WO2022147888A1 - 一种煤矿用多功能封堵剂及其制备方法 - Google Patents

一种煤矿用多功能封堵剂及其制备方法 Download PDF

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Publication number
WO2022147888A1
WO2022147888A1 PCT/CN2021/076121 CN2021076121W WO2022147888A1 WO 2022147888 A1 WO2022147888 A1 WO 2022147888A1 CN 2021076121 W CN2021076121 W CN 2021076121W WO 2022147888 A1 WO2022147888 A1 WO 2022147888A1
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coal
plugging agent
liriodendron
multifunctional
coal mines
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English (en)
French (fr)
Inventor
程卫民
胡相明
颜丙瑞
赵艳云
薛迪
吴明跃
贺正龙
白光星
牟宗磊
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Shandong University of Science and Technology
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Shandong University of Science and Technology
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Priority to JP2023541045A priority Critical patent/JP7454170B2/ja
Priority to KR1020237026349A priority patent/KR102674060B1/ko
Priority to AU2021417688A priority patent/AU2021417688B2/en
Publication of WO2022147888A1 publication Critical patent/WO2022147888A1/zh
Priority to US17/868,037 priority patent/US11691043B2/en
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/005—Dispersions; Emulsions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F15/00—Methods or devices for placing filling-up materials in underground workings
    • E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F5/00—Means or methods for preventing, binding, depositing, or removing dust; Preventing explosions or fires

Definitions

  • the invention belongs to the technical field of coal mine fire prevention and fire-extinguishing materials, relates to a multifunctional plugging agent for coal mines and a preparation method thereof, and in particular relates to a multifunctional plugging agent for coal mines and a preparation method thereof based on the biological extract of Ligustrum japonicus.
  • the high-level cracks are blocked by accumulation in the goaf, but it is easy to lose water and rupture, and the blocking function is lost.
  • the polyurethane plugging material can effectively block the gaps in the coal seam and isolate oxygen, the polyurethane itself is an organic combustible material, which not only cannot inhibit the spontaneous combustion of the coal seam, And once the coal seam catches fire, the organic plugging agent will also burn and carbonize to release a lot of heat to promote coal mine fire, and release a large amount of toxic gas to endanger the life safety of mine workers.
  • the present invention provides a multifunctional plugging agent for coal mines and a preparation method.
  • the multifunctional plugging agent for coal mines contains an extract of Ligustrum edulis, and the extract of Liriodendron is preferably a biological extract of Liriodendron.
  • the raw material of the plugging agent is abundant, easy to obtain, non-toxic and harmless. It can not only block coal fractures twice in the mine, but also play an efficient role in the whole cycle of coal spontaneous combustion (including low temperature, medium temperature and high temperature). Flame retardant effect.
  • the technical scheme adopted in the present invention is:
  • a multifunctional plugging agent for coal mines based on the biological extract of Liriodendron is as follows:
  • step (3) adding urea into the biological extract of Liriodendron chinensis obtained in step (2), neutralizing and stirring for 20 minutes, heating to 60° C., stirring under nitrogen atmosphere, and sequentially adding inorganic catalysts with a mass fraction of 0.5-2% and a mass fraction of 1 -3% melamine to fully react and mix to obtain a bio-based plugging synergist solution;
  • step (3) After the bio-based plugging synergist solution obtained in step (3) is cooled, the solution is weighed and uniformly mixed with pentaerythritol and ammonium polyphosphate, so as to obtain a multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis .
  • the plugging agent prepared by the biological extraction method is directly prepared by using natural organisms as raw materials, and the utilization rate of the material is higher, the utilization rate can reach more than 40%, the process is simple, the effect is remarkable, and the economic benefit is very high.
  • the bio-based plugging synergist solution obtained in step (4) After cooling the bio-based plugging synergist solution obtained in step (4), weigh 100-105 parts by weight of the solution, 3-5 parts by weight of pentaerythritol and 2-5 parts by weight of ammonium polyphosphate and evenly stir and mix
  • the present invention also includes the multifunctional plugging agent for coal mine obtained by the above preparation method, and the preparation containing the multifunctional plugging agent for coal mine.
  • the multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis of the present invention can seal the cracks of the coal body twice in the mine, and can achieve high efficiency flame retardant in the whole cycle of coal spontaneous combustion.
  • the multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis adhered to the surface of coal and rock through its own bio-adhesion to isolate the contact between coal and oxygen.
