阅读说明：本技术 贵金属催化剂加氢缩合生产6ppd的方法 (Method for producing 6PPD by noble metal catalyst hydrogenation condensation ) 是由 陆平 李霞 刘海良 贾楠楠 何秀萍 于 2020-12-29 设计创作，主要内容包括：本发明属于橡胶助剂领域,具体涉及一种贵金属催化剂加氢缩合生产6PPD的方法,包括下述步骤：在高压釜中依次加入RT陪司、甲基异丁基酮、以及催化剂,投料结束封闭高压釜,氢气置换,控制反应压力,开启搅拌,控制恒温反应时间；反应完毕,泄压,过滤样品采用气相色谱分析；其中,所述的催化剂为铂金属羧基催化剂。本发明开发了一种贵金属催化剂加氢缩合生产6PPD的方法。主要解决目前国内铜锌铝固定床工艺,RT陪司无法完全转化6PPD,少量MIBK转化MIBC等缺点。验证贵金属催化剂寿命,实现催化剂多次套用,稳定产品质量等优势。(The invention belongs to the field of rubber auxiliaries, and particularly relates to a method for producing 6PPD by hydrogenation condensation of a noble metal catalyst, which comprises the following steps: sequentially adding RT cose, methyl isobutyl ketone and a catalyst into the high-pressure kettle, closing the high-pressure kettle after the feeding is finished, replacing hydrogen, controlling the reaction pressure, starting stirring, and controlling the constant-temperature reaction time; after the reaction is finished, pressure is released, and a filtered sample is analyzed by gas chromatography; wherein the catalyst is a platinum metal carboxyl catalyst. The invention develops a method for producing 6PPD by the hydrogenation and condensation of a noble metal catalyst. Mainly solves the defects that RT coss can not completely convert 6PPD and a small amount of MIBK can not convert MIBC in the prior domestic copper-zinc-aluminum fixed bed process. The service life of the noble metal catalyst is verified, and the advantages of repeated application of the catalyst, stable product quality and the like are realized.)

1. A method for producing 6PPD by the hydrogenation and condensation of a noble metal catalyst is characterized by comprising the following steps: sequentially adding RT cose, methyl isobutyl ketone and a catalyst into the high-pressure kettle, closing the high-pressure kettle after the feeding is finished, replacing hydrogen, controlling the reaction pressure, starting stirring, and controlling the constant-temperature reaction time; after the reaction is finished, pressure is released, and a filtered sample is analyzed by gas chromatography; wherein the catalyst is a platinum metal carboxyl catalyst.

2. The method of claim 1, wherein the catalyst is T3H 5X.

3. The method for producing 6PPD by the catalytic hydrocondensation of noble metals according to claim 1, wherein the catalyst is filtered and used mechanically after the reaction.

4. The method for producing 6PPD by the hydrocondensation of noble metal catalyst according to claim 1, wherein the platinum metal content in the catalyst is 1-5%, and the water content in the catalyst is 20-70%.

5. The method for producing 6PPD by the catalytic hydrocondensation of noble metals according to claim 1, wherein the catalyst contains 3% of platinum metal and 60% of water.

6. The method for producing 6PPD by noble metal catalyst hydrocondensation according to claim 1, wherein the molar ratio of RT cose to MIBK feed is 1.2-1.8; the feeding amount of the catalyst is 0.8-1.5% of the mass of RT cose; the reaction pressure is controlled to be 1-4MPa, and the reaction temperature is controlled to be 100-170 ℃.

7. The method for producing 6PPD by noble metal catalyst hydrocondensation according to claim 1, wherein the molar ratio of RT cose to MIBK feed is 1.4; the feeding amount of the catalyst is 1% of the mass of the RT coss; the reaction pressure is controlled to be 3MPa, and the reaction temperature is controlled to be 150 ℃.

8. The method for producing 6PPD by the hydrocondensation of a noble metal catalyst according to claim 3, wherein the catalyst replenishment amount for each set is 0.1-0.5% of the mass of RT coss.

9. The method for producing 6PPD by the catalytic hydrocondensation of noble metals according to claim 3, wherein the catalyst make-up for each set is 0.3% of the mass of RT coss.

Technical Field

The invention belongs to the field of rubber auxiliaries, and particularly relates to a method for producing 6PPD by hydrogenation condensation of a noble metal catalyst.

Background

The rubber antioxidant 6PPD (also abbreviated as 4020) has the chemical name of N- (1, 3-dimethylbutyl) -N-phenyl-p-phenylenediamine, belongs to a p-phenylenediamine antioxidant with high performance, solvent resistance and low toxicity, and is widely applied to the field of rubber additives.

Condensation equation:

reduction equation: s

The production process is one-step RT cose and methyl isobutyl ketone (MIBK) condensation to produce Schefflerine, and in-situ one-step hydrogenation is carried out to synthesize 6 PPD.

At present, the domestic industrial production of 6PPD is represented by southern chemical company, a copper-zinc-aluminum catalyst fixed bed is adopted for production, the product purity is different from foreign products, the RT coss conversion rate is lower than 99.5%, a small amount of RT coss residue exists in the product, MIBK can be converted into MIBC in the hydrogenation process, MIBC needs to be separated, dehydrogenation is converted into MIBK, the MIBK is put into subsequent production, the technological process is complex, and the one-time investment of the device is high. And a small amount of copper catalyst powder enters the product, which can affect the quality of the tire.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a method for producing 6PPD by hydrogenating and condensing a noble metal catalyst.

