WO2019127106A1 - 一种环保型高分子凝胶阻化剂及其制备方法和应用 - Google Patents

一种环保型高分子凝胶阻化剂及其制备方法和应用 Download PDF

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WO2019127106A1
WO2019127106A1 PCT/CN2017/119020 CN2017119020W WO2019127106A1 WO 2019127106 A1 WO2019127106 A1 WO 2019127106A1 CN 2017119020 W CN2017119020 W CN 2017119020W WO 2019127106 A1 WO2019127106 A1 WO 2019127106A1
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environment
gel inhibitor
polymer gel
friendly polymer
friendly
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PCT/CN2017/119020
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顾全
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常州坤宇环保科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

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  • the invention relates to a resisting agent, in particular to an environment-friendly polymer gel inhibitor and a preparation method and application thereof.
  • Coal spontaneous combustion can cause huge property losses, affect mining efficiency, and even cause gas explosions or underground fires, which seriously threaten the personal safety of mines and miners.
  • the main reason for the spontaneous combustion of coal is that the coal gradually releases heat during the oxidation process to achieve the environment required for spontaneous combustion. Therefore, the main principle of preventing spontaneous combustion of coal is to inhibit oxidation of coal and prevent heat accumulation.
  • the main inhibitors at this stage are mainly inorganic salt physical flame retardants such as NaCl, MgCl 2 and CaCl 2 . These flame retardants only absorb water on or around the coal to reduce the temperature of the coal. As time goes by, the coal The purpose of self-ignition can be achieved, and coal spontaneous combustion cannot be fundamentally suppressed.
  • the gel-based inhibitor can form a barrier film on the surface of the coal body to isolate the oxidation reaction between the coal body and the oxygen in the air to achieve a resistive effect; however, the water glass gel inhibitor has a large amount, a large volume shrinkage, and is easy to dry. Disadvantages such as cracking, organogel inhibitors tend to be poor in thermal stability, easy to burn, and costly.
  • the dust of the mine is mainly composed of ore particles and other powders, and is divided into dry dust and wet dust.
  • dust generation is mainly concentrated in the process of drilling and blasting, crushing, screening and belt conveying, transportation and reloading.
  • a complete mine processing production line needs to be crushed, sieved, ground, transported, aggregated, etc.
  • Each process, along with the fragmentation and movement of the ore, the fine-grained particles will be gradually separated, resulting in more and more More dust.
  • the smaller the particle size of the dust the less likely it is to settle in the air, which is difficult to capture.
  • the air flows it causes long-term and large-scale pollution, and it is easy to inhale into the deep part of the respiratory tract with the air, and the harm to the human body is also greater.
  • Some flammable mine dust can even have an explosive hazard.
  • Superabsorbent resin is a macromolecule containing a hydrophilic group and a crosslinked structure. It is classified into starch-based derivatives (grafts, carboxymethylated, etc.), cellulose-based derivatives (carboxymethylated, grafted, etc.), and synthetic polymers (polyacrylic acid, polyvinyl alcohol). , polyoxyethylene, etc.) several major categories.
  • Superabsorbent resin can generally absorb water equivalent to 100 times the volume of the resin, and is widely used in disposable sanitary products, agricultural water retention agents, industrial dust suppressants, and the like.
  • the superabsorbent resin needs to be formulated into a solution.
  • the superabsorbent resin tends to agglomerate during the formulation of the solution, which may cause the phenomenon of clogging the nozzle, the pipe, etc., thereby increasing the use cost, which is not conducive to large-scale promotion.
  • the solid dust suppressant can dilute the product with water when diluted, add water, or stir while adding water.
  • the stirring speed is controlled at 50-100 rpm, the stirring time is 3-5 minutes, and the time is slightly longer. If the addition is too fast, there will be agglomeration such as agglomeration or dead fish eyes, and mechanical agitation may cause inconvenience in the actual field operation.
  • Another method is to formulate the solid superabsorbent resin into a thicker one. The solution is diluted with water when used. This method adds a lot of transportation and packaging costs, and it is inconvenient/actual for large-scale applications (such as large sprinklers).
  • an object of the present invention is to provide an environmentally friendly polymer gel inhibitor and a preparation method and application thereof.
  • the present invention provides an environmentally friendly polymer gel inhibitor, comprising the following components by mass percentage: 30%-90% of polymer base; 10%-70% of inorganic flame retardant Surfactant 0-0.5%; intelligent regulator 0-20%, the sum of the important percentages of the above components is 100%.