  • the abundant hydroxyl groups in the inorganic catalyst were linked with the active carboxyl groups on the surface of coal through hydrogen bonding.
  • the stability of the coal surface is improved; with the water slowly evaporating to dryness, the multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis, which completely loses water, self-foams and expands to realize secondary filling on the surface of the coal, and the acid is mixed with alcohol.
  • free radicals such as PO are released, and the free radicals generated by the coal-oxygen complex are captured, and the combustion reaction chain is cut off, and then the phase changes into a solid dense carbon layer and adsorbs the acid gases generated during the combustion process, which significantly reduces the CO release rate, heat Radiation, improve the temperature point of coal spontaneous combustion characteristic.
  • the advantages of air blocking and fire prevention are mainly reflected in the following aspects:
  • the multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis according to the present invention can effectively plug the coal seam cracks for many times. Before water loss, the plugging agent effectively adheres to the coal surface and fills in the coal cracks through its own bioadhesion; The self-foaming foam layer expands to more than 50 times its own volume, and the secondary filling of coal seam cracks achieves effective sealing.
  • the multifunctional plugging agent for coal mines based on the biological extract of Liriodendron chinensis according to the present invention can play a good inhibitory role in all stages of coal oxidative decomposition. In the low temperature stage, the plugging agent can retain water to infiltrate the coal body for a long time, and take away a lot of heat through the evaporation of water.
  • the plugging agent is linked with the functional groups on the coal surface through hydrogen bonds to enhance the stability of the coal active functional groups; Diphosphorus and urea products, ammonium polyphosphate and alcohols in the plugging agent are melted and esterified under the catalysis of metal composite hydroxide and release PO and other free radicals to cut off the combustion reaction chain, while melamine, part of ammonium polyphosphate and
  • the metal composite hydroxide decomposes and releases a large amount of inert gases (such as NH 3 , CO 2 , etc.) to dilute the oxygen around the coal; when the temperature rises to about 300 ° C, the expanded esterification carbonizes into a solid carbon layer, and the metal composite hydroxide is also Under the action of temperature, it is further decomposed to form metal composite oxides, and the two intersect to form a dense three-dimensional network structure to prevent heat transfer.
  • This series of processes enables the plugging agent to have a longer working temperature range and higher flame retardant efficiency than ordinary plugging agents.
  • the plugging agent When encountering a high temperature fire source, the plugging agent loses water quickly, decomposes and releases a large amount of inert gas and takes away part of the heat, and at the same time rapidly expands to form a dense porous carbon layer, which can be accumulated in the goaf and effectively cover the high ignition point.
  • the basic nature of the metal composite oxide inside it can adsorb the acid gas generated during the combustion process, and has a certain smoke suppression function.
  • Figure 1 shows the DSC curves of pulverized coal before and after the plugging agent is used
  • Figure 2 shows the TG/DTG curves of pulverized coal before and after the plugging agent is used
  • Figure 3 is a macroscopic topography of the porous three-dimensional plugging carbon layer (where a is the surface topography of the carbon layer, and b is the internal topography of the carbon layer);
  • Figure 4 shows the microscopic topography of the porous three-dimensional plugging carbon layer.
  • Vegetable Powder
  • the slurry is transported through iron pipes, sprayed on the burning coal pile or injected into the goaf.
  • There are a lot of hydroxyl groups between the Mg-Al-CO 3 hydrotalcite layers in the slurry these -OH can be connected with -COO- in coal through hydrogen bonds, and some -COO- functional groups can also complex with metal ions in hydrotalcite,
  • the liquid foam layer When the temperature exceeds 300°C, the liquid foam layer is phase-transformed and carbonized into a solid carbon layer, which fills in the coal cracks, isolates oxygen and heat during combustion, and covers more than 55% of the coal cracks.
  • Mg-Al-CO 3 hydrotalcite is dehydrated at high temperature to form metal composite oxides, which intersect with carbon chains to form a three-dimensional network structure, which enhances the density of the carbon layer and greatly improves the flame retardant efficiency.
  • Vegetable Powder
  • the slurry and compressed air are simultaneously transported to the underground of the coal mine, sprayed through the atomizing nozzle, and sprayed on the burning coal pile or the goaf.
  • these -OH can be connected with -COO- in coal through hydrogen bonds, and some -COO- functional groups can also be connected with the metal ions in the hydrotalcite.
  • the plugging agent retains a large amount of water and covers the coal surface to isolate the coal oxygen.
