CN102489306A - Low-mercury catalyst for synthesizing vinyl chloride - Google Patents
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Abstract
一种合成氯乙烯用的低汞触媒，其特征在于：按重量计，包括以下成份：HgCl2：2.5～3.5％；BiCl3：0.1～12.5％；ZnCl2：0.15～15％；TiCl4：0.1～7.00％；CuCl2：2.75～3.25％；VCl3：0.3～8.3％；氯化稀土：0.3～8.3％；BaCl23～8.5％；C：62.5～75％。采用具有催化性能的廉价BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土替代部分HgCl2制取低汞触媒，在充分保障催化性能的同时可使触媒中HgCl2含量降低到3.5％以下，不仅降低了资源消耗，同时降低了触媒的生产成本。本发明采用分步浸渍方法，工艺简单、有效、节能、环保，操作方便，同时能克服现有技术存在的问题。适用于合成氯乙烯二段工序用。A low-mercury catalyst for synthesizing vinyl chloride, characterized in that: by weight, it comprises the following components: HgCl 2 : 2.5-3.5%; BiCl 3 : 0.1-12.5%; ZnCl 2 : 0.15-15%; TiCl 4 : 0.1-7.00%; CuCl 2 : 2.75-3.25%; VCl 3 : 0.3-8.3%; rare earth chloride: 0.3-8.3%; BaCl 2 3-8.5%; C: 62.5-75%. Use cheap BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride with catalytic performance to replace part of HgCl 2 to prepare low-mercury catalyst, which can make HgCl 2 in the catalyst while fully guaranteeing catalytic performance The content is reduced to less than 3.5%, which not only reduces resource consumption, but also reduces the production cost of the catalyst. The invention adopts a step-by-step impregnation method, has simple, effective, energy-saving, environmental protection, convenient operation, and can overcome the problems existing in the prior art at the same time. It is suitable for the second-stage process of synthesizing vinyl chloride.
Description
技术领域 technical field
本发明涉及一种合成氯乙烯用的低汞触媒的制备方法；属于合成氯乙烯技术领域。The invention relates to a preparation method of a low-mercury catalyst for synthesizing vinyl chloride, belonging to the technical field of synthesizing vinyl chloride.
背景技术 Background technique
汞污染是一个严重的全球环境问题。国际禁汞的呼声越来越高涨。我国年用汞量占全球的30％～40％，其中电石法聚氯乙烯用汞量占全国用汞量的60％。目前，我国聚氯乙烯生产企业104家，总产能为1781万吨，其中电石法94家，产能为1362万吨，占总产能的76.5％。2009年我国聚氯乙烯总产量为915万吨，其中电石法聚氯乙烯产量580万吨，占总产量的63.4％。受资源结构制约，我国聚氯乙烯生产行业以电石为主的状况无法改变。Mercury pollution is a serious global environmental problem. The call for an international ban on mercury is getting louder and louder. my country's annual mercury consumption accounts for 30% to 40% of the world's total, and the mercury consumption of calcium carbide polyvinyl chloride accounts for 60% of the national mercury consumption. At present, there are 104 PVC production enterprises in my country, with a total production capacity of 17.81 million tons, of which 94 are based on calcium carbide method, with a production capacity of 13.62 million tons, accounting for 76.5% of the total production capacity. In 2009, the total output of polyvinyl chloride in my country was 9.15 million tons, of which the output of calcium carbide polyvinyl chloride was 5.8 million tons, accounting for 63.4% of the total output. Constrained by the resource structure, the situation that my country's PVC production industry is dominated by calcium carbide cannot be changed.
我国政府对汞污染防治非常重视：环境保护部、工业和信息化部等8部门联合发布文，提出到2015年底，电石法聚氯乙烯生产企业要全部使用低汞触媒，明确重金属污染防治目标。The Chinese government attaches great importance to the prevention and control of mercury pollution: the Ministry of Environmental Protection, the Ministry of Industry and Information Technology and other 8 departments jointly issued a document, proposing that by the end of 2015, all enterprises producing calcium carbide polyvinyl chloride should use low-mercury catalysts, and clarify the goals of heavy metal pollution prevention and control.
本专利发明人在先申请的专利：氯化汞低汞催化剂及其制备方法，专利申请号200910102437，采用活性炭为载体吸附氯化汞，该催化剂配方中的氯化汞为8.0％～10.0％，其氯化汞含量仍然偏高，不能满足要求。The inventor of this patent has previously applied for a patent: mercuric chloride low-mercury catalyst and its preparation method, patent application number 200910102437, which uses activated carbon as a carrier to adsorb mercuric chloride, and the mercuric chloride in the catalyst formula is 8.0% to 10.0%. Its mercury chloride content is still on the high side, which cannot meet the requirements.