  • the polymer binder is one or a combination of starch, a cellulose derivative, a polyacrylate, a polyvinyl alcohol or a polyoxyethylene derivative.
  • the polymer binder is potassium polyacrylate.
  • the inorganic flame retardant is one or a combination of sodium chloride, potassium chloride, sodium hydrogencarbonate, potassium hydrogencarbonate, magnesium chloride, calcium chloride, aluminum chloride or calcium hydroxide.
  • the surfactant is one or a combination of an aliphatic sodium sulfamate or sodium carbonate.
  • the smart regulator is one or a combination of two of citric acid or tartaric acid.
  • the present invention also provides a preparation method of the above environmentally-friendly polymer gel inhibitor, which is weighed according to the formula, mixed, and uniformly stirred to obtain the environmentally-friendly polymer gel inhibitor.
  • the present invention further provides a use of the above-mentioned environment-friendly polymer gel inhibitor for preventing spontaneous combustion or dust reduction of coal.
  • the environmentally-friendly polymer gel inhibitor is added to the water in an amount of 400-2000 times its solid weight, stirred, and dissolved.
  • stirring speed is 0-60 rpm.
  • stirring speed is 0 rpm.
  • the environment-friendly polymer gel inhibitor of the invention can be dissolved without using or slight mechanical stirring, and is convenient to use; wherein the smart regulator reduces hydrogen bonding between polymer matrix molecules in the initial stage of dissolution To prevent caking.
  • the intelligent regulator also generates bubbles with the bicarbonate to block the polymer bases from approaching each other to further prevent agglomeration; the generated bubbles are carbon dioxide, which is non-toxic and tasteless and does not pollute people and the environment.
  • the environmentally-friendly polymer gel inhibitor according to the invention is applied to coal mining process, pre-filling water through coal seam, spraying to goaf, spraying to coal wall cracks and fracture zone, high temperature and high temperature It is sprayed in the area and sprayed in the coal storage bin. It is a flowable liquid before gel formation. It is evenly covered on the surface of the coal after gel formation, and the contact between coal and air is isolated, thereby reducing the oxidation reaction process on the surface of the coal body. Spraying (coating) to increase the thickness of the coating film, thereby improving the fireproof rating; it has strong permeability and strong adherence, and the formed protective film has good compactness, high strength, resistance rate of 50% or more and long resistive life. It uses water as a solvent, is non-toxic, odorless, does not produce harmful gases and harmful waste, and does not pollute people and the environment.
  • the environment-friendly polymer gel inhibitor according to the present invention can suppress the dust, and the degree of crosslinking between the molecules of the polymer base forms a network structure, and various ionic groups exist between the molecules. It has a strong affinity with ions; its mechanism of action is to capture, adsorb, and agglomerate dust particles, and lock them into the network structure to moisturize, bond, coagulate, absorb moisture, and prevent dust. Anti-corrosion and anti-scour effect.
  • the smart regulator is diluted 400 to 2000 times, and the hydrogen bond between the polymer matrix molecules is no longer reduced.
  • the acidity of the smart conditioner captures heavy metals such as lead and reduces air pollution.
  • the environment-friendly polymer gel inhibitor according to the invention is a solid powder, which is convenient for transportation/storage than a liquid; and is diluted 400 to 2000 times with water when used, so that the actual use cost is lowered.
  • An environmentally friendly polymer gel inhibitor comprising the following components by mass percentage: potassium polyacrylate 70%; surfactant (sodium aliphatic sulfamate) 0.1%; inorganic flame retardant 21% and intelligent adjustment
  • the agent is 8.9%.
  • An environmentally friendly polymer gel inhibitor comprising the following components by mass percentage: potassium polyacrylate 80%; inorganic inhibitor 11% and smart regulator 9%.
