CN112237924B - Catalyst for synthesizing promoter TBBS and application thereof - Google Patents
Catalyst for synthesizing promoter TBBS and application thereof Download PDFInfo
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- CN112237924B CN112237924B CN202011479216.2A CN202011479216A CN112237924B CN 112237924 B CN112237924 B CN 112237924B CN 202011479216 A CN202011479216 A CN 202011479216A CN 112237924 B CN112237924 B CN 112237924B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the field of chemical and physical methods, and particularly relates to a catalyst for synthesizing a promoter TBBS and application thereof. The catalyst is prepared by the following method: dissolving metal salt of the active component of the catalyst into ionic water to form a metal ion aqueous solution; adding excessive alkali metal aqueous solution into the metal ion aqueous solution rapidly to make the reaction system show strong basicity, and forming mixed precipitate of oxide or hydroxide by the metal ions in the solution; adding the precipitation slurry into a grinder for grinding; mixing the ground slurry with carrier particles, and filtering to obtain catalyst particles; and roasting the catalyst particles to obtain the finished catalyst. According to the invention, the Cu/Co/Mn trimetal oxide is loaded on the alumina as a solid catalyst, so that the yield of TBBS can be improved, the problem that the wastewater contains heavy metal ions is thoroughly solved, and the difficulty in wastewater treatment is greatly reduced.
Description
Technical Field
The invention belongs to the field of chemical and physical methods, and particularly relates to a catalyst for synthesizing a promoter TBBS and application thereof.
Background
In the course of producing various rubber products of tyre, rubber tube and rubber shoe, five major auxiliary agents must be used, these are rubber vulcanization accelerator (accelerator for short), rubber anti-ageing agent, rubber vulcanization and vulcanization activator, processing type rubber auxiliary agent and special functional auxiliary agent. Vulcanization accelerators are referred to as accelerators for short. A substance capable of promoting vulcanization. Can shorten the vulcanizing time, reduce the vulcanizing temperature, reduce the consumption of vulcanizing agents, improve the physical and mechanical properties of rubber and the like.
The rubber vulcanization accelerator TBBS (chemical name of N-tertiary butyl-2-benzothiazole sulfonamide, also known as NS) is one of important varieties of sulfenamide accelerators, is safe and low-toxic, and does not generate carcinogenic nitrosamine. The rubber vulcanization accelerator NS has the functions of scorching prevention, no toxicity, quick vulcanization and the like, and is called as a standard accelerator which is mainly applied to natural rubber, butadiene rubber, styrene butadiene rubber and isoprene rubber.
At present, the rubber vulcanization accelerator TBBS is produced by using sodium hypochlorite as an oxidant and oxidizing an accelerator MBT or sodium salt thereof and tert-butylamine to generate the accelerator TBBS. Wherein, the sodium hypochlorite method oxidation has the advantages of mature process, mild reaction condition, better product quality and higher yield (generally about 90-92 percent). But the production wastewater amount is large, about 8 tons of wastewater are produced by 1 ton of products, the salt content is high, the COD is high (generally more than 30000 ppm), the biochemical treatment is difficult (the biotoxicity exists), and the environmental protection is not favorable.
The oxygen catalytic oxidation method is favorable for environmental protection due to the great reduction of the wastewater yield, and colleges and enterprises have been researched in recent years. However, the oxygen oxidation process has the problems of low conversion rate, slow reaction speed, high process risk, large equipment investment and the like, and the feasibility of further industrial conversion is influenced. The oxidation-reduction potential of the hydrogen peroxide is not matched with the potential required by TBBS generation, so that the reaction yield is extremely low.
In summary, the TBBS synthesis processes reported at present all have certain disadvantages in terms of safety, environmental protection, etc., and a new TBBS synthesis process needs to be developed to solve or alleviate the above problems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a catalyst for synthesizing a promoter TBBS and application thereof.