  • the liquid foam layer is phase-transformed and carbonized into a solid carbon layer, which is wrapped around the coal surface to isolate heat, and the coverage rate of the coal cracks reaches more than 60%.
  • Zn-Al-CO 3 hydrotalcite is dehydrated at high temperature to form metal composite oxides, which intersect with carbon chains to form a three-dimensional network structure, which enhances the density of the carbon layer and greatly improves the flame retardant efficiency.
  • Vegetable Powder
  • the slurry is transported through iron pipes, sprayed on the burning coal pile or injected into the goaf.
  • There are a lot of hydroxyl groups between the Ca-Mg-Al-CO 3 hydrotalcite layers in the slurry these -OH can connect with -COO- in coal through hydrogen bonds, and some -COO- functional groups can also complex with metal ions in the hydrotalcite.
  • a large amount of water retained by the plugging agent covers the coal surface to isolate the coal oxygen. Under the action of the coal pile temperature, the water in the slurry gradually evaporates and takes away the heat on the coal surface.
  • the liquid foam layer changes phase and carbonizes into a solid carbon layer, which fills the coal cracks, isolates oxygen and heat during combustion, and covers more than 60% of the coal cracks.
  • the Ca-Mg-Al-CO 3 hydrotalcite is dehydrated at high temperature to form metal composite oxides, which interlace with carbon chains to form a three-dimensional network structure, which enhances the density of the carbon layer and greatly improves the flame retardant efficiency.
  • Test Example 1 The CO release amount in the oxidation process of pulverized coal before and after the use of the multifunctional plugging agent for coal mines of the present invention is shown in Table 1, and the specific test conditions and methods are as follows:
  • Test Example 2 The DSC curves of pulverized coal before and after use of the multifunctional plugging agent for coal mines of the present invention are shown in Figure 1; Thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) were measured using a synchronous thermal analyzer (Labsys Evo STA, SETARAM; France) under a 50 mL/min air atmosphere to heat the samples from 30 °C at a rate of 10 k/min. Raised to 900°C.
  • TG Thermogravimetric analysis
  • DSC differential scanning calorimetry
  • the reduction of the heat release per unit mass can reach 20%.
  • the experimental data show that the plugging agent has obvious inhibitory effect on coal spontaneous combustion, and has a long flame retardant life. It can still play an efficient flame retardant effect in the later stage of oxidation.
  • Test Example 3 The macroscopic topography of the porous three-dimensional plugging carbon layer is shown in Figure 3, where a is the surface topography of the carbon layer, and b is the internal topography of the carbon layer.
  • the microscopic morphology was observed by scanning electron microscope.
  • the dried plugging agent sample was placed in an ark-shaped alumina crucible, heated at 500 °C for 30 min in a muffle furnace, and then taken out.
  • APREO scanning electron microscope (FEI Company, USA) Scanning with a voltage of 2kV above, the microscopic topography of the porous three-dimensional plugging carbon layer was observed as shown in Figure 4.
  • the multi-functional mining plugging agent expands in volume when it encounters high temperature, forming an expanded carbon layer.
  • the outer surface of the carbon layer is continuous and dense, which can isolate heat, flame and combustible gas during combustion; its interior is staggered.
  • the connected network structure is accompanied by closed holes with a diameter of about 30-50 ⁇ m.
  • the gas in the small holes is mostly a mixture of ammonia, carbon dioxide and air generated during thermal decomposition, which can reduce the heat transfer efficiency. , to provide the possibility to suppress combustion.

