WO2020108535A1 - Preparation method for polyvinyl chloride-based carbon powder - Google Patents

Preparation method for polyvinyl chloride-based carbon powder Download PDF

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WO2020108535A1
WO2020108535A1 PCT/CN2019/121294 CN2019121294W WO2020108535A1 WO 2020108535 A1 WO2020108535 A1 WO 2020108535A1 CN 2019121294 W CN2019121294 W CN 2019121294W WO 2020108535 A1 WO2020108535 A1 WO 2020108535A1
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powder
polyvinyl chloride
carbon powder
alkaline solution
synthesis method
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PCT/CN2019/121294
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French (fr)
Chinese (zh)
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徐金铭
樊斯斯
黄延强
段洪敏
张涛
黄庆连
洪万墩
陈玉振
吴建慧
郑雅文
温明宪
张朝钦
黄朝晟
廖于涵
葉律真
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中国科学院大连化学物理研究所
台湾塑胶工业股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials

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  • the invention belongs to the field of material preparation, and in particular relates to a preparation method of polyvinyl chloride carbon powder.
  • Polyvinyl chloride is a widely used material with an annual output of about 40 million tons, which is cheap and easily available. It is a very challenging task to directly prepare carbon materials with various shapes from polyvinyl chloride.
  • Polyvinyl chloride is a thermoplastic polymer that begins to melt when heated to about 180°C. Therefore, when traditionally preparing carbon materials from polyvinyl chloride, polyvinyl chloride pitch is first prepared, and then activated carbon or carbon fiber is prepared from the pitch And other carbon materials.
  • Carbon powder is often used as a carrier for catalysts, electrode materials and adsorbent materials.
  • the way to prepare carbon powder is usually to crush large particles of carbon into a powder of a certain particle size.
  • the shape of the powder is irregular, and its fluidity and processing performance are not good.
  • the preparation of the present invention provides a method for preparing carbon powder from polyvinyl chloride powder, which can maintain the shape of polyvinyl chloride powder. Firstly, using polyvinyl chloride powder as a raw material and quaternary ammonium salt as a catalyst, a part of hydrogen chloride is removed in an alkaline solution, and after crosslinking and solidification, pyrolysis is performed to obtain carbon powder.
  • the carbon powder particles can maintain the shape of spherical particles of polyvinyl chloride powder, and the particles have good fluidity, which is convenient for secondary processing and application.
  • the method is simple and easy.
  • the carbon powder material can be used as a catalyst or a carrier of the catalyst, and can also be used as a metal ion adsorbent and a battery electrode material. It has broad application prospects in catalysis, adsorption and electrode materials.
  • the object of the present invention is to provide a method for preparing polyvinyl chloride carbon powder.
  • polyvinyl chloride powder is used as the raw material, and quaternary ammonium salt is used as the catalyst.
  • Part of hydrogen chloride is removed in the alkaline solution, and then carbonized by crosslinking and solidification to obtain carbon powder.
  • the particle size of the polyvinyl chloride powder is 10 nm to 300 ⁇ m;
  • the particle size of the carbon powder is 5nm-200 ⁇ m;.
  • the object of the present invention can be achieved by the following technical solutions.
  • a preparation method of polyvinyl chloride carbon powder the specific steps are:
  • the mass ratio of the polyvinyl chloride powder to the alkali solution described in the above step (1) is 1:2 to 1:100; the mass concentration of alkali in the alkali solution is 1% to 50%;
  • the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 10%.
  • the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:50; the mass concentration of alkali in the alkali solution is 5% to 30%.
  • the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:20; the mass concentration of alkali in the alkali solution is 5% to 20%.
  • the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:20; the mass concentration of alkali in the alkali solution is 5% to 15%.
  • the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 8%.
  • the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 5%.
  • the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 2%.
  • the alkaline solution described in the above step (1) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the quaternary ammonium salt in the above step (1) is one or more of the following general formulas;
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrocarbon groups having 1 to 24 carbon atoms; the anion X ⁇ is one of halogen anions or acid radicals.
  • the four hydrocarbon groups R 1 , R 2 , R 3 and R 4 having 1 to 24 carbon atoms may be the same or different, and may be substituted or unsubstituted hydrocarbons, and may be saturated or unsaturated hydrocarbons , May have branches or no branches, may have a cyclic structure or a linear structure, or may be aromatic or aromatic substitutes;
  • Anions X ⁇ are F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , HSO 4 ⁇ , HCO 3 ⁇ , RCOO ⁇ , H 2 PO 4 ⁇ , NO 3 ⁇ , NO 2 ⁇ , SO 4 2 ⁇ , CO 3 2 ⁇ , PO 4 One of 3 ⁇ .
  • the temperature of the alkaline solution treatment in the above step (1) is 60°C to 240°C; the treatment time of the alkaline solution is 0.2 to 30 hours.
  • the curing temperature is 80°C to 250°C; the curing time is 0.5 hour to 24 hours.
  • the carbonization atmosphere in the above step (3) is one or more of nitrogen, argon or helium.
