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环保涂料用酯类单体与绿色溶剂高效制备技术项目启动

文章出处: 网责任编辑: 人气: 发表时候:2018-10-19 15:26:06 关键字:

1赢创SIPERNAT 2200 沉淀法二2月4日,中国橡胶工业协会就《环境保护综合名录(2017年版)(征求意见稿)》(以下简称:《名录》)中第728~734条目中包含橡胶主流促进剂和防老剂问题,向环保部提出反馈意见,建议根据橡胶助剂行业目前的整体生产现状和橡胶行业的使用情况对《名录》进行调整:首先将防老剂6PPD、TMQ、IPPD从《名录》中撤销;其次在《目录》中标明使用清洁生产工艺的促进剂MBT、CBS、DCBS产品不属于“双高”(GHW/GHF)产品。

据了解,11月23日,国家环保部网站发布了的《名录》涵盖了887个被列入高污染或高环境风险的产品以及各类环境保护重点装备,意见征求期截止至12月6日。《名录》中列入了目前我国橡胶助剂行业的主要促进剂及防老剂产品,其中,728~730条将促进剂MBT、CBS和DCBS列为高污染和高环境风险产品,732~734条将防老剂6PPD、TMQ和IPPD列为高环境风险产品。

为此,中橡协于12月1日召集8家橡胶促进剂和防老剂主要生产企业召开紧急会议,分析这两种产品的安全环保情况及在我国橡胶行业的使用情况,并向环保部提出行业的建议。

“入围”产品用量大无替代品

“没有橡胶助剂,就没有橡胶工业。”中橡协助剂专业委员会秘书长高波说,我国橡胶工业2016年总产值超过万亿元,占有非常重要的地位。同时,橡胶助剂是橡胶工业的重要原材料,橡胶助剂的发展和稳定供应是我国橡胶工业正常发展的保证。

我国助剂行业从本世纪初开始就大力推行清洁生产工艺,已主动逐渐淘汰了如促进剂NOBS、防老剂D等具有污染性的产品,目前橡胶助剂产品从生产过程到废物处理等环节的工艺都是朝着无毒无害化方向前进的。

高波补充道,促进剂和防老剂的产量占橡胶助剂总产量的63%。在促进剂中,次磺酰胺类促进剂产量达16.4万吨,占促进剂总量的49.5%。在防老剂中,酮胺类和对苯二胺类防老剂是轮胎胶料的主要防老体系产品,胺类防老剂约占防老剂总量的90%,其中防老剂6PPD、IPPD和TMQ产品占83.2%。而且此次所列出的6种橡胶助剂目前没有替代产品,如果这些产品被限产将严重影响市场供应。

据中国橡胶网记者了解,由于今年国家加大了环保力度,助剂用原材料不仅大幅提价,而且货源紧张,导致橡胶助剂货紧价扬,加上一批不环保的小企业停产,橡胶助剂供应紧张已经严重影响了我国轮胎等橡胶制品的正常生产。另外,由于我国橡胶助剂产量占世界总产量75%左右,因此目前的供应紧张态势甚至导致了世界范围内的“恐慌”气氛。

采用环保工艺的产品应排除

山东尚舜化工有限公司总经理刘经福提到,通过清洁生产工艺的实现,国内橡胶助剂行业的整体技术水平得到了大幅度的提高,目前行业内还从未出现过安全及污染事故。

促进剂MBT作为次磺酰胺类促进剂生产不可替代的原料,为了橡胶工业的健康可持续发展,必须保证其稳定供应;CBS是促进剂商品量好大的一个品种,物美价廉,而且还是不产生亚硝胺的伯胺类促进剂,已经列入工信部绿色轮胎原材料目录中。

为此,刘经福建议将使用清洁生产工艺的促进剂MBT和促进剂CBS产品从《名录》中去除,如溶剂法工艺、管道连续法生产工艺生产的MBT;双氧水氧化工艺、氧气氧化工艺生产的CBS。

科迈化工股份有限公司董事长王树华认为,目前国内助剂行业的清洁工艺发展是有目共睹的,我国橡胶助剂总产量占全球75%以上的成绩,是我们坚持发展了30年的绿色化生产的有力见证。

他提到,橡胶促进剂DCBS是迟延硫化效果好长的促进剂品种,虽然是仲胺类促进剂,但是其热稳定性较高,在橡胶加工过程中产生N-亚硝基二环己胺的可能性很小,在德国“危险物质技术规则”TRGS 552法规中明确此物质不具致癌作用,使用过程安全。同时,在欧盟Regulation (EU) No. 1272/2008(关于物质和混合物分类、标签和包装的法规)中,该产品被归为普通化学品而并非危险化学品;2017年欧盟GLP实验室证明该产品对水体环境无污染,取消了水生慢性污染3级的标签。

王树华建议在DCBS替代物出现之前,可暂缓该产品列入《名录》,并且建议采用清洁生产工艺的产品除外,比如溶剂法工艺、双氧水氧化工艺、氧气氧化工艺。

对于防老剂TMQ王树华解释道,该产品是一种酮胺类防老剂,对热氧老化的防护非常有效,对金属的催化氧化也有极强的抑制作用,毒性小,同时目前也没有任何替代物,建议将其从《名录》中撤除。