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Abstract

本发明属于煤矿防灭火材料技术领域，具体涉及一种煤矿用多功能封堵剂及其制备方法。本发明以鹅掌菜为原料将鹅掌菜悬浮液与五氧化二磷混合反应后经过生物降解得到鹅掌菜生物提取液，加入尿素进行中和，将中和产物与无机催化剂、三聚氰胺混合反应得到生物基封堵协效剂溶液，最后将生物基封堵协效剂溶液冷却后与一定量季戊四醇和聚磷酸铵混合得到基于鹅掌菜生物提取液的煤矿用多功能封堵剂。本发明不仅可以长时间有效封堵煤体裂隙，而且对煤自燃全周期(包括低温、中温、高温)均能起到高效的阻燃作用。

Description

一种煤矿用多功能封堵剂及其制备方法 技术领域
本发明属于煤矿防灭火材料技术领域，涉及一种煤矿用多功能封堵剂及其制备方法，具体涉及一种基于鹅掌菜生物提取液的煤矿用多功能封堵剂及其制备方法。
背景技术
我国能源分布具有“富煤、贫油、少气”的特点，尽管近年来环保意识逐渐增强，新型能源的开发与利用逐渐发展起来，但受成本、技术的局限，我国能源消费的主体部分仍是煤炭。然而据统计,我国超过半数的国有重点煤矿存在自然发火的危险，其中有90％以上是由于煤自燃引起的。导致煤自燃的原因主要是煤层的氧化，这种反应在所有煤矿事故中发生最隐蔽，同时还会引发矿井瓦斯爆炸，产生有毒有害气体，甚至会引起煤尘爆炸等次生灾害，加上灭火过程中经常会引法的水煤汽爆炸，会给井下生命财产带来极大的安全威胁。所以，煤自燃灾害的防控对促进矿区经济发展和社会和谐进步，响应可持续发展有重要意义。
在当前矿井生产的实际应用过程中，常用泥浆、惰性气体、泡沫、聚氨酯等对煤表面裂隙封堵，但这些封堵材料各自存在一定局限性。其中灌浆技术在实际应用中，液体会沿地势由高向低流动，因而难以均匀覆盖煤体或采空区表面，更不能对采空区高出裂隙进行封堵；对于注惰性气体方法，由于采空区容易和外界连通难以形成封闭的空间，因此气体整体呈向外泄露的状态，浓度渐低，氧气也逐渐进入，使其防灭火效果不佳，灭火周期也比较长；泡沫虽可以在采空区堆积封堵高位裂隙，但容易失水破裂，丧失封堵功能； 聚氨酯封堵材料虽然可以有效封堵煤层空隙、隔绝氧气，但聚氨酯本身是有机可燃材料，不但无法抑制煤层的自燃，而且一旦煤层着火，该有机封堵剂也会燃烧炭化放出大量热量促进煤矿火灾，并释放大量有毒气体危害矿井工人的生命安全。
发明内容
本发提供了一种煤矿用多功能封堵剂及制备方法，该煤矿用多功能封堵剂中含有鹅掌菜提取液，鹅掌菜提取液优选为鹅掌菜生物提取液。该封堵剂原材料丰富易得且无毒无害，在矿井内不仅可以对煤体裂隙实现两次封堵，还能在煤自燃全周期(包括低温、中温、高温)均能起到高效的阻燃作用。本发明采用的技术方案：
一种基于鹅掌菜生物提取液的煤矿用多功能封堵剂，制备方法如下：
(1)将鹅掌菜放入不透光罐中淡水浸泡3-4小时，取出后用流动水冲洗2-3遍放入干燥箱，90-100℃干燥50-60min，放入粉碎机中破碎3-5min，筛选粒径小于120目的鹅掌菜粉末；
(2)将鹅掌菜粉末放入反应容器与水混合，得到鹅掌菜悬浮液，升温至45-55℃，空气气氛下搅拌并缓慢加入五氧化二磷，搅拌反应30min后加入复合酶继续搅拌30min，静置反应50-55h，过滤得到鹅掌菜生物提取液；
(3)在步骤(2)获得的鹅掌菜生物提取液中加入尿素中和搅拌20min，升温至60℃后在氮气气氛下搅拌并依次加入质量分数0.5-2％的无机催化剂和质量分数1-3％的三聚氰胺，使其充分反应与混合，得到生物基封堵协效剂溶液；
(4)待步骤(3)获得的生物基封堵协效剂溶液冷却后称取该溶液与季戊四醇、聚磷酸铵均匀搅拌混合，得到基于鹅掌菜生物提取液的煤矿用多功 能封堵剂。
本生物提取法制备的封堵剂，以自然界生物为原料直接进行制备，对材料的利用率更高，利用率可达40％以上，工艺简单，效果显著，具有很高经济效益。