  • the carbonization temperature is 450°C to 1200°C; the carbonization time is 0.5 hour to 24 hours.
  • the carbonization temperature in step (3) is 600°C to 1000°C; the carbonization time is 0.5 hour to 24 hours.
  • step (1) includes the following steps:
  • the preparation method is simple in process, the raw material is cheap, and the carbon powder particles can maintain the shape of the polyvinyl chloride powder particles, which is convenient for secondary processing and application, and has broad application prospects in the fields of catalysis, electrochemistry, and adsorption separation.
  • Figure 1 is a photograph of a carbon powder material obtained in Example 1 of the present invention.
  • Example 2 is a photograph of a carbon powder material obtained in Example 2 of the present invention.
  • FIG. 4 is a performance test of the carbon powder prepared in Examples 1 and 2 of the present invention in a lithium battery.
  • Polyvinyl chloride powder is provided by Taiwan Plastic Industry Co., Ltd. with models PR-L, S-65 and B-57.
  • polyvinyl chloride powder 25 g was dispersed in 150 mL of absolute ethanol to obtain an ethanol suspension of polyvinyl chloride.
  • 50g of NaOH was dissolved in 350mL of deionized water, added to the polyvinyl chloride ethanol suspension, and 1.0g of tetrabutylammonium bromide was added.
  • Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
  • the carbon powder obtained by adding the quaternary ammonium salt catalyst can maintain the shape of the original spherical particles of the polyvinyl chloride powder, the size is in the tens to hundreds of nanometers, the fluidity is good, and it is easy to process and use.
  • polyvinyl chloride powder 25 g was dispersed in 150 mL of absolute ethanol to obtain an ethanol suspension of polyvinyl chloride.
  • 50g of NaOH was dissolved in 350mL of deionized water, added to the polyvinyl chloride ethanol suspension, and 5.0g of tetrabutylammonium bromide was added.
  • the mixture was refluxed and stirred in a water bath at 80°C for 10 hours, filtered, and washed with deionized water until neutral to obtain partially dehydrochlorinated polyvinyl chloride powder.
  • Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
  • the carbon powder obtained by adding the quaternary ammonium salt catalyst can maintain the shape of the original spherical particles of the polyvinyl chloride powder, the size is in the range of tens to hundreds of nanometers, and the fluidity is good, which is convenient for processing and utilization.
  • polyvinyl chloride powder 25g was dispersed in 150mL of water to obtain an aqueous suspension of polyvinyl chloride.
  • 10g of NaOH was dissolved in 350mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 0.5g of tetraethylammonium chloride was added.
  • the partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 160°C, kept warm for 12 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 600°C under the protection of a nitrogen atmosphere, and held for 6 hours to obtain carbon powder.
  • PVC powder was dispersed in 100mL methanol to obtain PVC methanol suspension.
  • 20g of KOH was dissolved in 200mL of deionized water, added to the methanol suspension of PVC, and 3.0g of tetraoctylammonium bromide was added.
  • Partially dehydrochlorinated polyvinyl chloride powder was placed in an oven, heated to 200°C, kept for 6 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 1000°C under a nitrogen atmosphere, and kept for 1 hour to obtain carbon powder.
  • polyvinyl chloride powder 25 g was dispersed in 100 mL of water to obtain an aqueous suspension of polyvinyl chloride.
  • 30g of LiOH was dissolved in 200mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 3.0g of cetyltrimethylammonium bromide was added.
  • Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 750°C under the protection of an argon atmosphere, and held for 3 hours to obtain carbon powder.
  • polyvinyl chloride powder 25 g was dispersed in 100 mL of water to obtain an aqueous suspension of polyvinyl chloride.
  • 30g of LiOH was dissolved in 200mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 3.0g of tetrapropylammonium bromide was added. It was charged in a hydrothermal kettle and heated at 160°C for 4 hours, filtered, and washed with deionized water until neutral to obtain partially dehydrochlorinated polyvinyl chloride powder.
  • Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 800°C under the protection of a helium atmosphere, and held for 3 hours to obtain carbon powder.
  • PVC powder was dispersed in 150mL absolute ethanol to obtain PVC ethanol suspension.
  • 50g NaOH is dissolved in 350mL deionized water and added to the ethanol suspension of PVC without adding quaternary ammonium salt.
  • Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
  • the solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
  • Example 1 The carbon powder obtained in Example 1 was used as a catalyst after loading ammonium chloride with a mass fraction of 5%, and was used to test the catalytic performance in the reaction of 1,2-dichloroethane cracking to produce vinyl chloride.
  • the specific steps and conditions were :
  • the carbon powder made of polyvinyl chloride powder has excellent particle size and shape, and is suitable for development as a negative electrode material for lithium batteries.
  • the carbon powder prepared in Examples 1 and 2 has a lithium battery performance test result as shown in FIG. 4. After 150 charge-discharge cycles, the electric capacity can still be maintained close to that of commercially available carbon powder.