此外，氯乙烯合成工艺大都采用两段法，一段为高浓度合成，二段为低浓度合成。在一段工序中高浓度HCl和高浓度乙炔在汞催化剂的作用下合成氯乙烯，反应剧烈，放出大量热，进入二段工序后HCl和乙炔的浓度大大降低，反应温和。因而一段和二段所需的汞催化剂也因不同。In addition, the vinyl chloride synthesis process mostly adopts a two-stage method, one stage is high-concentration synthesis, and the second stage is low-concentration synthesis. In the first-stage process, high-concentration HCl and high-concentration acetylene synthesize vinyl chloride under the action of a mercury catalyst. The reaction is violent and a large amount of heat is released. After entering the second-stage process, the concentration of HCl and acetylene is greatly reduced, and the reaction is mild. Therefore, the mercury catalyst required for the first stage and the second stage is also different.
发明内容 Contents of the invention
本发明目的在于：提供一种合成氯乙烯用的低汞触媒的制备方法，达到进一步降低催化剂中的HgCl2含量的目的。The object of the present invention is to: provide a kind of preparation method of the low-mercury catalyst used for synthesizing vinyl chloride, reach the purpose of further reducing the HgCl content in the catalyst.
本发明是这样构成的：合成氯乙烯用的低汞触媒，按重量计，包括以下成份：HgCl2：2.5～3.5％；BiCl3：0.1～12.5％；ZnCl2：0.15～15％；TiCl4：0.1～7.00％；CuCl2：2.75～3.25％；VCl3：0.3～8.3％；氯化稀土：0.3～8.3％；BaCl23～8.5％；C：62.5～75％。The present invention is constituted as follows: the low-mercury catalyst for synthesizing vinyl chloride comprises the following components by weight: HgCl 2 : 2.5-3.5%; BiCl 3 : 0.1-12.5%; ZnCl 2 : 0.15-15%; TiCl 4 CuCl 2 : 2.75-3.25%; VCl 3 : 0.3-8.3%; rare earth chloride: 0.3-8.3%; BaCl 2 3-8.5%; C: 62.5-75%.
上述的一种合成氯乙烯用的低汞触媒，所述的BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土总量≤32％。In the aforementioned low-mercury catalyst for the synthesis of vinyl chloride, the total amount of BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride is ≤32%.
上述的一种合成氯乙烯用的低汞触媒，按重量计，包括以下成份：HgCl2：3.5％；BiCl3：3％；ZnCl2：4％；TiCl4：3％；CuCl2：3％；VCl3：4％；氯化稀土：4％；BaCl24％；余量为C。The aforementioned low-mercury catalyst for the synthesis of vinyl chloride comprises the following components by weight: HgCl 2 : 3.5%; BiCl 3 : 3%; ZnCl 2 : 4%; TiCl 4 : 3%; CuCl 2 : 3% ; VCl 3 : 4%; Rare earth chloride: 4%; BaCl 2 4%;
上述的一种合成氯乙烯用的低汞触媒，所述氯化稀土为钪、钇、镧和/或铈的氯化物之一，或任意两种以上的混合物。In the aforementioned low-mercury catalyst for the synthesis of vinyl chloride, the rare earth chloride is one of the chlorides of scandium, yttrium, lanthanum and/or cerium, or a mixture of any two or more.
申请人经实验发现，本发明原料中的BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土在合成氯乙烯的工艺条件下本身具备一定的催化作用。合理选择BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土的配比，利用其协同效应，可以用来替代部分HgCl2的催化功能，降低氯化汞的用量。同现有技术相比，本发明用廉价氯化物BiCl3、ZnCl2、TiCl4、CuCl2、VCl3和BaCl2替代昂贵的HgCl2，更加环保。配方中的TiCl4与氯化稀土的协同效应好，制备的低汞触媒使用时间长不易潮解，具有环保，操作方便、安全等优点；同时能进一步降低汞的用量，克服现有技术存在的问题。The applicant found through experiments that BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride in the raw materials of the present invention have a certain catalytic effect under the process conditions for synthesizing vinyl chloride. Reasonably choose the ratio of BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride, and use their synergistic effect to replace part of the catalytic function of HgCl 2 and reduce the amount of mercuric chloride. Compared with the prior art, the present invention uses cheap chlorides BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 and BaCl 2 to replace expensive HgCl 2 , which is more environmentally friendly. The synergistic effect of TiCl 4 in the formula and rare earth chloride is good, and the prepared low-mercury catalyst is not easy to deliquesce after a long service life, and has the advantages of environmental protection, convenient operation, and safety; at the same time, it can further reduce the amount of mercury and overcome the problems existing in the existing technology .