优选的，步骤(2)所述鹅掌菜粉末与水混合比例为质量比1:35-1:45；步骤(2)所述五氧化二磷添加量为(质量比)五氧化二磷:水＝1:13-1:42；步骤(2)所述的复合酶为葡萄糖内切酶、纤维二糖酶、羧肽酶、β葡萄糖苷酶中的一种或几种，添加量为质量分数0.5-1.5％。
优选的，步骤(3)所述无机催化剂为层状金属复合氢氧化物，主体层板的化学组成可调变，层间客体阴离子的种类和数量可调变，插层组装体的粒径尺寸和分布可调控；步骤(3)所述的尿素添加量为(质量比)尿素:五氧化二磷＝1:1-1:3。
优选的，步骤(4)中获得的生物基封堵协效剂溶液冷却后称取100-105重量份该溶液与3-5重量份季戊四醇、2-5重量份聚磷酸铵均匀搅拌混合
本发明还包括通过上述制备方法获得的煤矿用多功能封堵剂，以及含有煤矿用多功能封堵剂的制剂。
本发明基于鹅掌菜生物提取液的煤矿用多功能封堵剂在矿井内可对煤体裂隙实现两次封堵，并在煤自燃全周期实现高效阻燃。失水前，基于鹅掌菜生物提取液的煤矿用多功能封堵剂通过自身生物粘性附着在煤岩表面隔绝煤氧接触，同时无机催化剂中丰富羟基与煤表面活性羧基通过氢键作用链接，是的煤表面稳定性提高；随水分慢慢蒸干，完全失水的基于鹅掌菜生物提取液的煤矿用多功能封堵剂自发泡膨胀在煤表面实现二次填充，酸在与醇的酯化过程中释放PO·等自由基，捕捉煤氧复合产生的自由基，切断燃烧反应链， 继而相变为固态致密炭层并吸附燃烧过程中产生的酸性气体，显著降低CO释放速率、热辐射，提高煤自燃特征温度点。其堵漏风及防灭火的优势主要体现在以下几个方面：
(1)本发明所述的基于鹅掌菜生物提取液的煤矿用多功能封堵剂可对煤层裂隙实现多次有效封堵。失水前，该封堵剂通过自身生物粘附性在流动过程中有效附着在煤表面、充填在煤块裂隙中；完全失水后的封堵剂由一层固态薄膜相变为液态，并自发泡膨胀为自身体积50倍以上的泡沫层，二次填充煤层裂隙实现有效封堵。
(2)本发明所述的基于鹅掌菜生物提取液的煤矿用多功能封堵剂在煤氧化分解的各个阶段均可起到良好的抑制作用。低温阶段封堵剂能长时间保有水分浸润煤体，通过水分的蒸发带走大量热量，同时封堵剂通过氢键与煤表面官能团链接增强煤活性官能团的稳定性；水分蒸发完毕后，五氧化二磷与尿素产物、聚磷酸铵与封堵剂中醇类物质在金属复合氢氧化物的催化下熔融酯化并释放出PO·等自由基切断燃烧反应链，同时三聚氰胺、部分聚磷酸铵和金属复合氢氧化物分解释放大量惰性气体(如NH 3、CO 2等)稀释煤周氧气；当温度升高至300℃左右时，膨胀酯化物炭化为固态炭层，金属复合氢氧化物也在温度作用下进一步分解生成金属复合氧化物，二者交错贯穿形成致密三维网络结构阻隔热量传递。这一系列过程使该封堵剂拥有比普通封堵剂更长的作用温度区间和更高的阻燃效率。
(3)遇到高温火源时封堵剂快速失水，分解释放大量惰性气体并带走部分热量，同时迅速膨胀生成致密的多孔炭层，可在采空区进行堆积，有效覆盖高位着火点。其内部的金属复合氧化物的碱性性质可吸附燃烧过程中产生的酸性气体，具有一定抑烟功能。
附图说明
图1为封堵剂使用前后煤粉DSC曲线；
图2为封堵剂使用前后煤粉TG/DTG曲线；
图3为多孔三维封堵炭层宏观形貌图(其中a为炭层表层形貌，b为炭层内部形貌)；
图4为多孔三维封堵炭层微观形貌图。
具体实施方式
下面结合具体实施例来进一步描述本发明，本发明的优点和特点将会随着描述而更为清楚。但实施例仅是范例性的，并不对本发明的范围构成任何限制。本领域技术人员应该理解的是，在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换，但这些修改和替换均落入本发明的保护范围内。
实施例1
将鹅掌菜放入不透光罐中淡水浸泡3小时，取出后用流动水冲洗2遍放入干燥箱，90℃干燥50min，放入粉碎机中破碎5min，筛选粒径小于120目的鹅掌菜粉末。称取25kg鹅掌菜粉末放入反应容器与1000kg水混合，得到鹅掌菜悬浮液，升温至45℃，空气气氛下搅拌并缓慢加入五氧化二磷至悬浮液ph＝5.5，搅拌反应30min后加入羧肽酶：β葡萄糖苷酶＝1：2的复合酶10.25kg继续搅拌30min，静置反应50h，过滤得到鹅掌菜生物提取液。
