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環保涂料用酯類單體與綠色溶劑高效制備技術項目啟動

文章出處: 網責任編輯: 人氣: 發表時候:2019-11-29 01:14:51 關鍵字:

1贏創SIPERNAT? 2200 沉淀法二2月4日,中國橡膠工業協會就《環境保護綜合名錄(2017年版)(征求意見稿)》(以下簡稱:《名錄》)中第728~734條目中包含橡膠主流促進劑和防老劑問題,向環保部提出反饋意見,建議根據橡膠助劑行業目前的整體生產現狀和橡膠行業的使用情況對《名錄》進行調整:S先將防老劑6PPD、TMQ、IPPD從《名錄》中撤銷;其次在《目錄》中標明使用清潔生產工藝的促進劑MBT、CBS、DCBS產品不屬于“雙高”(GHW/GHF)產品。

據了解,11月23日,國家環保部網站發布了的《名錄》涵蓋了887個被列入高污染或高環境風險的產品以及各類環境保護重點裝備,意見征求期截止至12月6日。《名錄》中列入了目前我國橡膠助劑行業的主要促進劑及防老劑產品,其中,728~730條將促進劑MBT、CBS和DCBS列為高污染和高環境風險產品,732~734條將防老劑6PPD、TMQ和IPPD列為高環境風險產品。

為此,中橡協于12月1日召集8家橡膠促進劑和防老劑主要生產企業召開緊急會議,分析這兩種產品的安全環保情況及在我國橡膠行業的使用情況,并向環保部提出行業的建議。

“入圍”產品用量大無替代品

“沒有橡膠助劑,就沒有橡膠工業。”中橡協助劑專業委員會秘書長高波說,我國橡膠工業2016年總產值超過萬億元,占有非常重要的地位。同時,橡膠助劑是橡膠工業的重要原材料,橡膠助劑的發展和穩定供應是我國橡膠工業正常發展的保證。

我國助劑行業從本世紀初開始就大力推行清潔生產工藝,已主動逐漸淘汰了如促進劑NOBS、防老劑D等具有污染性的產品,目前橡膠助劑產品從生產過程到廢物處理等環節的工藝都是朝著無毒無害化方向前進的。

高波補充道,促進劑和防老劑的產量占橡膠助劑總產量的63%。在促進劑中,次磺酰胺類促進劑產量達16.4萬噸,占促進劑總量的49.5%。在防老劑中,酮胺類和對苯二胺類防老劑是輪胎膠料的主要防老體系產品,胺類防老劑約占防老劑總量的90%,其中防老劑6PPD、IPPD和TMQ產品占83.2%。而且此次所列出的6種橡膠助劑目前沒有替代產品,如果這些產品被限產將嚴重影響市場供應。

據中國橡膠網記者了解,由于今年國家加大了環保力度,助劑用原材料不僅大幅提價,而且貨源緊張,導致橡膠助劑貨緊價揚,加上一批不環保的小企業停產,橡膠助劑供應緊張已經嚴重影響了我國輪胎等橡膠制品的正常生產。另外,由于我國橡膠助劑產量占世界總產量75%左右,因此目前的供應緊張態勢甚至導致了世界范圍內的“恐慌”氣氛。

采用環保工藝的產品應排除

山東尚舜化工有限公司總經理劉經福提到,通過清潔生產工藝的實現,國內橡膠助劑行業的整體技術水平得到了大幅度的提高,目前行業內還從未出現過安全及污染事故。

促進劑MBT作為次磺酰胺類促進劑生產不可替代的原料,為了橡膠工業的健康可持續發展,必須保證其穩定供應;CBS是促進劑商品量好大的一個品種,物美價廉,而且還是不產生亞硝胺的伯胺類促進劑,已經列入工信部綠色輪胎原材料目錄中。

為此,劉經福建議將使用清潔生產工藝的促進劑MBT和促進劑CBS產品從《名錄》中去除,如溶劑法工藝、管道連續法生產工藝生產的MBT;雙氧水氧化工藝、氧氣氧化工藝生產的CBS。

科邁化工股份有限公司董事長王樹華認為,目前國內助劑行業的清潔工藝發展是有目共睹的,我國橡膠助劑總產量占 全Q75%以上的成績,是我們堅持發展了30年的綠色化生產的有力見證。

他提到,橡膠促進劑DCBS是遲延硫化效果好長的促進劑品種,雖然是仲胺類促進劑,但是其熱穩定性較高,在橡膠加工過程中產生N-亞硝基二環己胺的可能性很小,在德國“危險物質技術規則”TRGS 552法規中明確此物質不具致癌作用,使用過程安全。同時,在歐盟Regulation (EU) No. 1272/2008(關于物質和混合物分類、標簽和包裝的法規)中,該產品被歸為普通化學品而并非危險化學品;2017年歐盟GLP實驗室證明該產品對水體環境無污染,取消了水生慢性污染3級的標簽。

王樹華建議在DCBS替代物出現之前,可暫緩該產品列入《名錄》,并且建議采用清潔生產工藝的產品除外,比如溶劑法工藝、雙氧水氧化工藝、氧氣氧化工藝。

對于防老劑TMQ王樹華解釋道,該產品是一種酮胺類防老劑,對熱氧老化的防護非常有效,對金屬的催化氧化也有極強的抑制作用,毒性小,同時目前也沒有任何替代物,建議將其從《名錄》中撤除。

江蘇圣奧化學科技有限公司副總經理夏海洋提出,助劑行業的清潔生產普及度在不斷加大,自動化和智能化水平不斷提高,已經使產品對于環境的危害性不斷降低。

他指出6PPD是對苯二胺類防老劑,是天然橡膠和合成橡膠用抗臭氧劑和抗氧劑,對臭氧龜裂和屈撓疲勞的防護效能優良。6PPD是輪胎主要防老劑,其生產工藝目前已實現了理論化學的“零排放”,并獲得國家科技進步二等獎。6PPD是目前 防老劑,零排放、環境風險小,建議將其從《名錄》中撤除。

同時,夏海洋提到防老劑IPPD是6PPD投入使用前的主要產品,目前已退居二線, 2016年產量不足1萬噸,但從其理化性質分析,也不應當被列入“高環境風險”產品中。

蔚林新材料科技股份有限公司總經理王志強補充道,《中國橡膠助劑工業科技發展報告》《橡膠助劑工業的清潔生產》指導著我們助劑行業一直堅定地走在清潔生產工藝道路上,即使是在治污方面優良的歐盟也未對中國的產品做出限制,因此應當對高污染和高環境風險的界定添加限定條件。

中橡協技術經濟委員會主任朱紅也表示了同樣的觀點,我國助劑行業的技術進步在全世界范圍內都被公認,通過了國內外第三方機構的多次技術測試。同時,目前國內助劑產業集中度得到大幅度的提高,淘汰了不符合清潔生產工藝的高污染企業,實現了行業的轉型升級,相信龍頭企業會借助自身硬實力帶領助劑產品朝著綠色化方向不斷前行。

山東陽谷華泰化工股份有限公司副總經理杜孟成提出,行業應當聯合起來,從自身企業的產品做起,堅持綠色化生產,不斷進行清潔生產新工藝的技術攻關。

山東斯遞爾化工科技有限公司、中石化南京化學工業公司、河南開侖化工有限責任公司等企業代表也表示要推陳出新,助力橡膠助劑產品早日脫離“雙高”風險。

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.

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& 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.

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Products that adopt environmental protection process should be excluded

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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 .

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