江苏圣奥化学科技有限公司副总经理夏海洋提出,助剂行业的清洁生产普及度在不断加大,自动化和智能化水平不断提高,已经使产品对于环境的危害性不断降低。

他指出6PPD是对苯二胺类防老剂,是天然橡胶和合成橡胶用抗臭氧剂和抗氧剂,对臭氧龟裂和屈挠疲劳的防护效能优良。6PPD是轮胎主要防老剂,其生产工艺目前已实现了理论化学的“零排放”,并获得国家科技进步二等奖。6PPD是目前 防老剂,零排放、环境风险小,建议将其从《名录》中撤除。

同时,夏海洋提到防老剂IPPD是6PPD投入使用前的主要产品,目前已退居二线, 2016年产量不足1万吨,但从其理化性质分析,也不应当被列入“高环境风险”产品中。

蔚林新材料科技股份有限公司总经理王志强补充道,《中国橡胶助剂工业科技发展报告》《橡胶助剂工业的清洁生产》指导着我们助剂行业一直坚定地走在清洁生产工艺道路上,即使是在治污方面优良的欧盟也未对中国的产品做出限制,因此应当对高污染和高环境风险的界定添加限定条件。

中橡协技术经济委员会主任朱红也表示了同样的观点,我国助剂行业的技术进步在全世界范围内都被公认,通过了国内外第三方机构的多次技术测试。同时,目前国内助剂产业集中度得到大幅度的提高,淘汰了不符合清洁生产工艺的高污染企业,实现了行业的转型升级,相信龙头企业会借助自身硬实力带领助剂产品朝着绿色化方向不断前行。

山东阳谷华泰化工股份有限公司副总经理杜孟成提出,行业应当联合起来,从自身企业的产品做起,坚持绿色化生产,不断进行清洁生产新工艺的技术攻关。

山东斯递尔化工科技有限公司、中石化南京化学工业公司、河南开仑化工有限责任公司等企业代表也表示要推陈出新,助力橡胶助剂产品早日脱离“双高”风险。

These types of rubber chemicals should not be included in the "double high" directory

On December 4, China Rubber Industry Association included Main Rubber Accelerators and Anti-aging Articles on Items 728-734 in the "Comprehensive Environmental Protection Inventory (2017 Version) (Draft for Comment)" (hereinafter referred to as the "List") The Ministry of Environmental Protection proposed feedback on the proposal based on the overall situation of the rubber chemicals industry as a whole and the use of the rubber industry to adjust the "directory": first antioxidant 6PPD, TMQ, IPPD removed from the "directory"; Second, it is indicated in the "Catalog" that MBT, CBS and DCBS products that use cleaner production processes are not "Shuanggao" (GHW / GHF) products.

It is understood that on November 23, the "Directory" released by the Ministry of Environmental Protection website covers 887 products classified as high-risk or high-risk products and various key equipment for environmental protection. The opinion period As of December 6. The list includes the main accelerators and antioxidant products in China's rubber chemicals industry. Among them, 728 to 730 list MBT, CBS and DCBS as high-pollution and high-risk products, and 732 to 734 Antioxidants 6PPD, TMQ and IPPD are listed as high environmental risk products. To this end, the Rubber Association on December 1 convened 8 rubber accelerators and antioxidant manufacturers to hold an emergency meeting to analyze the safety of these two products, environmental protection and the use of the rubber industry in China , And make suggestions to the MEP over the industry.

& ldquo; Finalist & rdquo; Large amount of product without substitute

& ldquo; Without rubber chemicals, there is no rubber industry. "Gao Bo, secretary-general of the China Rubber Association's Auxiliary Committee, said that the total output value of China's rubber industry in 2016 exceeded one trillion yuan, occupying a very important position. At the same time, rubber chemicals is an important raw material for the rubber industry. The development and steady supply of rubber chemicals are the guarantee for the normal development of China's rubber industry.

China's auxiliary industry from the beginning of this century to vigorously promote cleaner production processes, has been gradually phased out, such as accelerator NOBS, antioxidant D and other polluting products, the current rubber chemicals from the production process To the waste treatment and other aspects of the process are towards non-toxic harmless direction.

Gao Bo added that the production of accelerators and anti-oxidants accounted for 63% of the total output of rubber chemicals. In the accelerator, sulfenamide accelerator production reached 164,000 tons, accounting for 49.5% of the total accelerator. Among the antioxidants, ketamine and p-phenylenediamine antioxidants are the main anti-aging system products of tire rubber. Amine anti-aging agents account for about 90% of the total amount of anti-aging agents. Antioxidants 6PPD, IPPD and TMQ products account for 83.2%. And the six kinds of rubber additives listed this time there is no alternative products, if these products are limited will seriously affect the market supply. According to the reporter learned from China Rubber Network, due to increased environmental protection efforts this year, not only a substantial price increase of raw materials for auxiliaries, but also tight supply, resulting in tight prices for rubber chemicals, coupled with a number of non-environmental protection Of small businesses to stop production, rubber additives tight supply has seriously affected China's rubber tires and other normal production. In addition, due to the fact that the output of rubber chemicals in China accounts for about 75% of the world's total output, the current tight supply situation has even led to the atmosphere of "panic" in the world.