在上述鹅掌菜生物提取液中加入尿素至溶液呈中性，搅拌20min，升温至60℃后在氮气气氛下搅拌并依次加入0.5kg的Mg-Al-CO 3水滑石层和10kg的三聚氰胺，使其充分反应与混合，得到生物基封堵协效剂溶液。待溶液冷却后称取50kg季戊四醇、20kg聚磷酸铵均匀搅拌混合，得到基于鹅掌菜生物提 取液的煤矿用多功能封堵剂。
通过铁管输送浆液，将其喷洒在燃烧的煤堆上或注入采空区。浆液中的Mg-Al-CO 3水滑石层板间有大量羟基，这些-OH可以和煤中的-COO-通过氢键连接，部分-COO-官能团还能与水滑石中金属离子络合，使得煤表面C＝O基团的稳定性提高，同时封堵剂保有的大量水分覆盖在煤表面将煤氧隔绝开来，当煤体温度升高至170℃左右时，五氧化二磷与尿素产物、聚磷酸铵与封堵剂中醇类物质(季戊四醇、海藻酸钠、果糖和半乳糖醛酸等)在Mg-Al-CO 3水滑石的催化下熔融酯化，并释放出PO·捕捉煤表面活性自由基并阻断其链反应，三聚氰胺和部分聚磷酸铵受热分解释放出大量惰性气体使熔融封堵剂膨胀形成自身厚度55倍的泡沫层，并稀释环境中的氧气。温度超过300℃时，液态泡沫层相变并炭化为固态炭层，填充在煤块裂隙中，在燃烧时隔绝氧气和热量，对煤块裂隙覆盖率达到55％以上。Mg-Al-CO 3水滑石在高温作用下脱水生成金属复合氧化物，与炭链交错贯穿形成三维网络结构，增强炭层致密度大大提高阻燃效率。
实施例2
将鹅掌菜放入不透光罐中淡水浸泡3小时，取出后用流动水冲洗2遍放入干燥箱，90℃干燥50min，放入粉碎机中破碎5min，筛选粒径小于120目的鹅掌菜粉末。称取25kg鹅掌菜粉末放入反应容器与1000kg水混合，得到鹅掌菜悬浮液，升温至45℃，空气气氛下搅拌并缓慢加入五氧化二磷至悬浮液ph＝6，搅拌反应30min后加入羧肽酶：纤维二糖酶：葡萄糖内切酶＝1：1：1的复合酶10.25kg继续搅拌30min，静置反应50h，过滤得到鹅掌菜生物提取液。
在上述鹅掌菜生物提取液中加入尿素至溶液呈中性，搅拌20min，升温至 60℃后在氮气气氛下搅拌并依次加入1kg的Zn-Al-CO 3水滑石层和10kg的三聚氰胺，使其充分反应与混合，得到生物基封堵协效剂溶液。待溶液冷却后称取40kg季戊四醇、10kg聚磷酸铵均匀搅拌混合，得到基于鹅掌菜生物提取液的煤矿用多功能封堵剂。
通过铁管将浆液和压缩空气同时输送至煤矿井下经雾化喷嘴喷出，喷洒在燃烧的煤堆上或采空区。封堵剂浆液中的Zn-Al-CO 3水滑石层板间有大量羟基，这些-OH可以和煤中的-COO-通过氢键连接，部分-COO-官能团还能与水滑石中金属离子络合，使得煤表面C＝O基团的稳定性提高。同时，封堵剂保有得到大量水分覆盖在煤表面将煤氧隔绝开来，在煤堆温度的作用下，浆液中水分逐渐蒸发并带走煤表面的热量。温度到达180℃左右时，五氧化二磷与尿素产物、聚磷酸铵与封堵剂中醇类物质(季戊四醇、海藻酸钠、果糖和半乳糖醛酸等)在Zn-Al-CO 3水滑石的催化下熔融酯化，并释放出PO·捕捉煤表面活性自由基并阻断其链反应，三聚氰胺和部分聚磷酸铵受热分解释放出大量惰性气体使熔融封堵剂膨胀形成自身厚度52倍的泡沫层，并稀释环境中的氧气。温度超过250℃时，液态泡沫层相变并炭化为固态炭层包裹在煤表面隔绝热量，对煤块裂隙覆盖率达到60％以上。Zn-Al-CO 3水滑石在高温作用下脱水生成金属复合氧化物，与炭链交错贯穿形成三维网络结构，增强炭层致密度大大提高阻燃效率。
实施例3
将鹅掌菜放入不透光罐中淡水浸泡3小时，取出后用流动水冲洗2遍放入干燥箱，90℃干燥50min，放入粉碎机中破碎5min，筛选粒径小于120目的鹅掌菜粉末。称取25kg鹅掌菜粉末放入反应容器与1000kg水混合，得到鹅掌菜悬浮液，升温至45℃，空气气氛下搅拌并缓慢加入五氧化二磷至悬浮液 ph＝5.8，搅拌反应30min后加入纤维二糖酶：葡萄糖内切酶＝1：1的复合酶10.25kg继续搅拌30min，静置反应50h，过滤得到鹅掌菜生物提取液。
