CN111925307A - Method for preparing ex-situ pre-vulcanizing agent by mixed alkali method - Google Patents
Method for preparing ex-situ pre-vulcanizing agent by mixed alkali method Download PDFInfo
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- CN111925307A CN111925307A CN201910395203.8A CN201910395203A CN111925307A CN 111925307 A CN111925307 A CN 111925307A CN 201910395203 A CN201910395203 A CN 201910395203A CN 111925307 A CN111925307 A CN 111925307A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0243—Other after-treatment of sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
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Abstract
The invention discloses a method for preparing an external pre-vulcanizing agent by a mixed alkali method, belonging to the technical field of synthesis of organic sulfides of an acyclic unsaturated carbon skeleton, wherein the synthesis method comprises the following steps: adding elemental sulfur and a solvent into a reaction kettle, heating to 130-180 ℃, slowly adding isobutene into the reaction kettle, reacting for 2-6h at constant temperature, and finishing the reaction. And standing and separating the product, and filtering an organic phase to obtain a finished product. The invention has the characteristics of low product odor, high yield, low cost, low equipment requirement and the like.
Description
Technical Field
The invention relates to the technical field of synthesis of organic sulfides with an acyclic unsaturated carbon skeleton, in particular to a method for preparing an ex-situ pre-vulcanizing agent by a mixed alkali method.
Background
In the 20 th century and 80 th year, an ex-situ presulfurization technology was developed, which combines an ex-situ presulfurization agent and a catalyst outside a reactor by a dipping or kneading method, so that the ex-situ presulfurization agent is uniformly distributed on the surface and in micropores of the catalyst, and hydrogen is introduced for activation before use. The method overcomes the defect of in-situ presulfurization, and the catalyst after vulcanization has high activity and tends to gradually replace in-situ presulfurization. Whether in-situ presulfiding or ex-situ presulfiding, the activation of the hydrogenation catalyst must be accomplished in the presence of an ex-situ presulfiding agent. The conventional industrial ex-situ presulfurizing agents mainly include carbon disulfide (CS2), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), n-butyl mercaptan (n-BM), Ethanethiol (EM), etc. Most of the sulfur-containing organic sulfur-.
The ex-situ presulfurizing agent can promote the addition synthesis reaction of sulfur and C-containing olefin such as isobutene or butadiene in an alkaline environment, and the alkaline matter can be inorganic base such as ammonia water, sodium carbonate and the like; organic base organic amines: such as triethylamine, diethylamine, etc., it is also possible to use a thiazulene-type catalyst. However, the cost of the files catalyst is very high, and the files catalyst is not suitable for the requirement of large-scale production; organic alkalis, organic catalysts and finished products are difficult to separate, the production process waste water is difficult to treat, and the method is not suitable for large-scale production. The inorganic alkali ammonia water is also a good catalyst, the cost is low, the process water can be recycled, but the reaction product contains ammonia, methyl mercaptan, methyl sulfide, hydrogen sulfide and the like which are difficult to control and treat, and malodorous gas is not an ideal catalyst.
Disclosure of Invention
In order to realize the purpose of the invention, the invention provides a method for preparing the ex-situ presulfurizing agent by a mixed alkali method, which solves the problems of foul smell, more low sulfur substances, bromine content, corrosiveness, difficult control of reaction process and the like in the synthesis of the existing ex-situ presulfurizing agent, and meets the requirement of large-scale production.
The invention provides the following technical scheme:
a method for preparing an ex-situ presulfurizing agent by a mixed alkali method comprises the following steps:
1) adding sulfur and a catalyst solvent into a reaction kettle, performing nitrogen replacement, heating to 130-180 ℃, then slowly adding isobutene into the reaction kettle, reacting at a constant temperature for 2-6 hours, and cooling to room temperature;
2) and (3) standing and separating the cooled reaction liquid to obtain the ex-situ pre-vulcanizing agent.
Preferably, the catalyst solvent is a metal alkali mixed solution formed by mixing strong alkali based on sodium hydroxide or potassium hydroxide and then adding other weak alkali.
Further, the concentration of the metal-alkali mixed solution is 0.3mol/L-6 mol/L.