Abstract

A preparation method for the polyvinyl chloride-based carbon powder, specifically comprising: taking the polyvinyl chloride powder as the raw material, taking quaternary ammonium salts as a catalyst, removing a part of hydrogen chloride in an alkaline solution, performing cross-linking and curing, and performing thermolysis to obtain the carbon powder. The preparation method is simple in process, and cheap in raw materials. Carbon powder particles can maintain the shape of the polyvinyl chloride powder particles. The method has wide application prospects in the fields of catalysis, electrochemistry, and adsorption separation.

Description

一种聚氯乙烯基炭粉的制备方法Preparation method of polyvinyl chloride carbon powder 技术领域Technical field
本发明属于材料制备领域，具体涉及一种聚氯乙烯基炭粉的制备方法。The invention belongs to the field of material preparation, and in particular relates to a preparation method of polyvinyl chloride carbon powder.
背景技术Background technique
聚氯乙烯为一种广泛应用的材料，年产量在四千万吨左右，廉价易得。直接从聚氯乙烯出发制备形成各种形貌的炭材料是一件非常有挑战的工作。聚氯乙烯为一种热塑性高聚物，加热至180℃左右开始熔化，因此传统上从聚氯乙烯出发制备炭材料时，都是首先制备聚氯乙烯基沥青，然后由沥青出发制备活性炭或碳纤维等各种炭材料。Polyvinyl chloride is a widely used material with an annual output of about 40 million tons, which is cheap and easily available. It is a very challenging task to directly prepare carbon materials with various shapes from polyvinyl chloride. Polyvinyl chloride is a thermoplastic polymer that begins to melt when heated to about 180°C. Therefore, when traditionally preparing carbon materials from polyvinyl chloride, polyvinyl chloride pitch is first prepared, and then activated carbon or carbon fiber is prepared from the pitch And other carbon materials.
炭粉常用作催化剂的载体，电极材料和吸附材料，制备炭粉的途径通常是将大颗粒的炭粉碎为一定粒度粉末。对于粒度要求在几十纳米到几十微米的炭粉，需要长时间的研磨破碎和筛选，需要昂贵的设备和消耗大量的能量，无疑这会造成炭粉成本大大增加；并且，粉碎后的炭粉形状不规则，其流动性和加工性能不佳。Carbon powder is often used as a carrier for catalysts, electrode materials and adsorbent materials. The way to prepare carbon powder is usually to crush large particles of carbon into a powder of a certain particle size. For carbon powders with a particle size of tens of nanometers to tens of micrometers, it takes a long time to grind and screen, requires expensive equipment and consumes a lot of energy, which will undoubtedly cause the carbon powder cost to increase greatly; The shape of the powder is irregular, and its fluidity and processing performance are not good.
本发明制备提供了一种从聚氯乙烯粉出发制备炭粉的方法，炭粉能够保持聚氯乙烯粉的形貌。首先以聚氯乙烯粉体为原料，季铵盐为催化剂，在碱溶液中脱去部分氯化氢，经交联固化后热解得到炭粉。该炭粉颗粒能够保持聚氯乙烯粉球形颗粒的形状，颗粒的流动性好，便于二次加工和应用。该法简便易行，炭粉材料可以作为催化剂或催化剂的载体，还可以用做金属离子吸附剂和电池电极材料，在催化、吸附和电极材料方面有广阔的应用前景。The preparation of the present invention provides a method for preparing carbon powder from polyvinyl chloride powder, which can maintain the shape of polyvinyl chloride powder. Firstly, using polyvinyl chloride powder as a raw material and quaternary ammonium salt as a catalyst, a part of hydrogen chloride is removed in an alkaline solution, and after crosslinking and solidification, pyrolysis is performed to obtain carbon powder. The carbon powder particles can maintain the shape of spherical particles of polyvinyl chloride powder, and the particles have good fluidity, which is convenient for secondary processing and application. The method is simple and easy. The carbon powder material can be used as a catalyst or a carrier of the catalyst, and can also be used as a metal ion adsorbent and a battery electrode material. It has broad application prospects in catalysis, adsorption and electrode materials.
发明内容Summary of the invention
本发明的目的在于提供一种聚氯乙烯基炭粉的制备方法。本方法以聚氯乙烯粉体为原料，季铵盐为催化剂，在碱溶液中脱去部分氯化氢，经交联固化后炭化得到炭粉。The object of the present invention is to provide a method for preparing polyvinyl chloride carbon powder. In this method, polyvinyl chloride powder is used as the raw material, and quaternary ammonium salt is used as the catalyst. Part of hydrogen chloride is removed in the alkaline solution, and then carbonized by crosslinking and solidification to obtain carbon powder.
可选地，所述聚氯乙烯粉体的粒径为10nm～300μm；Optionally, the particle size of the polyvinyl chloride powder is 10 nm to 300 μm;
所述炭粉的粒径为5nm～200μm；。The particle size of the carbon powder is 5nm-200μm;.
本发明的目的可以通过以下技术方案实现。The object of the present invention can be achieved by the following technical solutions.