在上述鹅掌菜生物提取液中加入尿素至溶液呈中性，搅拌20min，升温至60℃后在氮气气氛下搅拌并依次加入1kg的Ca-Mg-Al-CO 3水滑石层和10kg的三聚氰胺，使其充分反应与混合，得到生物基封堵协效剂溶液。待溶液冷却后称取40kg季戊四醇、10kg聚磷酸铵均匀搅拌混合，得到基于鹅掌菜生物提取液的煤矿用多功能封堵剂。
通过铁管输送浆液，将其喷洒在燃烧的煤堆上或注入采空区。浆液中的Ca-Mg-Al-CO 3水滑石层板间有大量羟基，这些-OH可以和煤中的-COO-通过氢键连接，部分-COO-官能团还能与水滑石中金属离子络合，使得煤表面C＝O基团的稳定性提高。同时，封堵剂保有的大量水分覆盖在煤表面将煤氧隔绝开来，在煤堆温度的作用下，浆液中水分逐渐蒸发并带走煤表面的热量。温度到达200℃左右时，五氧化二磷与尿素产物、聚磷酸铵与封堵剂中醇类物质(季戊四醇、海藻酸钠、果糖和半乳糖醛酸等)在Ca-Mg-Al-CO 3水滑石的催化下熔融酯化，并释放出PO·捕捉煤表面活性自由基并阻断其链反应，三聚氰胺和部分聚磷酸铵受热分解释放出大量惰性气体使熔融封堵剂膨胀形成自身厚度50倍的泡沫层，并稀释环境中的氧气。温度超过250℃时，液态泡沫层相变并炭化为固态炭层，填充在煤块裂隙中，在燃烧时隔绝氧气和热量，对煤块裂隙覆盖率达到60％以上。Ca-Mg-Al-CO 3水滑石在高温作用下脱水生成金属复合氧化物，与炭链交错贯穿形成三维网络结构，增强炭层致密度大大提高阻燃效率。
试验例1：本发明煤矿用多功能封堵剂使用前后煤粉氧化过程中CO释放量如表1所示，具体测试条件及方法如下：
分别制备纯煤粉、含封堵剂质量分数10％的阻化煤粉和含传统卤盐阻化剂(CaCl 2)质量分数10％的阻化煤粉。通过程序升温设备对样品以1.0℃/min的速率升温至210℃，每次测试将50g样品置于设备反应器中，干空气以50mL/min速度进入反应器，待反应器加热至预定的初始温度后记录煤样和炉体温度，并从40℃开始，通过气相色谱以10℃为间隔分析反应器出口的废气中CO含量。
表1
Figure PCTCN2021076121-appb-000001
Figure PCTCN2021076121-appb-000002
从表1中数据可以看出，经过封堵剂处理的煤样在低温阶段的CO释放量明显低于传统CaCl 2处理煤样，根据阻化率计算公式
Figure PCTCN2021076121-appb-000003
(其中E为样品阻化率，Cr为原煤样CO的释放量，单位ppm；Ct为经过阻化处理煤样在温度为t时的CO释放量，单位ppm)，经计算，70℃下矿用多功能封堵剂处理煤粉的阻化率为47％，高出传统CaCl 2阻化率百分之15.8％，矿用多功能封堵剂处理煤粉100℃下阻化率为53.5％，高出传统CaCl 2阻化率百分之23.1％。该矿用多功能封堵剂不仅在低温阶段有优越的阻化效果，且效果随温度升高持续增强。
试验例2：本发明煤矿用多功能封堵剂使用前后煤粉DSC曲线如图1所示；本发明煤矿用多功能封堵剂使用前后煤粉TG/DTG曲线如图2所示。热重分析(TG)和差示扫描量热(DSC)测试使用的仪器为同步热分析仪(Labsys Evo STA，SETARAM；法国)在50mL/min空气气氛下将样品从30℃以10k/min速率升温到900℃。
结果分析：从TG曲线可以看出，经过处理的煤样吸氧增重阶段变得不明显，说明煤与氧的复合过程受到抑制；同时DTG曲线反映样品失重速率，经处理的煤粉达到最大失重速率的温度点推迟60℃，而传统卤盐类阻化剂在阻化后期会产生催化作用，使最大失重速率温度点提前；根据DSC曲线可以看出，经多功能封堵剂处理的煤样的热释放量有明显减少，放热时间也被明显 推迟，根据积分计算，单位质量减少的放热量可达20％。实验数据表明该封堵剂对煤自燃的抑制效果明显，且阻燃寿命长，氧化后期依然可以起到高效阻燃作用。
