的方法 |
CN115055052A (zh) * | 2022-05-27 | 2022-09-16 | 广东能源集团科学技术研究院有限公司 | 一种高效催化脱硫剂及其应用 |
Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB561549A (en) * | 1942-08-17 | 1944-05-24 | Percy Parrish | Process of treating waste pickle liquors |
JPS5232896A (en) * | 1975-09-10 | 1977-03-12 | Mitsubishi Heavy Ind Ltd | Improved wet recovery process of sulfur in the waste gas as gypsum wit h lime |
DE2727196A1 (de) * | 1976-06-18 | 1977-12-22 | Patrick John Mcgauley | Verfahren zur herstellung und verwendung von absorbierenden feststoffen |
FR2459209A1 (fr) * | 1979-06-14 | 1981-01-09 | Ustav Pro Vyzkum Rud | Procede pour l'elimination de composes indesirables a partir de matieres brutes contenant de la magnesite |
CA2159521A1 (en) * | 1994-10-07 | 1996-04-08 | Shigeo Iiyama | Method for Desulfurizing Exhaust Gas |
JP2000288338A (ja) * | 1999-04-07 | 2000-10-17 | Ishikawajima Harima Heavy Ind Co Ltd | 排煙脱硫廃棄物の処理方法及びその装置 |
CN1524819A (zh) * | 2003-09-15 | 2004-09-01 | 吴太洲 | 菱镁矿清洁循环经济加工生产方法 |
CN1727055A (zh) * | 2005-07-26 | 2006-02-01 | 六合天融(北京)环保科技有限公司 | 利用菱镁矿石粉进行烟气脱硫的方法 |
CN1733656A (zh) * | 2005-08-01 | 2006-02-15 | 六合天融(北京)环保科技有限公司 | 利用锅炉烟气制取七水硫酸镁肥料的方法 |
CN101480565A (zh) * | 2008-01-07 | 2009-07-15 | 宝山钢铁股份有限公司 | 一种镁质用后耐材用于烟气脱硫后的产物回收的方法 |
CN102225307A (zh) * | 2011-04-20 | 2011-10-26 | 成都信息工程学院 | 有机酸强化电石渣烟气脱硫技术 |
CN203342639U (zh) * | 2013-06-20 | 2013-12-18 | 义马煤业集团煤生化高科技工程有限公司 | 一种含硫化氢的化工酸性废气的回收治理装置 |
CN105457479A (zh) * | 2015-12-31 | 2016-04-06 | 上海世渊环保科技有限公司 | 一种烟气脱硫零排放资源处理系统及方法 |
WO2016086733A1 (zh) * | 2014-12-03 | 2016-06-09 | 童裳慧 | 烟气脱硫生产水泥的装置及方法 |
CN107365092A (zh) * | 2017-07-24 | 2017-11-21 | 辽宁东和新材料股份有限公司 | 一种尾矿生产高品位电熔镁的生产装置 |
RU2674967C1 (ru) * | 2017-08-24 | 2018-12-13 | Закрытое акционерное общество "ЦТК-Евро" | Способ очистки высокотемпературных аэрозолей |
CN109422284A (zh) * | 2017-08-24 | 2019-03-05 | 程相魁 | 烟气脱硫与燃气脱氨污染物资源化以废治废的联合方法 |
JP2019055383A (ja) * | 2017-09-22 | 2019-04-11 | 宇部マテリアルズ株式会社 | 排煙脱硫方法及びそれに用いる水酸化マグネシウムスラリー |
CN110090550A (zh) * | 2019-04-17 | 2019-08-06 | 昆明理工大学 | 一种基于镁盐预热分解的焦炉烟气脱硫方法 |
CN111330439A (zh) * | 2020-03-25 | 2020-06-26 | 韩建英 | 一种船舶烟气催化氧化脱硫方法 |
CN111495165A (zh) * | 2020-06-05 | 2020-08-07 | 昆明理工大学 | 一种含镁矿石脱硫脱硝浆液和一种同步脱硫脱硝的方法 |
CN112320826A (zh) * | 2020-10-29 | 2021-02-05 | 刘峰 | 用低品位菱镁矿联合制备高纯氧化镁和精制硫酸铵的方法 |
CN112691644A (zh) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | 一种双金属MOFs负载氧化铝小球的制备方法与应用 |
-
2021
- 2021-08-25 CN CN202110984039.1A patent/CN113634587B/zh active Active
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB561549A (en) * | 1942-08-17 | 1944-05-24 | Percy Parrish | Process of treating waste pickle liquors |