一种聚氯乙烯基炭粉的制备方法，具体步骤为：A preparation method of polyvinyl chloride carbon powder, the specific steps are:
具体步骤为：The specific steps are:
(1)将聚氯乙烯粉体在含有季铵盐的碱溶液中加热处理，催化脱去部分氯化氢；(1) Heat-treat the polyvinyl chloride powder in the alkaline solution containing quaternary ammonium salt to catalytically remove part of the hydrogen chloride;
(2)将部分脱氯化氢的聚氯乙烯粉体加热交联固化；(2) Heat and cross-link and cure the partially dehydrochlorinated PVC powder;
(3)将固化后的粉体在高温下炭化得到炭粉。(3) The solidified powder is carbonized at high temperature to obtain carbon powder.
上述步骤(1)所述的聚氯乙烯粉体与碱溶液的质量比为1:2到1:100；碱溶液中碱的质量浓度为1％到50％；The mass ratio of the polyvinyl chloride powder to the alkali solution described in the above step (1) is 1:2 to 1:100; the mass concentration of alkali in the alkali solution is 1% to 50%;
所述的季铵盐在碱溶液中的质量浓度为0.1％到10％。The mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 10%.
可选地，上述步骤(1)所述的聚氯乙烯粉体与碱溶液的质量比为1:5到1:50；碱溶液中碱的质量浓度为5％到30％。Optionally, the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:50; the mass concentration of alkali in the alkali solution is 5% to 30%.
可选地，上述步骤(1)所述的聚氯乙烯粉体与碱溶液的质量比为1:5到1:20；碱溶液中碱的质量浓度为5％到20％。Optionally, the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:20; the mass concentration of alkali in the alkali solution is 5% to 20%.
可选地，上述步骤(1)所述的聚氯乙烯粉体与碱溶液的质量比为1:5到1:20；碱溶液中碱的质量浓度为5％到15％。Optionally, the mass ratio of the polyvinyl chloride powder to the alkali solution in the above step (1) is 1:5 to 1:20; the mass concentration of alkali in the alkali solution is 5% to 15%.
可选地；所述的季铵盐在碱溶液中的质量浓度为0.1％到8％。Optionally; the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 8%.
可选地，所述的季铵盐在碱溶液中的质量浓度为0.1％到5％。Optionally, the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 5%.
可选地，所述的季铵盐在碱溶液中的质量浓度为0.1％到2％。Optionally, the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 2%.
上述步骤(1)所述的碱溶液为氢氧化钠、氢氧化钾和氢氧化锂中的一种或二种以上。The alkaline solution described in the above step (1) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
上述步骤(1)所述的季铵盐为如下通式中的一种或二种以上；The quaternary ammonium salt in the above step (1) is one or more of the following general formulas;
Figure PCTCN2019121294-appb-000001
Figure PCTCN2019121294-appb-000001
其中，R 1，R 2，R 3和R 4独立地选自碳原子数1到24的烃基；阴离子X ˉ为卤素阴离子或酸根中的一种。 Among them, R 1 , R 2 , R 3 and R 4 are independently selected from hydrocarbon groups having 1 to 24 carbon atoms; the anion X ˉ is one of halogen anions or acid radicals.
其中，碳原子数为1到24四个烃基R 1、R 2、R 3和R 4可以相同，也可以不相同，可以为取代的或非取代的烃，可以为饱和的或不饱和 的烃，可以有分支或没有分支，可以为环状结构或直链结构，也可以是芳香族或芳香族取代物； Among them, the four hydrocarbon groups R 1 , R 2 , R 3 and R 4 having 1 to 24 carbon atoms may be the same or different, and may be substituted or unsubstituted hydrocarbons, and may be saturated or unsaturated hydrocarbons , May have branches or no branches, may have a cyclic structure or a linear structure, or may be aromatic or aromatic substitutes;
阴离子X ˉ为F ˉ、Cl ˉ、Br ˉ、I ˉ、HSO 4 ˉ、HCO 3 ˉ、RCOO ˉ、H 2PO 4 ˉ、NO 3 ˉ、NO 2 ˉ、SO 4 2ˉ、CO 3 2ˉ、PO 4 3ˉ中的一种。 Anions X ˉ are F ˉ , Cl ˉ , Br ˉ , I ˉ , HSO 4 ˉ , HCO 3 ˉ , RCOO ˉ , H 2 PO 4 ˉ , NO 3 ˉ , NO 2 ˉ , SO 4 2ˉ , CO 3 2ˉ , PO 4 One of 3ˉ .
上述步骤(1)碱溶液处理的温度为60℃到240℃；碱溶液处理的时间为0.2小时到30小时。The temperature of the alkaline solution treatment in the above step (1) is 60°C to 240°C; the treatment time of the alkaline solution is 0.2 to 30 hours.
上述步骤(2)固化温度为温度为80℃到250℃；固化时间为0.5小时到24小时。In the above step (2), the curing temperature is 80°C to 250°C; the curing time is 0.5 hour to 24 hours.
上述步骤(3)炭化气氛为氮气、氩气或氦气中的一种或二种以上。The carbonization atmosphere in the above step (3) is one or more of nitrogen, argon or helium.