The technical scheme adopted by the invention is as follows:
a catalyst for synthesizing a promoter TBBS is characterized in that: the preparation method comprises the following steps:
firstly, dissolving metal salt of a catalyst active component into ionic water to form a metal ion water solution; the active components of the catalyst are Cu, Co and Mn;
secondly, under the state of stirring at normal temperature, quickly adding excessive alkali metal aqueous solution into the metal ion aqueous solution to ensure that a reaction system presents strong basicity, and the metal ions in the solution form mixed precipitates of oxides or hydroxides;
thirdly, after the alkali metal aqueous solution is added, adding the precipitation slurry into a grinding machine, and grinding to form oxide or hydroxide slurry;
fourthly, mixing the ground slurry with carrier particles, and filtering to obtain catalyst particles;
fifthly, roasting the catalyst particles to obtain the finished catalyst.
Preferably, the molar ratio of the active components Cu, Co and Mn in the first step is 6:3: 1-2.
Preferably, the molar ratio of the active components Cu, Co and Mn in the first step is 6:3: 1.
Preferably, the total molar concentration of metal ions in the first step is 1 mol/L.
Preferably, the mass ratio of the carrier to the slurry in the fourth step is 1-2: 2-1.
The invention also comprises the application of the catalyst for synthesizing the promoter TBBS, which comprises the following steps:
(1) mixing MBT, tert-butylamine and a solvent under the stirring condition, and taking the mixture as a raw material solution for a synthetic reaction after the MBT is completely dissolved;
(2) introducing the prepared raw material solution and hydrogen peroxide into a reactor filled with the catalyst for synthesizing the promoter TBBS for oxidation reaction;
(3) collecting the material flowing out of the reactor, settling, layering, collecting the upper organic phase, cooling the organic phase to separate out organic matters, filtering and washing to obtain coarse TBBS;
(4) and washing the crude product obtained by filtering with water to obtain a TBBS wet material, and drying to obtain a TBBS finished product.
The mass ratio of MBT, tert-butylamine and solvent in step (1) is as follows: 1:1-10: 2.5-5; the concentration of the hydrogen peroxide in the step (2) is 1 to 27 weight percent; preferably, the concentration of the hydrogen peroxide is 5-20 wt%; the mass ratio of the MBT in the raw material slurry to the effective content of the hydrogen peroxide is 1: 0.1-0.3; the reaction temperature is 0-60 ℃.
The feeding mass space velocity of the raw material MBT is 0.1h-1-10h-1Preferably 0.2h-1-1h-1。
And (4) in the step (3), the temperature of the cooling crystallization process is 0-10 ℃.
The reactor is one or more of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor and a micro-channel reactor; preferably a fixed bed reactor.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the Cu/Co/Mn trimetal oxide is loaded on the alumina as the solid catalyst, so that the yield of TBBS can be improved, and the solid catalyst is used for replacing a common water-soluble catalyst, so that the problem that the wastewater contains heavy metal ions is thoroughly solved, and the difficulty in wastewater treatment is greatly reduced.
Meanwhile, according to the process disclosed by the patent, MBT and tert-butylamine are used as raw materials, hydrogen peroxide is used as an oxidant, the use of sodium hypochlorite, hydrochloric acid, liquid caustic soda or liquid chlorine is avoided, the generation of a byproduct sodium chloride is solved from the source, and the problem that the wastewater contains salt is further thoroughly solved.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1: a catalyst for synthesizing a promoter TBBS is prepared by the following steps:
firstly, dissolving metal salt of active components of a catalyst into deionized water to form a metal ion aqueous solution; the catalyst comprises the active components of Cu, Co and Mn, and the metal salt is CuCl2，CoCl2，MnCl2(ii) a Secondly, rapidly adding excessive alkali metal aqueous solution into the metal ion aqueous solution under the state of stirring at normal temperature to ensure that the reaction system presents strong basicity, and the metal ions in the solution form mixed precipitates of oxides or hydroxides; thirdly, after the alkali metal aqueous solution is added, adding the precipitation slurry into a grinding machine, selecting a grinding ball of 0.5cm, grinding for 1 hour at normal temperature, and grinding to form oxide or hydroxide slurry; fourthly, mixing the ground slurry with carrier particles, and filtering to obtain catalyst particles; the fifth stepAnd roasting the catalyst particles at 400 ℃ for 1.5h to obtain the finished catalyst. The catalysts are shown in table 1 for different Cu, Co, Mn contents.
