CN107926973A - 一种环保型杀菌剂及其制备方法 - Google Patents
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Classifications
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- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
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- A—HUMAN NECESSITIES
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
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- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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Abstract
本发明公开了一种环保型杀菌剂及其制备方法,以质量份数,首先将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,在搅拌和加热状态下将混合物的一半加入反应釜中,待物料熔融后,再加入另一半混合物进行反应,当反应结束后得到产品A;然后将100份硝酸铵和143份尿素在熔融条件下,加入7份催化剂,经反应得到产品B;最后将8‑10份产品A和1份产品B混合后加入2‑3份胺类化合物先加热熔融,后升温反应,然后降温至室温,得到预制品,将预制品和1‑2份月桂酰类化合物复配后即得到压裂用环保型杀菌剂。本发明可以有效解决利用植物胶压裂后返排液受细菌影响容易腐败的问题,对压裂返排液回收再利用过程中液体保存具有重要的作用。
Description
技术领域
本发明属于油田增产领域,具体涉及一种环保型杀菌剂及其制备方法。
背景技术
压裂作为油气藏的主要增产、增注措施已得到迅速发展和广泛应用。压裂就是利用压力将地层压开形成裂缝,并用支撑剂将它支撑起来,以减小流体流动阻力的增产、增注措施。压裂的目的就是在地层中形成具有导流能力的裂缝,采用的压裂液在很大程度上决定了压裂效果,同时对压裂液的粘度有一定要求,使其在压裂后能称为低粘度的流体容易返排,以避免对地层中的油气层造成损坏。
水力压裂技术是低渗储层改造的关键技术,水力压裂需要消耗大量淡水,对当地水资源造成影响,而在水资源匮乏地区,这种影响尤为严重。目前国内环保要求显著提高,随着油田开发的深入,长庆油田每年压裂现场有大量的压裂返排液,无害化处理成本高效率低。压裂用水供求矛盾日益突出,因此,如果能使用压裂返排液配制压裂液,对于油田的绿色开发和降本增效意义重大。
压裂返排液在回收后保存时,细菌会大量繁殖,引起返排液水质变质,变黑变臭,从而影响压裂返排液重复再利用,尤其是植物胶类压裂液,影响尤其严重。因此需要加入一种杀菌剂以抑制细菌的繁殖。
目前油田所使用的杀菌剂按其杀菌机理可分为有氧型和非氧型杀菌剂。但是在长庆油田,压裂返排液中有机质含量很高,通常需要大量的氧化剂才能达到杀菌的目的,杀菌效果不佳,而且会增加腐蚀。非氧化性杀菌剂用的最多的是季铵盐类、季鏻盐、烷基胍及复合杀菌剂,季鏻盐类杀菌剂由于其成本高难易工业化推广,季铵盐是最普通和最有效的杀菌剂之一,不仅具有杀菌作用,而且对杀菌活性组分还具有增效作用,对黏泥也有很强的剥离作用,但是季铵盐也有不足,如水中含有许多悬浮颗粒、乳化油珠等负电性的物质,它们都会与季铵盐发生相互作用,使其不能与细胞壁产生静电吸引作用而减低其杀菌活性甚至失效。
发明内容
本发明的目的在于提供一种环保型杀菌剂及其制备方法,以克服上述现有技术存在的缺陷,本发明通过溶解脂质,改变细菌细胞膜的通透性,使菌体内的代谢发生障碍而抗菌,以满足压裂返排液保存的需要。
为达到上述目的,本发明采用如下技术方案:
一种环保型杀菌剂,以质量份数计,环保性杀菌剂的制备原料包括:8-10份产品A,1份产品B,2-3份胺类化合物以及1-2份月桂酰类化合物;
以质量份数计,所述产品A的制备原料包括:336份双氰胺,400份氯化铵以及20份碳酸铵;
以质量份数计,所述产品B的制备原料包括:100份硝酸铵,143份尿素以及7份催化剂。
进一步地,所述的胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺。
进一步地,所述的月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺。
进一步地,所述的催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝。
一种环保型杀菌剂的制备方法,包括以下步骤:
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,在搅拌和加热状态下将混合物的一半加入反应釜中,待物料熔融后,再加入另一半混合物进行反应,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在熔融条件下,加入7份催化剂,经反应得到产品B;