上述步骤(3)炭化温度为450℃到1200℃；炭化时间为0.5小时到24小时。In the above step (3), the carbonization temperature is 450°C to 1200°C; the carbonization time is 0.5 hour to 24 hours.
可选地，步骤(3)炭化温度为600℃到1000℃；炭化时间为0.5小时到24小时。Optionally, the carbonization temperature in step (3) is 600°C to 1000°C; the carbonization time is 0.5 hour to 24 hours.
作为一种实施方式，步骤(1)包括以下步骤：As an embodiment, step (1) includes the following steps:
(1)将聚氯乙烯粉体分散于溶液中，得到分散液；将碱溶液、季铵盐、分散液混合，加热处理，催化脱去部分氯化氢，经分离，洗涤，得到部分脱氯化氢的聚氯乙烯粉体。(1) Disperse the polyvinyl chloride powder in the solution to obtain a dispersion liquid; mix the alkaline solution, quaternary ammonium salt and dispersion liquid, heat treatment, catalytically remove part of the hydrogen chloride, and after separation and washing, obtain a partially dehydrochlorinated polymer Vinyl chloride powder.
本发明能产生的有益效果包括：The beneficial effects of the present invention include:
该制备方法工艺简单，原料廉价，且炭粉颗粒能够保持聚氯乙烯粉颗粒的形状，便于二次加工和应用，在催化、电化学和吸附分离领域具有广阔的应用前景。The preparation method is simple in process, the raw material is cheap, and the carbon powder particles can maintain the shape of the polyvinyl chloride powder particles, which is convenient for secondary processing and application, and has broad application prospects in the fields of catalysis, electrochemistry, and adsorption separation.
附图说明BRIEF DESCRIPTION
图1是本发明实施例1得到炭粉材料照片。Figure 1 is a photograph of a carbon powder material obtained in Example 1 of the present invention.
图2是本发明实施例2得到炭粉材料照片。2 is a photograph of a carbon powder material obtained in Example 2 of the present invention.
图3是本发明对比例1得到炭粉材料照片。3 is a photograph of a carbon powder material obtained in Comparative Example 1 of the present invention.
图4是本发明实施例1和2制备的炭粉在锂电池性能测试。FIG. 4 is a performance test of the carbon powder prepared in Examples 1 and 2 of the present invention in a lithium battery.
具体实施方式detailed description
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application will be described in detail below in conjunction with examples, but the present application is not limited to these examples.
如无特别说明，本申请的实施例中的原料均通过商业途径购买。Unless otherwise specified, the raw materials in the examples of this application are all purchased through commercial channels.
聚氯乙烯粉末由台湾塑胶工业股份有限公司提供，型号有PR-L，S-65和B-57。Polyvinyl chloride powder is provided by Taiwan Plastic Industry Co., Ltd. with models PR-L, S-65 and B-57.
本申请的实施例中分析方法如下：The analysis methods in the embodiments of the present application are as follows:
扫描电子显微镜(scanning electron microscopy，SEM)是在JSM-7800F仪器上进行测定的，获取炭粉的形貌结构，加速电压为1.5～10kV。测试前将粉末样品在80℃烘箱中干燥，然后取微量粉末置于导电胶上进行测试。Scanning electron microscope (scanning electron microscopy, SEM) is measured on the JSM-7800F instrument to obtain the morphological structure of the carbon powder, the acceleration voltage is 1.5 ~ 10kV. Before testing, the powder sample was dried in an oven at 80°C, and then a small amount of powder was placed on the conductive adhesive for testing.
实施例1Example 1
25g聚氯乙烯粉分散于150mL无水乙醇中，得到聚氯乙烯的乙醇悬浮液。50g NaOH溶于350mL去离子水中，加入至聚氯乙烯的乙醇悬浮液中，加入1.0g四丁基溴化铵。80℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25 g of polyvinyl chloride powder was dispersed in 150 mL of absolute ethanol to obtain an ethanol suspension of polyvinyl chloride. 50g of NaOH was dissolved in 350mL of deionized water, added to the polyvinyl chloride ethanol suspension, and 1.0g of tetrabutylammonium bromide was added. Stir at reflux in a 80°C water bath for 10 hours, filter, and wash to neutrality with deionized water to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至180℃，保温20小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氮气气氛保护下升温至800℃，保温3小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
由图1可以看出添加季铵盐催化剂得到的炭粉能够保持原来聚氯乙烯粉的球形颗粒的形状，尺寸在几十到几百纳米，流动性好，便于加工和利用。It can be seen from Figure 1 that the carbon powder obtained by adding the quaternary ammonium salt catalyst can maintain the shape of the original spherical particles of the polyvinyl chloride powder, the size is in the tens to hundreds of nanometers, the fluidity is good, and it is easy to process and use.