Further, the molar ratio of the basic strong base to the weak base is as follows: 0.05-30.
Furthermore, the metal base mixed solution is one of a mixed solution of sodium hydroxide and sodium carbonate, a mixed solution of potassium hydroxide and potassium carbonate, a mixed solution of sodium hydroxide and sodium bicarbonate, a mixed solution of potassium hydroxide and potassium bicarbonate, a mixed solution of sodium hydroxide, potassium carbonate and potassium bicarbonate, and a mixed solution of potassium hydroxide, sodium carbonate and sodium bicarbonate.
Preferably, the molar ratio of the added sulfur to the added isobutene is 1.8:1-4: 1.
Preferably, the catalyst solvent is used in an amount of 1.01 to 1.03 times the amount of the conventional catalyst.
Preferably, after the isobutene is slowly added into the reaction kettle, the pressure in the reaction kettle is kept between 0.07 and 3.2MPa for constant-temperature reaction.
Advantageous effects
The invention provides a method for preparing an external pre-vulcanizing agent by a mixed alkali method, which has the following beneficial effects:
1) the invention adopts mixed alkali as a catalyst, particularly uses hydroxide as an auxiliary catalyst, improves alkalinity, can open the ring of sulfur simple substance under the condition of lower temperature, and leads the simple substance sulfur to be broken into low-chain sulfur molecules under the action of strong alkali and temperature, such as S-S for short sulfur 2, S-S-S for short sulfur 3, S-S-S-S for short sulfur 4, S-S-S-S for short sulfur 5 and the like; carrying out synthetic reaction on low-chain sulfur and isobutene in an alkaline environment; because the invention adopts the metal hydroxide strong base as the ring-opening agent of the sulfur, the reaction is rapid, the relative pressure of the system is lower (the pressure is lower than that of the traditional single catalyst by more than 1-1.5 MPA), the requirement on equipment is low, the manufacturing cost of the equipment is low, the reaction temperature is lower than that of other similar single catalysts (generally lower by 5-10 ℃), and the cost of synthetic energy is low.
2) The invention adopts mixed alkali as a catalyst, generally adopts slightly excessive alkali, the excessive part is 1 to 3 percent of the normal usage value, malodorous gases such as mercaptan, hydrogen sulfide, methyl mercaptan and the like in a reaction system are synthesized into metal salts in an alkaline system, such as sodium mercaptan, sodium methoxide or potassium mercaptan and the like, and the produced product is tasteless; sodium and potassium mercaptide and other substances are easily dissolved in water and are easy to separate, the content of the product is very low, and the purity of the product is ensured.
3) The product prepared by adopting the mixed alkali is easy to separate from the mixture, the density difference between the reaction organic phase and the alkali liquor is large, the product is easy to separate from the mixed solution, and the process is simple.
4) The adopted mixed catalyst is common chemicals, and the cost is low.
5) The reaction process water as a solvent can be recycled in the reaction system, and the process water amount is small.
6) Compared with the current domestic common vulcanizing agent, the off-site pre-vulcanizing agent developed by the project has the following advantages:
1. the smell is low;
2. the vulcanization time is shortened;
3. no corrosive elements of bromine and chlorine;
4. the sulfur content of the ex-situ presulfurizing agent prepared by the method is 46-56%.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
The reaction mechanism is as follows:
wherein R is isobutene
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Raw materials and dosage: 270kg of sulfur, 120kg of sodium hydroxide solution and 225kg of sodium carbonate solution, wherein the concentration of metal ions in the mixed alkali liquor is 0.3mol/L, 165kg of isobutene,
the preparation process comprises the following steps: adding sulfur into a reaction kettle, mixing a sodium hydroxide solution and a sodium carbonate solution to prepare a mixed alkali liquor, adding the prepared mixed alkali liquor into the reaction kettle, performing nitrogen displacement, stirring and heating to 130 ℃, then keeping the temperature of 130 ℃, slowly metering and introducing isobutene, then keeping the pressure at 3MPa, keeping the temperature for 2 hours, cooling to room temperature after the reaction is finished, discharging the mixture, and separating to obtain a product; in addition, the inorganic phase can be prepared into solution again for recycling.