步骤三:以质量份数计,将8-10份产品A和1份产品B混合后加入2-3份胺类化合物先加热至110-130℃熔融反应1小时,后升温至180℃后反应2小时,通过降温将体系降温至室温,得到预制品,将预制品和1-2份月桂酰类化合物复配后即得到压裂用环保型杀菌剂。
进一步地,步骤一整个过程中反应釜的温度保持在180-200℃,加入另一半混合物后反应2-3小时。
进一步地,步骤二中熔融的温度为180℃,加入催化剂后反应5小时得到产品B。
进一步地,所述的催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝。
进一步地,所述的胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺。
进一步地,所述的月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺。
与现有技术相比,本发明具有以下有益的技术效果:
本发明的环保型杀菌剂具有有效浓度低、作用速度快、性质稳定、易溶于水的优良性能;可在常温下使用;能够长期抑菌、无副作用;无腐蚀性;无色、无嗅;无毒;不燃、不爆、使用安全;价格适中;运输方便。其抗菌作用主要是通过溶解脂质,改变细菌细胞膜的通透性,使菌体内的代谢发生障碍而抗菌,以满足压裂返排液保存的需要。
本发明的环保型杀菌剂可以在超低浓度0.01%-0.05%条件下,保持压裂返排液保存30天以上,性能下降率小于2%,细菌含量控制在102以内;该杀菌剂属于中性产品,对金属容器没有腐蚀;溶于水中不会电离,与压裂返排液中的悬浮物、污油等带电荷的物质不会产生吸附;不会与压裂返排液反应结垢;通过阻止细菌代谢进行杀菌,从根本上抑制可以细菌滋生;属于环保清洁型产品,无毒无害,杀菌效果明显。
本发明方法制备的环保型杀菌剂可以有效解决利用植物胶压裂后返排液受细菌影响容易腐败的问题,具有良好的配伍性,能有效杀灭并抑制植物胶类压裂返排液中的铁细菌、腐生菌、硫酸盐还原菌,对压裂返排液回收再利用过程中液体保存具有重要的作用。
附图说明
图1是本发明实施例1所得产品的红外谱图;
图2是本发明实施例2所得产品的核磁共振表征图;
图3是本发明实施例3所得产品的红外谱图。
具体实施方式
下面对本发明的实施方式做进一步详细描述:
一种环保型杀菌剂,以质量份数计,环保性杀菌剂的制备原料包括:8-10份产品A,1份产品B,2-3份胺类化合物以及1-2份月桂酰类化合物,其中,胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺,月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺;
以质量份数计,所述产品A的制备原料包括:336份双氰胺,400份氯化铵以及20份碳酸铵;
以质量份数计,所述产品B的制备原料包括:100份硝酸铵,143份尿素以及7份催化剂,其中催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝。
一种环保型杀菌剂的制备方法,包括以下步骤:
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,将混合物的一半加入180-200℃的反应釜中,边加入边搅拌,待物料熔融后,再加入另一半混合物进行反应2-3小时,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在180℃熔融条件下,加入7份催化剂,经反应5小时得到产品B,其中催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝;
步骤三:以质量份数计,将8-10份产品A和1份产品B混合后加入2-3份胺类化合物先加热至110-130℃熔融反应1小时,后升温至180℃后反应2小时,通过降温将体系降温至室温,得到常温下白色或乳白色的预制品,将预制品和1-2份月桂酰类化合物复配后即得到压裂用环保型杀菌剂,其中胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺,月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺。
下面结合实施例对本发明做进一步详细描述:
实施例1
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,将混合物的一半加入190℃的反应釜中,边加入边搅拌,待物料熔融后,再加入另一半混合物进行反应3小时,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在180℃熔融条件下,加入7份颗粒硅胶,经反应5小时得到产品B;
步骤三:以质量份数计,将10份产品A和1份产品B混合后加入3份1,6-己二胺先加热至120℃熔融反应1小时,后急剧升温至180℃后反应2小时,通过快速降温将体系降温至室温,得到常温下白色或乳白色的预制品,将预制品和2份月桂酰二亚丙基二胺复配后即得到压裂用环保型杀菌剂。