实施例2Example 2
25g聚氯乙烯粉分散于150mL无水乙醇中，得到聚氯乙烯的乙醇悬浮液。50g NaOH溶于350mL去离子水中，加入至聚氯乙烯的乙醇悬浮液中，加入5.0g四丁基溴化铵。80℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉 体。25 g of polyvinyl chloride powder was dispersed in 150 mL of absolute ethanol to obtain an ethanol suspension of polyvinyl chloride. 50g of NaOH was dissolved in 350mL of deionized water, added to the polyvinyl chloride ethanol suspension, and 5.0g of tetrabutylammonium bromide was added. The mixture was refluxed and stirred in a water bath at 80°C for 10 hours, filtered, and washed with deionized water until neutral to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至180℃，保温20小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氮气气氛保护下升温至800℃，保温3小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
由图2可以看出添加季铵盐催化剂得到的炭粉能够保持原来聚氯乙烯粉的球形颗粒的形状，尺寸在几十到几百纳米，流动性好，便于加工和利用。It can be seen from FIG. 2 that the carbon powder obtained by adding the quaternary ammonium salt catalyst can maintain the shape of the original spherical particles of the polyvinyl chloride powder, the size is in the range of tens to hundreds of nanometers, and the fluidity is good, which is convenient for processing and utilization.
实施例3Example 3
25g聚氯乙烯粉分散于150mL水中，得到聚氯乙烯的水悬浮液。10g NaOH溶于350mL去离子水中，加入至聚氯乙烯的水悬浮液中，加入0.5g四乙基氯化铵。80℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25g of polyvinyl chloride powder was dispersed in 150mL of water to obtain an aqueous suspension of polyvinyl chloride. 10g of NaOH was dissolved in 350mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 0.5g of tetraethylammonium chloride was added. Stir at reflux in a 80°C water bath for 10 hours, filter, and wash to neutrality with deionized water to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至160℃，保温12小时，加热交联固化。The partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 160°C, kept warm for 12 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氮气气氛保护下升温至600℃，保温6小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 600°C under the protection of a nitrogen atmosphere, and held for 6 hours to obtain carbon powder.
实施例4Example 4
25g PVC粉分散于100mL甲醇中，得到PVC的甲醇悬浮液。20g KOH溶于200mL去离子水中，加入至PVC的甲醇悬浮液中，加入3.0g四辛基溴化铵。60℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25g PVC powder was dispersed in 100mL methanol to obtain PVC methanol suspension. 20g of KOH was dissolved in 200mL of deionized water, added to the methanol suspension of PVC, and 3.0g of tetraoctylammonium bromide was added. Stir at reflux in a 60°C water bath for 10 hours, filter, and wash to neutrality with deionized water to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至200℃，保温6小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder was placed in an oven, heated to 200°C, kept for 6 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氮气气氛保护下升温至1000℃，保温1小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 1000°C under a nitrogen atmosphere, and kept for 1 hour to obtain carbon powder.
实施例5Example 5
25g聚氯乙烯粉分散于100mL水中，得到聚氯乙烯的水悬浮液。30g LiOH溶于200mL去离子水中，加入至聚氯乙烯的水悬浮液中，加入3.0g十六烷基三甲基溴化铵。95℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25 g of polyvinyl chloride powder was dispersed in 100 mL of water to obtain an aqueous suspension of polyvinyl chloride. 30g of LiOH was dissolved in 200mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 3.0g of cetyltrimethylammonium bromide was added. Stir at reflux in a 95°C water bath for 10 hours, filter, and wash to neutrality with deionized water to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至180℃，保温20小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氩气气氛保护下升温至750℃，保温3小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 750°C under the protection of an argon atmosphere, and held for 3 hours to obtain carbon powder.
实施例6Example 6
25g聚氯乙烯粉分散于100mL水中，得到聚氯乙烯的水悬浮液。30g LiOH溶于200mL去离子水中，加入至聚氯乙烯的水悬浮液中，加入3.0g四丙基溴化铵。装入水热釜中160℃加热4小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25 g of polyvinyl chloride powder was dispersed in 100 mL of water to obtain an aqueous suspension of polyvinyl chloride. 30g of LiOH was dissolved in 200mL of deionized water, added to the aqueous suspension of polyvinyl chloride, and 3.0g of tetrapropylammonium bromide was added. It was charged in a hydrothermal kettle and heated at 160°C for 4 hours, filtered, and washed with deionized water until neutral to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至180℃，保温20小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氦气气氛保护下升温至800℃，保温3小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 800°C under the protection of a helium atmosphere, and held for 3 hours to obtain carbon powder.
对比例1Comparative Example 1
25g PVC粉分散于150mL无水乙醇中，得到PVC的乙醇悬浮液。50g NaOH溶于350mL去离子水中，加入至PVC的乙醇悬浮液中，不加入季铵盐。80℃水浴中回流搅拌10小时，过滤，用去离子水洗涤至中性得到部分脱氯化氢的聚氯乙烯粉体。25g PVC powder was dispersed in 150mL absolute ethanol to obtain PVC ethanol suspension. 50g NaOH is dissolved in 350mL deionized water and added to the ethanol suspension of PVC without adding quaternary ammonium salt. Stir at reflux in a 80°C water bath for 10 hours, filter, and wash to neutrality with deionized water to obtain partially dehydrochlorinated polyvinyl chloride powder.