TABLE 1
| Metal species | Molar ratio of | Mass ratio of carrier to slurry | |
| M1 | Cu、Co | 2:1 | 1:1 |
| M2 | Cu、Co、Mn | 6:3:1 | 1:1 |
| M3 | Cu、Co、Mn | 6:3:2 | 1:1 |
| M4 | Cu、Co、Fe | 6:3:1 | 1:1 |
| M5 | Cu、Co、Mn | 6:3:1 | 1:2 |
| M6 | Cu、Co、Mn | 6:3:1 | 2:1 |
Example 2: the application of the catalyst for synthesizing the promoter TBBS comprises the following steps:
(1) mixing MBT, tert-butylamine and a solvent under the stirring condition, wherein the solvent is a mixture of water, isopropanol and cyclohexane; mixing for 0.6h under stirring; after the MBT is completely dissolved, performing synthetic reaction by using the MBT as a raw material solution;
(2) introducing the prepared raw material solution and 20% hydrogen peroxide into a reactor filled with 50g of the catalyst for synthesizing the promoter TBBS for oxidation reaction;
(3) collecting the material flowing out of the reactor, settling, layering, collecting the upper organic phase, cooling the organic phase to separate out organic matters, filtering and washing to obtain coarse TBBS;
(4) washing the crude product obtained by filtering with clear water for 3 times, wherein the water amount is 0.5 times of the mass of the wet material each time, thus obtaining a TBBS wet material, and drying to obtain a TBBS finished product.
Table 2 shows the yield and purity of TBBS under different reaction conditions.
TABLE 2
| Examples | Catalyst and process for preparing same | MBT: tert-butylamine: solvent(s) | Space velocity h of raw material slurry feeding-1 | Mass ratio of MBT to effective content in hydrogen peroxide | Reaction temperature (. degree.C.) | Yield (%) | Purity (%) |
| Example 1 | M1 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 79.2 | 87.1 |
| Example 2 | M2 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 93.0 | 99.3 |
| Example 3 | M3 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 90.5 | 92.5 |
| Example 4 | M4 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 85.9 | 94.2 |
| Example 5 | M5 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 95.7 | 99.4 |
| Example 6 | M6 | 1:6.6:4 | 0.5 | 1:0.2 | 40 | 84.6 | 99.2 |
| Example 7 | M5 | 1:1:2.5 | 0.5 | 1:0.2 | 40 | 74.6 | 89.9 |
| Example 8 | M5 | 1:10:5 | 0.5 | 1:0.2 | 40 | 85.5 | 99.6 |
| Example 9 | M5 | 1:6.6:4 | 0.2 | 1:0.2 | 40 | 93.4 | 98.9 |
| Example 10 | M5 | 1:6.6:4 | 1 | 1:0.2 | 40 | 92.1 | 97.1 |
| Example 11 | M5 | 1:6.6:4 | 0.5 | 1:0.2 | 0 | 94.0 | 99.4 |
| Example 12 | M5 | 1:6.6:4 | 0.5 | 1:0.2 | 60 | 95.6 | 98.9 |
| Example 13 | M5 | 1:6.6:4 | 0.5 | 1:0.1 | 40 | 90.6 | 99.1 |
| Example 14 | M5 | 1:6.6:4 | 0.5 | 1:0.3 | 40 | 89.6 | 96.2 |
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.
Claims (6)
1. A catalyst for synthesizing a promoter TBBS is characterized in that: the preparation method comprises the following steps:
firstly, dissolving metal salt of a catalyst active component into ionic water to form a metal ion water solution; the active components of the catalyst are Cu, Co and Mn; the mol ratio of the active components Cu, Co and Mn is 6:3: 1-2;
secondly, under the state of stirring at normal temperature, quickly adding excessive alkali metal aqueous solution into the metal ion aqueous solution to ensure that a reaction system presents strong basicity, and the metal ions in the solution form mixed precipitates of oxides and hydroxides;
thirdly, after the alkali metal aqueous solution is added, adding the precipitation slurry into a grinding machine, and grinding to form slurry of oxide and hydroxide;
fourthly, mixing the ground slurry with carrier particles, and filtering to obtain catalyst particles; the mass ratio of the carrier to the slurry is 1-2: 2-1; the carrier is alumina;
fifthly, roasting the catalyst particles to obtain the finished catalyst.