  • the detection equipment includes: KB-120F intelligent TSP-PM10 flow sampler SCT-SB-059-1, KB-2400 intelligent constant current atmospheric sampler SCT-SB-031-1, BT125D electronic balance SCT-SB- 055, T6 New Century UV-Vis Spectrophotometer SCT-SB-054, AA-7000 Shimadzu Atomic Absorption Spectrophotometer SCT-SB-067.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及一种环保型高分子凝胶阻化剂，包含以下质量百分比的各组分：高分子基料30％-90％；无机阻燃剂10％-70％；表面活性剂0-0.5％；智能调节剂0-20％，上述各组分重要百分比之和为100％。本发明所述的环保型高分子凝胶阻化剂，其为固体粉末，运输/储存比液体方便；使用时用水稀释400到2000倍，使得实际使用成本降低；可在没有或轻微机械搅拌下溶解，使用方便。

Description

一种环保型高分子凝胶阻化剂及其制备方法和应用 技术领域
本发明涉及一种阻化剂，特别是关于一种环保型高分子凝胶阻化剂及其制备方法和应用。
背景技术
煤自燃可以造成巨大的财产损失，影响了开采效率，甚至引发瓦斯爆炸或井下火灾，严重威胁着矿井和矿工的人身安全。根据煤氧复合机理，煤发生自燃的主要原因是煤在氧化的过程中，逐渐放出热量，达到自燃所需要的环境。因此防治煤自燃的主要原则是抑制煤氧化，防止热量积聚。现阶段的主要阻化剂主要是NaCl、MgCl 2、CaCl 2等无机盐物理阻燃剂，这些阻燃剂只是在煤表面或周围吸收水分，降低煤的温度，随着时间的延长，煤又可以达到自燃的目的，不能从根本上抑制煤自燃。凝胶类阻化剂可在煤体表面形成阻隔膜，隔绝煤体与空气中氧气的氧化反应，达到阻化效果；但水玻璃凝胶阻化剂具有用量大、体积收縮大、干燥后易开裂等缺点，有机凝胶阻化剂往往热稳定性差、易燃烧且成本较高。
矿山的粉尘主要由矿石微粒和其他粉状物组成，状态上分为干粉尘和湿粉尘。在矿山开采以及后续加工生产过程中，粉尘产生主要集中在钻爆过程、破碎、筛分和皮带传送、运输、转载过程中。一条完整的矿山加工生产线，需要经过破碎、筛分、研磨、运输、集料等工序，每一道工序，伴随着矿石的碎裂与移动，细微级颗粒会逐步分离出来，从而会产生越来越多的粉尘。一般情况下粉尘粒径越小，在空气中越不易沉降，难以捕集，随着空气的流动，造成长期大范围污染，并易于随空气吸入呼吸道深部，对人体的危害亦越大。一些可燃性矿山粉尘，甚至还会存在爆炸性危害。
高吸水树脂(PAM)是含有亲水基团和交联结构的大分子。按原料划分为淀 粉系衍生物(接枝物、羧甲基化等)、纤维素系衍生物(羧甲基化、接枝物等)以及合成聚合物系(聚丙烯酸系、聚乙烯醇系、聚氧乙烯系等)几大类。
高吸水树脂(PAM)一般可以吸收相当于树脂体积100倍以上的水分，被广泛应用于一次性卫生用品，农用保水剂，工业抑尘剂等。在用于农用保水剂，工业抑尘剂等时，高吸水树脂需要被配制成溶液。但是高吸水树脂在配成溶液过程中容易结块，这会造成堵塞喷头，管道等现象，从而增加使用成本，不利于大规模推广。例如，http://www.rqbaoshuiji.com/有家PAM生产企业承认：“聚丙烯酰胺PAM溶解时会出现成团或死鱼眼的现象，”“固体PAM接触水时先膨胀，然后才溶解，而加入聚丙烯酰胺的速度和量也是有一定技巧的，必须要均速缓慢的投加，如果加入太快太多，势必使先接触水进而溶胀的聚丙烯酰胺包裹住后来未接触水的产品，就形成了上面所说的问题，这就是为何水处理药剂PAM溶于水会粘结成团。”
目前，高吸水树脂防止结块有两个方法：一是严格控制高吸水树脂加入的速度和量，并充分搅拌。如有家PAM生产企业“http://www.enoah.86mai.com/
”的固体抑尘剂在稀释时可用水稀释本产品，再加水，也可边加水边进行搅拌，搅拌速度控制在50-100转/分，搅拌时间为3-5分钟，时间略长效果更佳。如果加入太快太多，势必出现成团或死鱼眼等结块现象，而且机械搅拌在实际野外操作时存在使用不便等问题。另一个方法是将固体高吸水树脂配制成较浓的溶液，使用时再用水稀释。此方法增加了不少运输和包装成本，而且在较大规模应用时(例如大型洒水车)，操作很不方便/实际。