And (3) product performance testing:
| item | Test results | Test method |
| Colour(s) | Light yellow | |
| Smell(s) | Has no pungent odor | |
| Sulfur content,% (m/m) | 56.5 | SH/T03032) |
| Kinematic viscosity (40 ℃ C.), mm2/s | 3.62 | GB/T265 |
| Copper sheet corrosion (121 ℃, 3h), grade | >4B | GB/T50963) |
Example 2
Raw materials and dosage: 194kg of sulfur, 185kg of sodium hydroxide solution, 128kg of sodium carbonate solution and 15kg of water, wherein the concentration of metal ions in the mixed alkali liquor is 0.5mol/L, 221kg of isobutene,
the preparation process comprises the following steps: adding sulfur into a reaction kettle, mixing a sodium hydroxide solution and a sodium carbonate solution to prepare a mixed alkali liquor, adding the prepared mixed alkali liquor into the reaction kettle, performing nitrogen displacement, stirring and heating to 150 ℃, then keeping the temperature of 150 ℃, slowly metering and introducing isobutene, then keeping the pressure at 3.2MPa, keeping the temperature for 3 hours, cooling to room temperature after the reaction is finished, discharging the mixture, and separating to obtain a product; in addition, the inorganic phase can be prepared into solution again for recycling.
And (3) product performance testing:
| item | Test results | Test method |
| Colour(s) | Amber colour | |
| Smell(s) | Has no pungent odor | |
| Sulfur content,% (m/m) | 57.3 | SH/T03032) |
| Kinematic viscosity (40 ℃ C.), mm2/s | 3.75 | GB/T265 |
| Copper sheet corrosion (121 ℃, 3h), grade | >4B | GB/T50963) |
Example 3
Raw materials and dosage: 220kg of sulfur, 200kg of sodium hydroxide solution, 125kg of sodium carbonate solution and 35kg of water, wherein the concentration of metal ions in the mixed alkali liquor is 0.7mol/L, and 252kg of isobutene
The preparation process comprises the following steps: adding sulfur into a reaction kettle, mixing a sodium hydroxide solution and a sodium carbonate solution to prepare a mixed alkali liquor, adding the prepared mixed alkali liquor into the reaction kettle, performing nitrogen displacement, stirring and heating to 160 ℃, then keeping the temperature of 160 ℃, slowly metering and introducing isobutene, then keeping the pressure at 3.2MPa, keeping the temperature for 4 hours, cooling to room temperature after the reaction is finished, discharging the mixture, and separating to obtain a product; in addition, the inorganic phase can be prepared into solution again for recycling.
And (3) product performance testing:
| item | Test results | Test method |
| Colour(s) | Amber colour | |
| Smell(s) | Has no pungent odor | |
| Sulfur content,% (m/m) | 58.66 | SH/T03032) |
| Kinematic viscosity (40 ℃ C.), mm2/s | 3.51 | GB/T265 |
| Copper sheet corrosion (121 ℃, 3h), grade | >4B | GB/T50963) |
Example 4
78kg of sulfur, 100kg of potassium hydroxide solution, 15.5kg of potassium carbonate solution and 10kg of water, wherein the concentration of metal ions in the mixed alkali liquor is 0.5mol/L, 10kg of water and 68kg of isobutene
The preparation process comprises the following steps: adding sulfur into a reaction kettle, mixing and blending a potassium hydroxide solution and a potassium carbonate solution to prepare a mixed alkali liquor, then adding the prepared mixed alkali liquor into the reaction kettle, performing nitrogen displacement, stirring and heating to 180 ℃, then keeping the temperature of 180 ℃, slowly metering and introducing isobutene, then keeping the pressure at 3.2MPa, keeping the temperature for 6 hours, cooling to room temperature after the reaction is finished, discharging the mixture, and separating to obtain a product; in addition, the inorganic phase can be prepared into solution again for recycling.