将部分脱氯化氢的聚氯乙烯粉体放置于烘箱内，升温至180℃，保温20小时，加热交联固化。Partially dehydrochlorinated polyvinyl chloride powder is placed in an oven, heated to 180°C, kept for 20 hours, and heated to crosslink and solidify.
固化的粉末置于石英管内，氮气气氛保护下升温至800℃，保温3小时，得到炭粉。The solidified powder was placed in a quartz tube, heated to 800°C under a nitrogen atmosphere, and held for 3 hours to obtain carbon powder.
由图3可以看出未添加季铵盐催化剂得到的炭粉，原来聚氯乙烯粉的球形颗粒发生融并不能保持原来聚氯乙烯粉的形状。It can be seen from FIG. 3 that the carbon powder obtained without adding the quaternary ammonium salt catalyst, the original spherical particles of the polyvinyl chloride powder are melted and cannot maintain the shape of the original polyvinyl chloride powder.
实施例7 炭粉在催化中的应用Example 7 Application of carbon powder in catalysis
将实施例1得到的炭粉在负载质量分数为5％的氯化铵后作为催化剂，用于1,2-二氯乙烷裂解制氯乙烯反应中的催化性能进行测试，具体步骤和条件为：The carbon powder obtained in Example 1 was used as a catalyst after loading ammonium chloride with a mass fraction of 5%, and was used to test the catalytic performance in the reaction of 1,2-dichloroethane cracking to produce vinyl chloride. The specific steps and conditions were :
以恒流泵将1,2-二氯乙烷液体在蒸发器内预热汽化后，通入载有催化剂的固定床反应器，反应器温度250℃，1,2-二氯乙烷的体积空速(GHSV)为100h -1。 After preheating and vaporizing the 1,2-dichloroethane liquid in the evaporator with a constant flow pump, it is led to a fixed-bed reactor loaded with a catalyst. The reactor temperature is 250°C and the volume of 1,2-dichloroethane The airspeed (GHSV) is 100h -1 .
反应结果显示，1,2-二氯乙烷转化率为32％，氯乙烯选择性为99％。The reaction results showed that the conversion rate of 1,2-dichloroethane was 32% and the selectivity of vinyl chloride was 99%.
实施例8 炭粉在锂离子电池负极材料中的应用Example 8 Application of carbon powder in anode materials of lithium ion batteries
利用聚氯乙烯粉制成炭粉，具有优异颗粒尺寸与形状，适合开发成锂电池负极材料。The carbon powder made of polyvinyl chloride powder has excellent particle size and shape, and is suitable for development as a negative electrode material for lithium batteries.
由实施例1和2制备的炭粉，在锂电池性能测试结果如图4所示，经过150次充放电循环后，电容量仍可与市售炭粉维持相近。The carbon powder prepared in Examples 1 and 2 has a lithium battery performance test result as shown in FIG. 4. After 150 charge-discharge cycles, the electric capacity can still be maintained close to that of commercially available carbon powder.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few examples of this application, and are not intended to limit this application in any way. Although this application is disclosed in the preferred embodiments as above, it is not intended to limit this application. Any person skilled in the art, Without departing from the scope of the technical solution of the present application, making slight changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case and belongs to the scope of the technical solution.

Claims (14)

  1. 一种聚氯乙烯基炭粉的制备方法，其特征在于，包括以下步骤：A preparation method of polyvinyl chloride carbon powder is characterized by comprising the following steps:
    以聚氯乙烯粉体为原料，季铵盐为催化剂，在碱溶液中脱去部分氯化氢，经交联固化后炭化得到炭粉。Using polyvinyl chloride powder as raw material and quaternary ammonium salt as catalyst, some hydrogen chloride is removed in the alkaline solution, and then carbonized by crosslinking and solidification to obtain carbon powder.
  2. 按照权利要求1所述的聚氯乙烯基炭粉的制备方法，其特征在于：所述聚氯乙烯粉体的粒径为10nm～300μm；The method for preparing polyvinyl chloride carbon powder according to claim 1, wherein the particle size of the polyvinyl chloride powder is 10 nm to 300 μm;
    所述炭粉的粒径为5nm～200μm。The particle size of the carbon powder is 5 nm to 200 μm.
  3. 按照权利要求1所述的合成方法，其特征在于，The synthesis method according to claim 1, wherein
    包括以下步骤：It includes the following steps:
    (1)将聚氯乙烯粉体在含有季铵盐的碱溶液中加热处理，催化脱去部分氯化氢；(1) Heat-treat the polyvinyl chloride powder in the alkaline solution containing quaternary ammonium salt to catalytically remove part of the hydrogen chloride;
    (2)将部分脱氯化氢的聚氯乙烯粉体加热交联固化；(2) Heat and cross-link and cure the partially dehydrochlorinated PVC powder;
    (3)将固化后的粉体在高温下炭化得到炭粉。(3) The solidified powder is carbonized at high temperature to obtain carbon powder.