经试验，该配比合理范围如下，按重量计，HgCl2：2.5～3.5％；BiCl3：0.1～12.5％；ZnCl2：0.15～15％；TiCl4：0.1～7.00％；CuCl2：2.75～3.25％；VCl3：0.3～8.3％；氯化稀土：0.3～8.3％；BaCl23～8.5％；C：62.5～75％。氯化稀土为钪、钇、镧和/或铈的氯化物之一，或任意两种以上氯化物的混合物。After testing, the reasonable range of the ratio is as follows, by weight, HgCl 2 : 2.5-3.5%; BiCl 3 : 0.1-12.5%; ZnCl 2 : 0.15-15%; TiCl 4 : 0.1-7.00%; CuCl 2 : 2.75% ～3.25%; VCl 3 : 0.3～8.3%; rare earth chloride: 0.3～8.3%; BaCl 2 3～8.5%; C: 62.5～75%. The rare earth chloride is one of the chlorides of scandium, yttrium, lanthanum and/or cerium, or a mixture of any two or more chlorides.
本发明研制合成新的低汞触媒，以大量廉价的BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土替代部分HgCl2制取低汞触媒，在充分保障催化性能的同时使触媒中降低HgCl2含量≤3.5％，不仅降低了资源消耗，同时降低了触媒的生产成本。本发明制备的一种合成氯乙烯用的低汞触媒适用于合成氯乙烯二段工序。The invention develops and synthesizes a new low-mercury catalyst, and substitutes a large amount of cheap BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride to replace part of HgCl 2 to produce a low-mercury catalyst, which fully guarantees the catalytic performance At the same time, the content of HgCl2 in the catalyst is reduced to ≤3.5%, which not only reduces resource consumption, but also reduces the production cost of the catalyst. The low-mercury catalyst for synthesizing vinyl chloride prepared by the invention is suitable for the second-stage process of synthesizing vinyl chloride.
具体实施方式 Detailed ways
本发明的实施例1：按照下述配比，HgCl2：3.5％；BiCl3：3％；ZnCl2：4％；TiCl4：3.5％；CuCl2：3％；VCl3：4.5％；氯化稀土：4.4％；BaCl26％；其余为C。C选择活性炭。先将BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl和氯化稀土溶解，然后在溶解的饱和溶液中加入用盐酸溶液低温浸泡过的活性炭(C)；加热至50℃浸渍24小时后，将浸渍后的活性炭放入含HgCl2的溶液中继续进行浸渍8小时取出，低温预干燥后继续干燥得到产品。Example 1 of the present invention: According to the following ratio, HgCl 2 : 3.5%; BiCl 3 : 3%; ZnCl 2 : 4%; TiCl 4 : 3.5%; CuCl 2 : 3%; VCl 3 : 4.5%; Rare earth oxide: 4.4%; BaCl 2 6%; the rest is C. C choose activated carbon. Dissolve BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl and rare earth chloride first, then add activated carbon (C) soaked in hydrochloric acid solution at low temperature into the dissolved saturated solution; heat to 50°C for 24 Hours later, the impregnated activated carbon was put into a solution containing HgCl 2 and continued to be impregnated for 8 hours to be taken out, followed by low-temperature pre-drying and continued drying to obtain the product.
经试验，该配比合理范围如下，按重量计，HgCl2：2.5～3.5％；BiCl3：0.1～12.5％；ZnCl2：0.15～15％；TiCl4：0.1～7.00％；CuCl2：2.75～3.25％；VCl3：0.3～8.3％；氯化稀土：0.3～8.3％；BaCl23～8.5％；C：62.5～75％。氯化稀土为钪、钇、镧和/或铈的氯化物之一，或任意两种以上氯化物的混合物。配方中，BiCl3、ZnCl2、TiCl4、CuCl2、VCl3、BaCl2和氯化稀土总量应≤32％，催化效果较好。After testing, the reasonable range of the ratio is as follows, by weight, HgCl 2 : 2.5-3.5%; BiCl 3 : 0.1-12.5%; ZnCl 2 : 0.15-15%; TiCl 4 : 0.1-7.00%; CuCl 2 : 2.75% ～3.25%; VCl 3 : 0.3～8.3%; rare earth chloride: 0.3～8.3%; BaCl 2 3～8.5%; C: 62.5～75%. The rare earth chloride is one of the chlorides of scandium, yttrium, lanthanum and/or cerium, or a mixture of any two or more chlorides. In the formula, the total amount of BiCl 3 , ZnCl 2 , TiCl 4 , CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride should be ≤32%, and the catalytic effect is good.