实施例2
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,将混合物的一半加入180℃的反应釜中,边加入边搅拌,待物料熔融后,再加入另一半混合物进行反应2小时,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在180℃熔融条件下,加入7份活性二氧化硅,经反应5小时得到产品B;
步骤三:以质量份数计,将8份产品A和1份产品B混合后加入2份三乙醇胺先加热至110℃熔融反应1小时,后急剧升温至180℃后反应2小时,通过快速降温将体系降温至室温,得到常温下白色或乳白色的预制品,将预制品和2份月桂酰胺两基甜菜碱复配后即得到压裂用环保型杀菌剂。
实施例3
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,将混合物的一半加入200℃的反应釜中,边加入边搅拌,待物料熔融后,再加入另一半混合物进行反应3小时,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在180℃熔融条件下,加入7份活性氧化铝,经反应5小时得到产品B;
步骤三:以质量份数计,将9份产品A和1份产品B混合后加入3份溴化四丁基铵先加热至130℃熔融反应1小时,后急剧升温至180℃后反应2小时,通过快速降温将体系降温至室温,得到常温下白色或乳白色的预制品,将预制品和1份月桂酰丙烯二胺复配后即得到压裂用环保型杀菌剂。
本发明实施例3制得的环保型杀菌剂与其他类型杀菌剂性能对比见表1:
表1实施例3的环保型杀菌剂与其他类型杀菌剂性能对比
本发明的环保型杀菌剂主要针对压裂返排液,压裂返排液具有易于细菌滋生的富氧条件,和细菌赖以生存的石油和稠化剂有机质,提供细菌喜欢的高温、潮湿环境,因此,细菌在此环境中具有超强的生存繁衍能力,同时压裂液在包括很多的表面活性剂、有机酸、聚合物及其弱酸弱碱等条件,这些无疑促进了细菌的滋生,因此,这种条件与一般杀菌剂使用的环境有着明显的差异,对杀菌剂性能提出了更高的要求。从表1可以看出,本发明的环保性杀菌剂对压裂返排液具有明显效果,可以在成份复杂的压裂返排液中使用较低浓度0.05%以内,保持性能95%以上以及30天以上,对细菌的抑制率在99%以上,可以控制细菌在102以内,配伍性良好,不结垢,不腐蚀,对带电物质没有吸附,中性,无毒无害,各项产品性能良好,效果明显。
Claims (10)
1.一种环保型杀菌剂,其特征在于,以质量份数计,环保性杀菌剂的制备原料包括:8-10份产品A,1份产品B,2-3份胺类化合物以及1-2份月桂酰类化合物;
以质量份数计,所述产品A的制备原料包括:336份双氰胺,400份氯化铵以及20份碳酸铵;
以质量份数计,所述产品B的制备原料包括:100份硝酸铵,143份尿素以及7份催化剂。
2.根据权利要求1所述的一种环保型杀菌剂,其特征在于,所述的胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺。
3.根据权利要求1所述的一种环保型杀菌剂,其特征在于,所述的月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺。
4.根据权利要求1所述的一种环保型杀菌剂,其特征在于,所述的催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝。
5.一种环保型杀菌剂的制备方法,其特征在于,包括以下步骤:
步骤一:以质量份数计,将336份双氰胺、400份氯化铵和20份碳酸铵混合均匀得到混合物,在搅拌和加热状态下将混合物的一半加入反应釜中,待物料熔融后,再加入另一半混合物进行反应,当反应结束后得到产品A;
步骤二:以质量份数计,将100份硝酸铵和143份尿素在熔融条件下,加入7份催化剂,经反应得到产品B;
步骤三:以质量份数计,将8-10份产品A和1份产品B混合后加入2-3份胺类化合物先加热至110-130℃熔融反应1小时,后升温至180℃后反应2小时,通过降温将体系降温至室温,得到预制品,将预制品和1-2份月桂酰类化合物复配后即得到压裂用环保型杀菌剂。
6.根据权利要求5所述的一种环保型杀菌剂的制备方法,其特征在于,
步骤一整个过程中反应釜的温度保持在180-200℃,加入另一半混合物后反应2-3小时。
7.根据权利要求5所述的一种环保型杀菌剂的制备方法,其特征在于,步骤二中熔融的温度为180℃,加入催化剂后反应5小时得到产品B。
8.根据权利要求5所述的一种环保型杀菌剂的制备方法,其特征在于,所述的催化剂为颗粒硅胶、活性二氧化硅或活性氧化铝。
9.根据权利要求5所述的一种环保型杀菌剂的制备方法,其特征在于,所述的胺类化合物为1,6-己二胺、三乙醇胺、二异丙胺、溴化四丁基铵或苯胺。
10.根据权利要求5所述的一种环保型杀菌剂的制备方法,其特征在于,所述的月桂酰类化合物为月桂酰胺两基甜菜碱、月桂酰二亚丙基二胺或月桂酰丙烯二胺。
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