试验例3：多孔三维封堵炭层宏观形貌图如图3所示，其中a为炭层表层形貌，b为炭层内部形貌。微观形貌通过扫描电子显微镜观察得到，将干燥过的封堵剂样品放入方舟形氧化铝坩埚，在马弗炉中以500℃加热30min后取出，在APREO扫描电子显微镜(FEI Company，USA)上以2kV电压进行扫描，观察到多孔三维封堵炭层微观形貌图如图4所示。
结果分析：该多功能矿用封堵剂遇到高温时体积膨大，形成膨胀炭层，炭层外表面连续而致密，可以在燃烧时将热量、火焰和可燃气体隔绝开来；其内部为交错连接的网状结构并伴随着一个个直径大约在30-50μm左右的、封闭的孔洞，小孔内的气体多为受热分解时产生的氨气、二氧化碳与空气的混合体，可以降低传热效率，为抑制燃烧提供可能。

Claims (10)

  1. 一种基于鹅掌菜生物提取液的煤矿用多功能封堵剂，其特征在于，所述煤矿用多功能封堵剂中含有鹅掌菜提取液。
  2. 根据权利要求1所述的煤矿用多功能封堵剂，其特征在于，所述鹅掌菜生物提取液为鹅掌菜生物提取液。
  3. 根据权利要求2所述的煤矿用多功能封堵剂，其特征在于，所述煤矿用多功能封堵剂的制备方法如下：
    (1)将鹅掌菜放入不透光罐中淡水浸泡3-4小时，取出后用流动水冲洗2-3遍放入干燥箱，90-100℃干燥50-60min，放入粉碎机中破碎3-5min，筛选粒径小于120目的鹅掌菜粉末；
    (2)将鹅掌菜粉末放入反应容器与水混合，得到鹅掌菜悬浮液，升温至45-55℃，空气气氛下搅拌并缓慢加入五氧化二磷，搅拌反应30min后加入复合酶继续搅拌30min，静置反应50-55h，过滤得到鹅掌菜生物提取液；
    (3)在步骤(2)获得的鹅掌菜生物提取液中加入尿素中和搅拌20min，升温至60℃后在氮气气氛下搅拌并依次加入质量分数0.5-2％的无机催化剂和质量分数1-3％的三聚氰胺，使其充分反应与混合，得到生物基封堵协效剂溶液；
    (4)待步骤(3)获得的生物基封堵协效剂溶液冷却后称取该溶液与季戊四醇、聚磷酸铵均匀搅拌混合，得到基于鹅掌菜生物提取液的煤矿用多功能封堵剂。
  4. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(2)所述鹅掌菜粉末与水混合比例为质量比1:35-1:45。
  5. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(2)所述五氧化二磷添加量为(质量比)五氧化二磷:水＝1:13-1:42。
  6. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(2)所述的复合酶为葡萄糖内切酶、纤维二糖酶、羧肽酶、β葡萄糖苷酶中的一种或几种，添加量为质量分数0.5-1.5％。
  7. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(3)所述无机催化剂为层状金属复合氢氧化物。
  8. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(3)所述的尿素添加量为(质量比)尿素:五氧化二磷＝1:1-1:3。
  9. 根据权利要求3所述的煤矿用多功能封堵剂，其特征在于，步骤(4)中获得的生物基封堵协效剂溶液冷却后称取100-105重量份该溶液与3-5重量份季戊四醇、2-5重量份聚磷酸铵均匀搅拌混合。
  10. 含有如权利要求1-9任一项所述煤矿用多功能封堵剂的制剂在煤矿封堵方面的应用。
PCT/CN2021/076121 2021-01-06 2021-02-09 一种煤矿用多功能封堵剂及其制备方法 Ceased WO2022147888A1 (zh)

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