发明内容
有鉴于此，本发明的目的在于提供一种环保型高分子凝胶阻化剂及其制备方法和应用。
为了达成上述的目的，本发明提供了一种环保型高分子凝胶阻化剂，包含以下质量百分比的各组分：高分子基料30％-90％；无机阻燃剂10％-70％；表面活性剂0-0.5％；智能调节剂0-20％，上述各组分重要百分比之和为100％。
进一步地，其中所述高分子基料为淀粉、纤维素系衍生物、聚丙烯酸盐、聚乙烯醇或聚氧乙烯系衍生物中的一种或多种组合。
进一步地，其中所述高分子基料为聚丙烯酸钾。
进一步地，其中所述无机阻燃剂为氯化钠、氯化钾、碳酸氢钠、碳酸氢钾、 氯化镁、氯化钙、氯化铝或氢氧化钙中的一种或多种组合。
进一步地，其中所述表面活性剂为脂肪族氨基磺酸钠或碳酸钠中的一种或两种组合。
进一步地，其中所述智能调节剂为柠檬酸或酒石酸中的一种或两种组合。
另外，本发明还提供了一种上述环保型高分子凝胶阻化剂的制备方法，按照配方称取各组分，混合，搅拌均匀，得到所述环保型高分子凝胶阻化剂。
本发明进一步提供了一种上述环保型高分子凝胶阻化剂在用于防止煤炭自燃或降尘中的用途。
进一步地，其中所述环保型高分子凝胶阻化剂在使用时加入占其固体重量400-2000倍的水，搅拌，溶解。
进一步地，其中所述搅拌的转速为0-60转/分钟。
进一步地，其中所述搅拌的转速为0转/分钟。
本发明所述的环保型高分子凝胶阻化剂，其可在没有或轻微机械搅拌下溶解，使用方便；其中的智能调节剂在溶解的初始阶段减少高分子基料分子间的氢键作用，防止结块。智能调节剂还和碳酸氢盐产生气泡，阻隔高分子基料互相靠近，进一步防止结块；所产生的气泡为二氧化碳，无毒、无味不会对人和环境产生污染。
本发明所述的环保型高分子凝胶阻化剂，其应用到煤矿开采过程中，通过煤层预注水、向采空区喷洒、向煤壁煤柱裂隙和破碎带喷洒、向高温和高冒区喷洒、在储煤仓喷洒等手段使用，成胶前为可流动液体，成胶后均匀覆盖在煤体表面，隔绝煤和空气的接触，从而降低煤体表面的氧化反应过程；其可多次喷洒(涂)以增加涂膜厚度，从而提高防火等级；其渗透性强、附壁性强，形成的保护膜致密性好、强度大、阻化率可达50％以上且阻化寿命长；其以水为溶剂，无毒、无味、不会产生有害气体和有害废物，不会对人和环境产生污染。
本发明所述的环保型高分子凝胶阻化剂，其可起到抑制粉尘作用，高分子基料分子间的交联度会形成网状结构，同时分子间存在各种离子基团，能与离子之间产生较强的亲合力；它的作用机理是通过捕捉、吸附、团聚粉尘微粒，将其紧锁于网状结构之内，起到湿润、粘接、凝结、吸湿、防尘、防浸蚀和抗冲刷的作用。这时候的智能调节剂因为被稀释400到2000倍，不会再减少高分子基料分子间的氢键作用。智能调节剂的酸根会捕捉鉛等重金属，减少空气污染。
本发明所述的环保型高分子凝胶阻化剂，其为固体粉末，运输/储存比液体方便；其使用时用水稀释400到2000倍，使得实际使用成本降低。
具体实施方式
下列实施例将进一步说明本发明的其它特征和优点，但该等实施例仅为示例而用，并非对本发明的限制。
实施例1
一种环保型高分子凝胶阻化剂，包含以下质量百分比的各组分：聚丙烯酸钾70％；表面活性剂(脂肪族氨基磺酸钠)0.1％；无机阻燃剂21％和智能调节剂8.9％。
根据MT/T 700-1997《煤矿防火用阻化剂通用技术条件》，使用容易自燃的褐煤(内蒙古平庄能源股份有限公司提供)对实施例1所述的环保型高分子凝胶阻化剂进行了阻化实验，其中，当所述环保型高分子凝胶阻化剂与水的重量百分比为1：400时，其阻化率为51.2％，阻化寿命为219.3分钟；当所述环保型高分子凝胶阻化剂与水的重量百分比为1：700时，其阻化率为43.6％，阻化寿命为201.8分钟。
实施例2
一种环保型高分子凝胶阻化剂，包含以下质量百分比的各组分：聚丙烯酸钾80％；无机阻化剂11％以及智能调节剂9％。
根据《环境空气-PM 10和PM 2.5的测定-重量法》HJ618-2011；《环境空气-总悬浮颗粒物的测定-重量法》GB/T15432-1995；《环境空气-二氧化硫的测定-甲醛吸收-副玫瑰苯胺分光光度法》HJ482-2009；《环境空气-氮氧化物(一氧化氮和二氧化氮)的测定-盐酸萘乙二胺》HJ479-2009；《固体污染源废气-铅的测定-火焰原子吸收分光光度法》HJ538-2009，在江苏某地道路对实施例2所述的环保型高分子凝胶阻化剂进行了抑尘性能实验，结果如表1所示。