Products that adopt environmental protection process should be excluded

Liu Jingfu, general manager of Shandong Shangshun Chemical Co., Ltd. mentioned that through the implementation of cleaner production technology, the domestic rubber chemicals industry The overall technical level has been greatly improved, the current industry has never seen a security and pollution incidents. Promoter MBT is an irreplaceable raw material for the production of sulfenamide accelerators. For the healthy and sustainable development of rubber industry, it must ensure its stable supply. CBS is the most widely promoted one. Lian, but also does not produce nitrosamines primary amine accelerator, has been included in the Ministry of Industry green tire raw materials directory. To this end, Liu Jingfu proposed to use the cleaner production process promoter MBT and accelerator CBS products from the "directory" to remove, such as solvent process, pipeline production of continuous production MBT; hydrogen peroxide oxidation process, Oxygen oxidation process to produce CBS.

Ko Mei Chemical Co., Ltd. Wang Shuhua, chairman of the view that the domestic additives industry clean process development is obvious to all, the total output of rubber chemicals in China accounted for more than 75% of the world's achievements, we insisted on the development of a 30 Years of strong testimony of green production.

He mentioned that the rubber accelerator DCBS is the delayed vulcanization accelerator with the longest effect, although it is a secondary amine accelerator, but its thermal stability is higher, resulting in the rubber processing N-sub Nitro dicyclohexylamine is unlikely, in the German "rule of hazardous substances" TRGS 552 regulations clearly this substance does not cause cancer, the use of safe process. In the meantime, in the EU Regulation (EU) No. 1272/2008 (Regulation on the Classification, Labeling and Packaging of Substances and Mixtures) the product is classified as a generic chemical and not as a hazardous chemical; in 2017, the EU GLP Laboratory certified Products on the water environment without pollution, Abolished aquatic chronic pollution level 3 label.

Wang Shuhua recommends that products be put on the "roster" before DCBS alternatives appear, and that products other than clean production processes, such as solvent processes, hydrogen peroxide oxidation processes, and oxygen oxidation processes, be recommended.

For antioxidant TMQ Wang Shuhua explained that the product is a ketone amine antioxidants, the protective effect of thermal aging is very effective, the catalytic oxidation of metals also have a strong inhibitory effect, toxicity is small, at the same time There are no substitutes at this time, so it is recommended that they be removed from the roster. Xiaoyang Yang, deputy general manager of Jiangsu Shengao Chemical Technology Co., Ltd., pointed out that the popularization of cleaner production in the auxiliary industry is continuously increasing, and the level of automation and intelligence is constantly improving, which has caused the products to be harmful to the environment reduce.

He pointed out that 6PPD is a p-phenylenediamine antioxidant, which is an antiozonant and an antioxidant for natural rubber and synthetic rubber and has excellent protection against ozone cracking and flex fatigue. 6PPD is the main anti-aging agent of the tire, the production process has now achieved the theoretical chemistry of "zero emissions", and won the second prize of national scientific and technological progress. 6PPD is the top antioxidant, zero emissions, environmental risk is small, it is recommended to remove it from the "directory." At the same time, Xia Haiyang mentioned antioxidant IPPD 6PPD is put into use before the main products, has now withdrawn second-line production in 2016 less than 10,000 tons, but from its physical and chemical properties of the analysis should not be listed Into "high environmental risk" products.

Wang Zhiqiang, general manager of Weilin New Materials Technology Co., Ltd. added that "China Rubber Auxiliary Industry Technology Development Report" and "Cleaner Production of Rubber Aid Industry" guide our auxiliary industry to always be firm Even on the road to cleaner production processes, even the leading EU in pollution control has not imposed any restrictions on Chinese products, so the definition of high pollution and high environmental risks should be added.

Zhu Hong, director of the Technical Committee of the Chinese Rubber Association, also expressed the same view that the technological progress of the additive industry in our country is universally acknowledged throughout the world and has passed many technical tests conducted by domestic and foreign third-party agencies. At the same time, the domestic concentration of additives industry has been greatly improved, out of non-compliance with cleaner production technology of high-polluting industries to achieve the transformation and upgrading of the industry, I believe leading enterprises will use their own hard-line auxiliaries toward green products Keep moving in the direction.

Du Mengcheng, deputy general manager of Shandong Yanggu Huatai Chemical Co., Ltd., proposed that the industry should unite to start from the products of its own enterprises, insist on green production and constantly carry out technological breakthroughs in the new technology of cleaner production.

Shandong Si Teer Chemical Technology Co., Ltd., Sinopec Nanjing Chemical Industry Company, Henan Kai Lun Chemical Co., Ltd. and other business representatives also said to introduce new and help rubber chemicals as soon as possible out of "double high" risk .