In order to achieve the purpose, the invention adopts the technical scheme that:

a method for producing 6PPD by the hydrogenation and condensation of a noble metal catalyst comprises the following steps: sequentially adding RT cose, methyl isobutyl ketone and a catalyst into the high-pressure kettle, closing the high-pressure kettle after the feeding is finished, replacing hydrogen, controlling the reaction pressure, starting stirring, and controlling the constant-temperature reaction time; after the reaction is finished, pressure is released, and a filtered sample is analyzed by gas chromatography; wherein the catalyst is a platinum metal carboxyl catalyst.

The catalyst is T3H5X, and is purchased from Shaanxi Rui New materials GmbH.

After the reaction is finished, the catalyst is filtered by heat and reused.

The content of platinum metal in the catalyst is 1-5%.

The content of platinum metal in the catalyst is 3%.

The feeding molar ratio of RT coss to MIBK is 1.2-1.8; the feeding amount of the catalyst is 0.8-1.5% of the mass of RT cose; the reaction pressure is controlled to be 1-4MPa, and the reaction temperature is controlled to be 100-170 ℃.

The molar ratio of the RT coss to the MIBK is 1.4; the feeding amount of the catalyst is 1% of the mass of the RT coss; the reaction pressure is controlled to be 3MPa, and the reaction temperature is controlled to be 150 ℃.

The supplement amount of the catalyst used for each set is 0.1-0.5% of the mass of RT cose.

The catalyst supplement amount of each set is 0.3 percent of the mass of RT coss.

Compared with the prior art, the invention has the beneficial effects that:

the invention develops a method for producing 6PPD by the hydrogenation and condensation of a noble metal catalyst. Mainly solves the defects that RT coss can not completely convert 6PPD and a small amount of MIBK can not convert MIBC in the prior domestic copper-zinc-aluminum fixed bed process. The service life of the noble metal catalyst is verified, and the advantages of repeated application of the catalyst, stable product quality and the like are realized.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the following provides a detailed description of the present invention with reference to the embodiments.

Example 1: a method for producing 6PPD by noble metal catalyst hydrogenation condensation adopts the following steps:

(1) sequentially adding RT-cose, methyl isobutyl ketone and a catalyst into the high-pressure kettle, controlling a certain molar ratio of RT and methyl isobutyl ketone, controlling a certain ratio (mass ratio) of the feeding amount of a fresh catalyst and RT-cose, closing the high-pressure kettle after feeding is finished, replacing hydrogen, controlling a certain reaction pressure, starting stirring, and controlling constant-temperature reaction time. After the reaction is finished, the pressure is released, and the hot filtration catalyst is used indiscriminately. The filtered sample was analyzed by gas chromatography.

(2) The influence of the platinum content of the catalyst is considered, and the catalyst is T3H5X which is purchased from Shaanxi Rui New materials GmbH. Controlling the content of noble metal to be 1-5%, the water content of the catalyst to be 60%, the reaction pressure to be 3MPa, the reaction temperature to be 150 ℃, the feeding molar ratio to be 1.4 and the reaction time to be 2 h.

Table 1 shows the effect of different catalyst platinum contents on the results.

TABLE 1

The results show that: a 3% platinum content catalyst is preferred for reasons of product purity and catalyst economy.

(3) And (3) observing the influence of the water content of the catalyst, controlling the water content of the catalyst to be 20-70%, controlling the reaction pressure to be 3MPa, controlling the reaction temperature to be 150 ℃, controlling the feed ratio to be 1.4, and analyzing data for 2h of reaction time, wherein the table 2 shows the influence of the water content of different catalysts on the result, and the result shows that the catalyst with the water content of 60% is preferred in consideration of the product purity factor.

TABLE 2

(4) The RT coss to MIBK feed ratio (molar ratio) was controlled between 1.2 and 1.8 and the analytical data, table 3 shows the effect of different feed ratios on the results. The 1.4 molar ratio is preferred for process energy consumption considerations.

TABLE 3

(5) The catalyst inventory (mass ratio to RT-coss) was controlled at 0.8-1.5% analytical data, and Table 4 shows the effect of different catalyst inventory on the results. The results show that 1% mass ratio catalyst is preferred in view of catalyst consumption, as well as RT conversion factors.

TABLE 4

(6) Controlling the reaction pressure to be 1-4MPa, and analyzing data. Table 5 shows the effect of different reaction pressures on the results, with 3MPa being preferred as the reaction pressure in view of reactor investment, conversion and safety.

TABLE 5

(7) The temperature is controlled to be 100 ℃ and 170 ℃, and the data are analyzed. Table 6 shows the effect of different temperatures on the results. The reaction temperature is suitable when the temperature is 150 DEG C

TABLE 6

(8) The catalyst application experiment shows that the addition amount of the catalyst for each application is controlled to be 0.3 percent.

Table 7 shows the effect of the number of different catalyst applications on the results. The results show that the catalyst is suitable for use in a supplementary amount, and the catalyst is kept stable

TABLE 7

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.