JPS5232896A (en) * | 1975-09-10 | 1977-03-12 | Mitsubishi Heavy Ind Ltd | Improved wet recovery process of sulfur in the waste gas as gypsum wit h lime |
DE2727196A1 (de) * | 1976-06-18 | 1977-12-22 | Patrick John Mcgauley | Verfahren zur herstellung und verwendung von absorbierenden feststoffen |
FR2459209A1 (fr) * | 1979-06-14 | 1981-01-09 | Ustav Pro Vyzkum Rud | Procede pour l'elimination de composes indesirables a partir de matieres brutes contenant de la magnesite |
CA2159521A1 (en) * | 1994-10-07 | 1996-04-08 | Shigeo Iiyama | Method for Desulfurizing Exhaust Gas |
JP2000288338A (ja) * | 1999-04-07 | 2000-10-17 | Ishikawajima Harima Heavy Ind Co Ltd | 排煙脱硫廃棄物の処理方法及びその装置 |
CN1524819A (zh) * | 2003-09-15 | 2004-09-01 | 吴太洲 | 菱镁矿清洁循环经济加工生产方法 |
CN1727055A (zh) * | 2005-07-26 | 2006-02-01 | 六合天融(北京)环保科技有限公司 | 利用菱镁矿石粉进行烟气脱硫的方法 |
CN1733656A (zh) * | 2005-08-01 | 2006-02-15 | 六合天融(北京)环保科技有限公司 | 利用锅炉烟气制取七水硫酸镁肥料的方法 |
CN101480565A (zh) * | 2008-01-07 | 2009-07-15 | 宝山钢铁股份有限公司 | 一种镁质用后耐材用于烟气脱硫后的产物回收的方法 |
CN102225307A (zh) * | 2011-04-20 | 2011-10-26 | 成都信息工程学院 | 有机酸强化电石渣烟气脱硫技术 |
CN203342639U (zh) * | 2013-06-20 | 2013-12-18 | 义马煤业集团煤生化高科技工程有限公司 | 一种含硫化氢的化工酸性废气的回收治理装置 |
WO2016086733A1 (zh) * | 2014-12-03 | 2016-06-09 | 童裳慧 | 烟气脱硫生产水泥的装置及方法 |
CN105457479A (zh) * | 2015-12-31 | 2016-04-06 | 上海世渊环保科技有限公司 | 一种烟气脱硫零排放资源处理系统及方法 |
CN107365092A (zh) * | 2017-07-24 | 2017-11-21 | 辽宁东和新材料股份有限公司 | 一种尾矿生产高品位电熔镁的生产装置 |
RU2674967C1 (ru) * | 2017-08-24 | 2018-12-13 | Закрытое акционерное общество "ЦТК-Евро" | Способ очистки высокотемпературных аэрозолей |
CN109422284A (zh) * | 2017-08-24 | 2019-03-05 | 程相魁 | 烟气脱硫与燃气脱氨污染物资源化以废治废的联合方法 |
JP2019055383A (ja) * | 2017-09-22 | 2019-04-11 | 宇部マテリアルズ株式会社 | 排煙脱硫方法及びそれに用いる水酸化マグネシウムスラリー |
CN110090550A (zh) * | 2019-04-17 | 2019-08-06 | 昆明理工大学 | 一种基于镁盐预热分解的焦炉烟气脱硫方法 |
CN112691644A (zh) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | 一种双金属MOFs负载氧化铝小球的制备方法与应用 |
CN111330439A (zh) * | 2020-03-25 | 2020-06-26 | 韩建英 | 一种船舶烟气催化氧化脱硫方法 |
CN111495165A (zh) * | 2020-06-05 | 2020-08-07 | 昆明理工大学 | 一种含镁矿石脱硫脱硝浆液和一种同步脱硫脱硝的方法 |
CN112320826A (zh) * | 2020-10-29 | 2021-02-05 | 刘峰 | 用低品位菱镁矿联合制备高纯氧化镁和精制硫酸铵的方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115055052A (zh) * | 2022-05-27 | 2022-09-16 | 广东能源集团科学技术研究院有限公司 | 一种高效催化脱硫剂及其应用 |
CN115055052B (zh) * | 2022-05-27 | 2023-06-16 | 广东能源集团科学技术研究院有限公司 | 一种高效催化脱硫剂及其应用 |
CN115026107A (zh) * | 2022-06-09 | 2022-09-09 | 北京科技大学 | 一种利用高碳石煤对脱硫石膏进行脱硫的方法 |
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