Figure PCTCN2017119020-appb-000001
Figure PCTCN2017119020-appb-000002
其中，检测设备包括：KB-120F智能TSP-PM10中流量采样器SCT-SB-059-1、KB-2400型智能恒流大气采样器SCT-SB-031-1、BT125D电子天平SCT-SB-055、T6新世纪紫外可见分光光度计SCT-SB-054、AA-7000岛津原子吸收分光光度计SCT-SB-067。
表1中的结果显示，在使用本实施例2所述的环保型高分子凝胶阻化剂三小时后PM10降低26％，铅降低42％。在使用24小时后PM 10降低55％，PM 2.5降低23％。地面灰尘负荷降低大于88％(使用前PM 10为0.548mg/m 3,PM 2.5为0.300mg/m 3,铅为0.167μg/m 3,地面灰尘负荷为0.777mg/m 3)。
综上所述，以上所述仅为本发明的较佳实施例，并非因此而限制本发明的专利保护范围，故举凡本发明说明书及附图所作等效变化等，皆应包括于本发明的保护范围内。

Claims (10)

  1. 一种环保型高分子凝胶阻化剂，其特征在于，包含以下质量百分比的各组分：高分子基料30％-90％；无机阻燃剂10％-70％；表面活性剂0-0.5％；智能调节剂0-20％，上述各组分重要百分比之和为100％。
  2. 如权利要求1所述的环保型高分子凝胶阻化剂，其特征在于，所述高分子基料为淀粉、纤维素系衍生物、聚丙烯酸盐、聚乙烯醇或聚氧乙烯系衍生物中的一种或多种组合。
  3. 如权利要求2所述的环保型高分子凝胶阻化剂，其特征在于，所述高分子基料为聚丙烯酸钾。
  4. 如权利要求1所述的环保型高分子凝胶阻化剂，其特征在于，所述无机阻化剂为氯化钠、氯化钾、碳酸氢钠、碳酸氢钾、氯化镁、氯化钙、氯化铝或氢氧化钙中的一种或多种组合。
  5. 如权利要求1所述的环保型高分子凝胶阻化剂，其特征在于，所述表面活性剂为脂肪族氨基磺酸钠或碳酸钠中的一种或两种组合。
  6. 如权利要求1所述的环保型高分子凝胶阻化剂，其特征在于，所述智能调节剂为柠檬酸或酒石酸中的一种或两种组合。
  7. 一种权利要求1-6任一项所述的环保型高分子凝胶阻化剂的制备方法，其特征在于，按照配方称取各组分，混合，搅拌均匀，得到所述环保型高分子凝胶阻化剂。
  8. 一种权利要求1-6任一项所述的环保型高分子凝胶阻化剂在用于防止煤炭自燃或降尘中的用途。
  9. 如权利要求8所述的用途，其特征在于，所述环保型高分子凝胶阻化剂在使用时加入占其固体重量400-2000倍的水，搅拌，溶解。
  10. 如权利要求9所述的用途，其特征在于，所述搅拌的转速为0-60转/分钟。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101793160A (zh) * 2010-01-29 2010-08-04 北京工业大学 一种用于防治煤炭自燃的环保阻燃高分子阻化剂
CN103388486A (zh) * 2013-07-18 2013-11-13 北京工业大学 一种阻燃性能优良的煤矿用喷涂堵漏风防灭火材料及其制备方法
JP2015132575A (ja) * 2014-01-15 2015-07-23 株式会社神戸製鋼所 石炭の自然発火予測方法
CN108192252A (zh) * 2017-12-27 2018-06-22 常州坤宇环保科技有限公司 一种环保型高分子凝胶阻化剂及其制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101793160A (zh) * 2010-01-29 2010-08-04 北京工业大学 一种用于防治煤炭自燃的环保阻燃高分子阻化剂
CN103388486A (zh) * 2013-07-18 2013-11-13 北京工业大学 一种阻燃性能优良的煤矿用喷涂堵漏风防灭火材料及其制备方法
JP2015132575A (ja) * 2014-01-15 2015-07-23 株式会社神戸製鋼所 石炭の自然発火予測方法
CN108192252A (zh) * 2017-12-27 2018-06-22 常州坤宇环保科技有限公司 一种环保型高分子凝胶阻化剂及其制备方法和应用

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