And (3) product performance testing:
| item | Test results | Test method |
| Colour(s) | Reddish brown | |
| Smell(s) | Has no pungent odor | |
| Sulfur content,% (m/m) | 53.8 | SH/T03032) |
| Kinematic viscosity (40 ℃ C.), mm2/s | 3.45 | GB/T265 |
| Copper sheet corrosion (121 ℃, 3h), grade | >4B | GB/T50963) |
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for preparing an external presulfurizing agent by a mixed alkali method is characterized by comprising the following steps: the method comprises the following steps:
1) adding sulfur and a catalyst solvent into a reaction kettle, performing nitrogen replacement, heating to 130-180 ℃, then slowly adding isobutene into the reaction kettle, reacting at a constant temperature for 2-6 hours, and cooling to room temperature;
2) and (3) standing and separating the cooled reaction liquid to obtain the ex-situ pre-vulcanizing agent.
2. The method for preparing the ex-situ presulfiding agent by the mixed-alkali method according to claim 1, wherein: the catalyst solvent is a metal alkali mixed solution which is formed by taking sodium hydroxide or potassium hydroxide as basic strong base and then adding other weak bases for mixing.
3. The method for preparing the ex-situ presulfiding agent by the mixed-alkali method according to claim 2, wherein: the concentration of the metal alkali mixed solution is 0.3-6 mol/L.
4. The method for preparing the ex-situ presulfiding agent by the mixed-alkali method according to claim 2, wherein: the molar ratio of the mixed basic strong alkali and weak alkali is as follows: 0.05-30.
5. The method for preparing the ex-situ presulfiding agent by the mixed-base method according to any one of claims 2 to 4, wherein: the metal alkali mixed solution is a mixture of one of a mixed solution of sodium hydroxide and sodium carbonate, a mixed solution of potassium hydroxide and potassium carbonate, a mixed solution of sodium hydroxide and sodium bicarbonate, a mixed solution of potassium hydroxide and potassium bicarbonate, a mixed solution of sodium hydroxide, potassium carbonate and potassium bicarbonate, and a mixed solution of potassium hydroxide, sodium carbonate and sodium bicarbonate.
6. The method for preparing the ex-situ presulfiding agent by the mixed-base method according to any one of claims 1 to 4, wherein: the molar ratio of the added sulfur to the added isobutene is 1.8:1-4: 1.
7. The method for preparing the ex-situ presulfiding agent by the mixed-base method according to any one of claims 1 to 4, wherein: the dosage of the catalyst solvent is 1.01 to 1.03 times of the dosage of the traditional catalyst.
8. The method for preparing the ex-situ presulfiding agent by the mixed-base method according to any one of claims 1 to 4, wherein: after isobutene is slowly added into the reaction kettle, the pressure in the kettle is kept between 0.07 and 3.2MPa for constant-temperature reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096353A (en) * | 2006-06-30 | 2008-01-02 | 山东联合化工股份有限公司 | Synthesis technique of sulfide isobutene by one-step method |
| CN105315182A (en) * | 2015-11-09 | 2016-02-10 | 定远县云森科技有限公司 | Method for efficiently preparing ex-situ presulfuration agent through medium-pressure solvothermal method |
| CN107868078A (en) * | 2016-09-26 | 2018-04-03 | 青岛九洲千和机械有限公司 | The synthesis technique of sulfide isobutene by one-step method |
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- 2019-05-13 CN CN201910395203.8A patent/CN111925307A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096353A (en) * | 2006-06-30 | 2008-01-02 | 山东联合化工股份有限公司 | Synthesis technique of sulfide isobutene by one-step method |
| CN105315182A (en) * | 2015-11-09 | 2016-02-10 | 定远县云森科技有限公司 | Method for efficiently preparing ex-situ presulfuration agent through medium-pressure solvothermal method |
| CN107868078A (en) * | 2016-09-26 | 2018-04-03 | 青岛九洲千和机械有限公司 | The synthesis technique of sulfide isobutene by one-step method |
Non-Patent Citations (2)
| Title |
|---|
| 罗海棠等: ""硫化异丁烯的制备工艺对其性能的影响"", 《合成润滑材料》 * |
| 黄锦霞: ""硫化异丁烯的合成"", 《精细化工》 * |
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Application publication date: 20201113 |