2. The catalyst for synthesis of a promoter, TBBS, according to claim 1, characterized in that: in the first step, the molar ratio of the active components Cu, Co and Mn is 6:3: 1.
3. Use of a catalyst for promoter TBBS synthesis according to any of claims 1-2, characterized in that it comprises the following steps:
(1) mixing MBT, tert-butylamine and a solvent under the stirring condition, and taking the mixture as a raw material solution for a synthetic reaction after the MBT is completely dissolved;
(2) introducing the prepared raw material solution and hydrogen peroxide into a reactor filled with the catalyst for synthesizing the promoter TBBS for oxidation reaction;
(3) collecting the material flowing out of the reactor, settling, layering, collecting an upper organic phase, cooling the organic phase to separate out an organic matter, filtering and washing to obtain crude TBBS; cooling and crystallizing;
(4) and washing the crude product obtained by filtering with water to obtain a TBBS wet material, and drying to obtain a TBBS finished product.
4. The use of the catalyst for the synthesis of a promoter TBBS according to claim 3, wherein the mass ratio of MBT, tert-butylamine and solvent in step (1) is: 1:1-10: 2.5-5; the mass ratio of the MBT in the raw material solution in the step (2) to the effective content of the hydrogen peroxide is 1: 0.1-0.3, and the reaction temperature is 0-60 ℃.
5. The application of the catalyst for synthesizing the promoter TBBS as claimed in claim 3, wherein the temperature of the temperature-reducing crystallization process in the step (3) is 0-10 ℃.
6. The use of the catalyst for the synthesis of the promoter TBBS as claimed in claim 3, wherein the reactor is one or more of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor, and a microchannel reactor.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
| CN102380404A (en) * | 2011-08-29 | 2012-03-21 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-cyclohexyl benzothiazole sulfonamide and its preparation method |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
| CN106866577A (en) * | 2017-01-24 | 2017-06-20 | 蔚林新材料科技股份有限公司 | The method that the oxidation of catalytic molecular oxygen prepares sulfenamide thiofide in water phase |
| CN110354900A (en) * | 2019-08-27 | 2019-10-22 | 聊城宝和化学科技有限公司 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
| CN110523414A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator CBS synthesis |
| EP3632973A1 (en) * | 2018-10-01 | 2020-04-08 | Trinseo Europe GmbH | Method of preparing vulcanizable rubber composites |
-
2020
- 2020-12-16 CN CN202011479216.2A patent/CN112237924B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717380A (en) * | 2009-12-09 | 2010-06-02 | 河南省开仑化工有限责任公司 | Clean production method of rubber vulcanizing accelerator TBBS |
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
| CN102380404A (en) * | 2011-08-29 | 2012-03-21 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-cyclohexyl benzothiazole sulfonamide and its preparation method |
| CN106866577A (en) * | 2017-01-24 | 2017-06-20 | 蔚林新材料科技股份有限公司 | The method that the oxidation of catalytic molecular oxygen prepares sulfenamide thiofide in water phase |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
| CN110523414A (en) * | 2018-05-25 | 2019-12-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of supported catalyst and its application in rubber accelerator CBS synthesis |
| EP3632973A1 (en) * | 2018-10-01 | 2020-04-08 | Trinseo Europe GmbH | Method of preparing vulcanizable rubber composites |
| CN110354900A (en) * | 2019-08-27 | 2019-10-22 | 聊城宝和化学科技有限公司 | Rubber vulcanization accelerator N-tertiary butyl -2-[4-morpholinodithio sulfenamide (NS) catalyst preparation and application method |
Non-Patent Citations (2)
| Title |
|---|
| Novel synthesis and shape-dependent catalytic performance of Cu-Mn oxides for CO oxidation;Zhixun Li etal.,;《Applied Surface Science》;20170123;第335-341页 * |
| 制备方法对Cu-Mn/ZrO2催化剂合成甲醇反应性能的影响;陈小平等;《茂名学院学报》;20010228;第7-11页 * |
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