  4. 按照权利要求3所述的合成方法，其特征在于，步骤(1)中，聚氯乙烯粉体与碱溶液的质量比为1:2到1:100；The synthesis method according to claim 3, characterized in that, in step (1), the mass ratio of the polyvinyl chloride powder to the alkaline solution is 1:2 to 1:100;
    碱溶液中碱的质量浓度为1％到50％；所述的季铵盐在碱溶液中的质量浓度为0.1％到10％。The mass concentration of the alkali in the alkaline solution is 1% to 50%; the mass concentration of the quaternary ammonium salt in the alkaline solution is 0.1% to 10%.
  5. 按照权利要求3或4所述的合成方法，其特征在于，步骤(1)所述的碱溶液为氢氧化钠、氢氧化钾和氢氧化锂中的一种或二种以上。The synthesis method according to claim 3 or 4, wherein the alkaline solution in step (1) is one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
  6. 按照权利要求3或4所述的合成方法，其特征在于，步骤(1)所述的季铵盐为如下通式中的一种或二种以上；The synthesis method according to claim 3 or 4, wherein the quaternary ammonium salt in step (1) is one or more than two in the following general formula;
    Figure PCTCN2019121294-appb-100001
    Figure PCTCN2019121294-appb-100001
    其中，R 1，R 2，R 3和R 4独立地选自碳原子数1到24的烃基；阴离子X ˉ为卤素阴离子或酸根中的一种。 Among them, R 1 , R 2 , R 3 and R 4 are independently selected from hydrocarbon groups having 1 to 24 carbon atoms; the anion X ˉ is one of halogen anions or acid radicals.
  7. 按照权利要求3或4所述的合成方法，其特征在于，The synthesis method according to claim 3 or 4, characterized in that
    阴离子X ˉ为F ˉ、Cl ˉ、Br ˉ、I ˉ、HSO 4 ˉ、HCO 3 ˉ、RCOO ˉ、H 2PO 4 ˉ、NO 3 ˉ、NO 2 ˉ、SO 4 2ˉ、CO 3 2ˉ、PO 4 3ˉ中的一种。 Anions X ˉ are F ˉ , Cl ˉ , Br ˉ , I ˉ , HSO 4 ˉ , HCO 3 ˉ , RCOO ˉ , H 2 PO 4 ˉ , NO 3 ˉ , NO 2 ˉ , SO 4 2ˉ , CO 3 2ˉ , PO 4 One of 3ˉ .
  8. 按照权利要求3或4所述的合成方法，其特征在于，步骤(1)中，碱溶液中加热处理的温度为60℃到240℃；碱溶液中加热处理的时间为0.2小时到30小时。The synthesis method according to claim 3 or 4, wherein in step (1), the temperature of the heat treatment in the alkaline solution is 60°C to 240°C; the time of the heat treatment in the alkaline solution is 0.2 hour to 30 hours.
  9. 按照权利要求3所述的合成方法，其特征在于，步骤(2)中，固化的温度为80℃到250℃；固化的时间为0.5小时到24小时。The synthesis method according to claim 3, wherein in step (2), the curing temperature is 80°C to 250°C; the curing time is 0.5 hour to 24 hours.
  10. 按照权利要求3所述的合成方法，其特征在于，步骤(3)中，炭化气氛为氮气、氩气或氦气中的一种或二种以上。The synthesis method according to claim 3, wherein in step (3), the carbonization atmosphere is one or more of nitrogen, argon, or helium.
  11. 按照权利要求3所述的合成方法，其特征在于，步骤(3)中，炭化温度为450℃到1200℃；炭化时间为0.5小时到24小时。The synthesis method according to claim 3, characterized in that, in step (3), the carbonization temperature is 450°C to 1200°C; the carbonization time is 0.5 hour to 24 hours.
  12. 按照权利要求3所述的合成方法，其特征在于，步骤(1)包括以下步骤：The synthesis method according to claim 3, wherein step (1) includes the following steps:
    (1)将聚氯乙烯粉体分散于溶液中，得到分散液；将碱溶液、季铵盐、分散液混合，加热处理，催化脱去部分氯化氢，经分离，洗涤，得到部分脱氯化氢的聚氯乙烯粉体；(1) Disperse the polyvinyl chloride powder in the solution to obtain a dispersion liquid; mix the alkaline solution, quaternary ammonium salt and dispersion liquid, heat treatment, catalytically remove part of the hydrogen chloride, after separation and washing, obtain the partially dehydrochlorinated Vinyl chloride powder;
    所述分散液中，聚氯乙烯粉末的质量浓度为0.1～1g/mL。In the dispersion liquid, the mass concentration of the polyvinyl chloride powder is 0.1 to 1 g/mL.
  13. 根据权利要求1至12任一项所述的方法制备的炭粉在催化1,2-二氯乙烷裂解制氯乙烯反应中的应用。The application of the carbon powder prepared by the method according to any one of claims 1 to 12 in the reaction of catalyzing the cracking of 1,2-dichloroethane to produce vinyl chloride.
  14. 根据权利要求1至12任一项所述的方法制备的炭粉在锂离子电池负极材料中的应用。Use of the carbon powder prepared by the method according to any one of claims 1 to 12 in a negative electrode material of a lithium ion battery.
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