CN106076405A - 一种去除草甘膦母液中甲醛催化剂及其制备方法和应用 - Google Patents
一种去除草甘膦母液中甲醛催化剂及其制备方法和应用 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000008367 deionised water Substances 0.000 claims description 8
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
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Abstract
本发明属于化学合成领域,一种去除草甘膦母液中甲醛催化剂,以过渡金属为活性组分,以MCM‑41分子筛为载体,其中活性组分与载体的质量比为5‑20:100。有益效果:与现有技术相比,本发明的优势在于:价格便宜、制备方法简单、易于工业化、具有很好的活性,去除草甘膦母液中甲醛的性能高。
Description
技术领域
本发明属于化学合成领域,尤其涉及一种去除草甘膦母液中甲醛催化剂及其制备方法和应用。
背景技术
草甘膦是20世纪70年代美国孟山都公司开发的一种灭生性除草剂,是目前世界上使用量最大的除草剂。草甘膦主要生产工艺路线之一是亚氨基二乙酸(IDA)路线,IDA路线是先经过亚氨基二乙酸合成双甘膦,双甘膦再氧化得到草甘膦。双甘膦氧化合成草甘膦是IDA路线的一个关键步骤,对整个IDA路线的生产效率和草甘膦质量起重要作用。双甘膦氧化分为化学氧化和催化氧化,其中双甘膦催化氧化一般采用氧气或者含氧气体做氧化剂,在催化剂的作用下,双甘膦催化氧化合成草甘膦,属于绿色化学范畴,并且产品收率和纯度均较高。
双甘膦催化氧化合成草甘膦通常采用活性炭做为催化剂,反应除生成草甘膦,还副产甲醛和甲酸。反应液经过过滤得到草甘膦盐,进一步得到草甘膦。甲醛和甲酸以及少量草甘膦盐溶解在过滤后的母液中,由于甲醛严重超标,直接排放会造成严重的环境污染。国内一般是是直接往母液中通氮生成盐后,浓缩制成10%的草甘膦氨盐水剂,直接作为商品销售。这种方法其实是甲醛随水剂产品的使用,转移到环境中,造成污染。国家农业部规定2010年起禁止生产10%含量的草甘膦水剂,要求作为商品的草甘膦含量不能低于30%。专利CN102206219 B公布了一种利用草甘膦母液中甲醛制备乌洛托品的方法,即含有草甘膦和甲醛组分的母液,经蒸发-冷凝分离或膜分离,获得甲醛稀溶液;然后将氨气通入甲醛稀溶液中,反应后生成乌洛托品稀溶液;在经过浓缩、结晶、分离、干燥得到乌洛托品产品。该方法工艺过程较复杂,能耗大,经济效益不高,特别是为了乌洛托品纯化,需要添加其他物质,不可避免地增加新的废物排放。
发明内容
本发明的目的是克服现有技术存在草甘膦母液中甲醛会以造成环境污染的缺陷,提供一种去除草甘膦母液中甲醛催化剂及其制备方法和应用。
本发明解决其技术问题所采用的技术方案是:一种去除草甘膦母液中甲醛催化剂,以过渡金属为活性组分,以MCM-41分子筛为载体,其中活性组分与载体的质量比为5-20:100。
进一步地,所述的过渡金属为Fe、Co、Ni、Mn、Cu和Zn中的一种或多种。
上述去除草甘膦母液中甲醛催化剂的制备方法,步骤如下:(1)分子筛溶胶的制备:将硅源加热溶于去离子水,在碱性条件下搅拌反应至溶液变为粘稠透明凝胶状,加入表面活性剂,搅拌反应形成白色凝胶状;
(2)将活性组分负载于载体:将过渡金属盐加入步骤(1)体系中,搅拌后静置,获得前驱体;
(3)将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在50-60℃烘箱内烘干20-24小时,经焙烧得到催化剂。
进一步地,步骤(1)所述在碱性条件下搅拌反应具体为,温度为40~50℃,滴加硫酸或氨水调节pH至8-9,搅拌反应10-60min;步骤(1)中加入表面活性剂后搅拌反应条件为在室温下搅拌10-60min。
作为优选,步骤(2)中搅拌时间为4-5h,静置之间为20-48h。
作为优选,步骤(3)中所述的烧焙条件为在400-600℃条件下烧焙3-10h。
进一步地,所述硅源为九水硅酸钠、正硅酸乙酯、硅酸四乙酯、硅溶胶或硅凝胶中的一种。
上述的催化剂应用于去除草甘膦母液中的甲醛。
具体地,将催化剂加入到草甘膦母液中进行搅拌反应,通入空气并保持0.5MPa的压力。
进一步地,所述催化剂与草甘膦母液质量体积比为1:100g/mL。
有益效果:与现有技术相比,本发明的优势在于:价格便宜、制备方法简单、易于工业化、具有很好的活性,去除草甘膦母液中甲醛的性能高。
具体实施方式
下面结合具体实施方案对本发明进行进一步描述,但本发明的保护范围并不限于此:
实施方案1
取10ml正硅酸乙酯加热至50℃溶于去离子水,滴加氨水至PH为8,搅拌20分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌30分钟,形成白色凝胶状,称取10g氯化铁加入混合液中,继续搅拌5小时,常温静置24小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在50℃烘箱内烘干24小时,之后取出在500℃焙烧6小时,得到分子筛催化剂A。
实施方案2
取10ml正硅酸乙酯加热至40℃溶于去离子水,滴加氨水至PH为9,搅拌10分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌10分钟,形成白色凝胶状,称取10g硝酸铁铁加入混合液中,继续搅拌4小时,常温静置20小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在60℃烘箱内烘干24小时,之后取出在600℃焙烧6小时,得到分子筛催化剂B。