本发明的实施例2：按照下述配比，HgCl2：3.5％；BiCl3：0.1％；ZnCl2：0.15％；TiCl4：0.1％；CuCl2：3.25％；VCl3：8.3％；氯化稀土：8.3％；BaCl28.5％；其余为C。先将BiCl3、ZnCl2、TiCl4溶解，在含有BiCl3、ZnCl2、TiCl4饱和溶液中加入用盐酸溶液低温浸泡过的活性炭；加热至50℃浸渍12小时后，将浸渍后的活性炭放入含CuCl2、VCl3、BaCl2和氯化稀土的溶液中控制温度50℃继续进行浸渍12小时取出，再将浸渍后的产品活性炭放入含3.5％HgCl2的溶液中浸渍8小时，取出低温预干燥后继续干燥得到产品。氯化稀土为氯化镧。Example 2 of the present invention: according to the following ratio, HgCl 2 : 3.5%; BiCl 3 : 0.1%; ZnCl 2 : 0.15%; TiCl 4 : 0.1%; CuCl 2 : 3.25%; VCl 3 : 8.3%; Rare earth: 8.3%; BaCl 2 8.5%; the rest is C. Dissolve BiCl 3 , ZnCl 2 , TiCl 4 first, add activated carbon soaked in hydrochloric acid solution at low temperature to the saturated solution containing BiCl 3 , ZnCl 2 , TiCl 4 ; Put it into a solution containing CuCl 2 , VCl 3 , BaCl 2 and rare earth chloride and control the temperature at 50°C to continue impregnating for 12 hours and take it out, then put the impregnated product activated carbon in a solution containing 3.5% HgCl 2 for 8 hours, take it out After low-temperature pre-drying, continue drying to obtain the product. The rare earth chloride is lanthanum chloride.
本发明的实施例3：最佳配比是，按重量计，按重量计，包括以下成份：HgCl2：3.5％；BiCl3：3％；ZnCl2：4％；TiCl4：3％；CuCl2：3％；VCl3：4％；氯化稀土：4％；BaCl24％；其余为C。先在含有BiCl3、ZnCl2的饱和溶液中加入用盐酸溶液低温浸泡过的活性炭；加热至50℃浸渍8小时后，将浸渍后的活性炭放入含TiCl4、CuCl2的饱和溶液中继续进行浸渍8小时，控制温度50℃，再将浸渍后的活性炭放入含VCl3、BaCl2和氯化稀土的溶液中浸渍8小时取出，此阶段仍然控制温度50℃，再将其放入含3％HgCl2的溶液中浸渍8小时，取出后低温预干燥后继续干燥得到产品。氯化稀土为钪、钇、和铈的氯化盐混合物。Embodiment 3 of the present invention: the optimal proportion is, by weight, by weight, including the following ingredients: HgCl 2 : 3.5%; BiCl 3 : 3%; ZnCl 2 : 4%; TiCl 4 : 3%; CuCl 2 : 3%; VCl 3 : 4%; rare earth chloride: 4%; BaCl 2 4%; First add activated carbon soaked in hydrochloric acid solution to the saturated solution containing BiCl 3 and ZnCl 2 at low temperature; after heating to 50°C for 8 hours, put the impregnated activated carbon into the saturated solution containing TiCl 4 and CuCl 2 to continue Immerse for 8 hours, control the temperature at 50°C, put the impregnated activated carbon in a solution containing VCl 3 , BaCl 2 and rare earth chloride for 8 hours and take it out. %HgCl 2 solution for 8 hours, after taking it out, pre-drying at low temperature and then continuing to dry to obtain the product. Rare earth chloride is a mixture of scandium, yttrium, and cerium chloride salts.
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| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN113131031A (en) * | 2021-04-09 | 2021-07-16 | 贵州理工学院 | Method for preparing ultra-low mercury catalyst by recycling waste batteries |
| CN113131031B (en) * | 2021-04-09 | 2022-07-15 | 贵州理工学院 | A method of recycling waste batteries to prepare ultra-low mercury catalyst |
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