实施方案3
取10ml硅酸四乙酯加热至45℃溶于去离子水,滴加氨水至PH为8.5,搅拌60分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌60分钟,形成白色凝胶状,称取10g硝酸镍加入混合液中,继续搅拌5小时,常温静置48小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在55℃烘箱内烘干20小时,之后取出在400℃焙烧10小时,得到分子筛催化剂C。
实施方案4
取10ml硅酸四乙酯加热至50℃溶于去离子水,滴加氨水至PH为9,搅拌40分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌30分钟,形成白色凝胶状,称取10g硝酸铜加入混合液中,继续搅拌4.5小时,常温静置24小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在50℃烘箱内烘干24小时,之后取出在600℃焙烧3小时,得到分子筛催化剂D。
实施方案5
取10g九水硅酸钠加热至50℃溶于去离子水,滴加硫酸至PH为8-9,搅拌20分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌30分钟,形成白色凝胶状,称取10g硫酸锰加入混合液中,继续搅拌5小时,常温静置24小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在60℃烘箱内烘干24小时,之后取出在600℃焙烧6小时,得到分子筛催化剂E。
实施方案6
取10g九水硅酸钠加热至50℃溶于去离子水,滴加硫酸至PH为8-9,搅拌20分钟,溶液变为粘稠透明凝胶状,加入2g十六烷基三甲基溴化铵,室温下搅拌30分钟,形成白色凝胶状,称取10g硝酸锌加入混合液中,继续搅拌5小时,常温静置24小时,获得前驱体,将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在50℃烘箱内烘干24小时,之后取出在500℃焙烧5小时,得到分子筛催化剂F。
量取草甘膦母液(初始甲醛浓度为50g/Kg)500ml,加入到反应釜中;称5g上述各实施例所制备的催化剂A-F,分别加入到反应釜中,反应釜内通入空气并保持压力0.5Mpa,搅拌速度为800r/min,5小时后,过滤,采用分光光度计分析反应后母液中甲醛含量,具体结果如表1,催化剂表现出很高的催化活性。
表1催化剂活性评价结果
催化剂 | A | B | C | D | E | F |
反应时间(小时) | 5 | 5 | 5 | 5 | 5 | 5 |
反应前甲醛浓度(g/kg) | 50 | 50 | 50 | 50 | 50 | 50 |
反应后甲醛浓度(g/kg) | 5.2 | 4.8 | 3.7 | 4.0 | 4.3 | 4.5 |
去除率(%) | 89.6 | 90.4 | 92.6 | 92 | 91.4 | 91 |
应当理解,以上所描述的具体实施例仅用于解释本发明,并不用于限定本发明。由本发明的精神所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (10)
1.一种去除草甘膦母液中甲醛催化剂,其特征在于:以过渡金属为活性组分,以MCM-41分子筛为载体,其中活性组分与载体的质量比为5-20:100。
2.根据权利要求1所述的去除草甘膦母液中甲醛催化剂,其特征在于:所述的过渡金属为Fe、Co、Ni、Mn、Cu和Zn中的一种或多种。
3.根据权利要求1或2所述的去除草甘膦母液中甲醛催化剂的制备方法,其特征在于:步骤如下:(1)分子筛溶胶的制备:将硅源加热溶于去离子水,在碱性条件下搅拌反应至溶液变为粘稠透明凝胶状,加入表面活性剂,搅拌反应形成白色凝胶状;
(2)将活性组分负载于载体:将过渡金属盐加入步骤(1)体系中,搅拌后静置,获得前驱体;
(3)将前驱体用布氏漏斗抽滤,蒸馏水洗去表面活性剂,在50-60℃烘箱内烘干20-24小时,经焙烧得到催化剂。
4.根据权利要求3所述的去除草甘膦母液中甲醛催化剂的制备方法,其特征在于:步骤(1)所述在碱性条件下搅拌反应具体为,温度为40~50℃,滴加硫酸或氨水调节pH至8-9,搅拌反应10-60min;步骤(1)中加入表面活性剂后搅拌反应条件为在室温下搅拌10-60min。
5.根据权利要求3所述的去除草甘膦母液中甲醛催化剂的制备方法,其特征在于:步骤(2)中搅拌时间为4-5h,静置之间为20-48h。
6.根据权利要求3所述的去除草甘膦母液中甲醛催化剂的制备方法,其特征在于:步骤(3)中所述的烧焙条件为在400-600℃条件下烧焙3-10h。
7.根据权利要求3所述的去除草甘膦母液中甲醛催化剂的制备方法,其特征在于:所述硅源为九水硅酸钠、正硅酸乙酯、硅酸四乙酯、硅溶胶或硅凝胶中的一种。
8.权利要求1~2任一项所述的催化剂应用于去除草甘膦母液中的甲醛。
9.根据权利要求8所述的应用,其特征在于:将催化剂加入到草甘膦母液中进行搅拌反应,通入空气并保持0.5MPa的压力。
10.根据权利要求9所述的应用,其特征在于:所述催化剂与草甘膦母液质量体积比为1:100g/mL。
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