Catalyst for synthesizing tert-dodecyl mercaptan as well as preparation method and application of catalyst
The catalyst is prepared by combining anhydrous aluminum chloride, ferric chloride, aromatic hydrocarbon additives and anisole homologues, which solves the problem of low selectivity of existing catalysts and realizes the highly selective synthesis of tert-dodecyl mercaptan, which is suitable for polymer polymerization processes.
Patent Information
- Application Number
- CN202510900192.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-01
- Publication Date
- 2025-10-10
AI Technical Summary
Existing catalysts for the synthesis of tert-dodecyl mercaptan are deficient in selectivity and stability, resulting in low synthesis efficiency.
A catalyst is prepared by combining anhydrous aluminum chloride, ferric chloride, aromatic hydrocarbon additives and anisole homologues through a mixed reaction in a specific ratio and under mild conditions, and is used to catalyze the addition reaction of tetrapropylene with hydrogen sulfide.
Under mild conditions, the selectivity of tert-dodecyl mercaptan reached over 95%, and the product is suitable for polymer polymerization processes such as ABS, SBR and nitrile latex.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of tertiary dodecyl mercaptan, in particular to a catalyst for synthesizing tertiary dodecyl mercaptan and a preparation method and application thereof. BACKGROUND
[0002] At present, the catalysts used in the synthesis of tertiary dodecyl mercaptan are mainly solid acid catalysts, which are realized by the addition reaction of olefins (such as tetrameric propylene) and hydrogen sulfide. The commonly used catalysts include the following types: (1) Y-type molecular sieve catalyst Y-type molecular sieves (such as HY, USY, mesoporous Y molecular sieves, etc.) are widely used in the synthesis of tertiary dodecyl mercaptan, which has high specific surface area and good acid sites, and is suitable for catalyzing the addition reaction of olefins and hydrogen sulfide. However, the thermal stability and carbon deposition resistance of Y-type molecular sieves are poor, and the catalyst activity decreases after long-term operation, resulting in low selectivity of tertiary dodecyl mercaptan.
[0003] (2) Acid resin catalyst Such as LXC-503 cation exchange resin and HND-33 solid acid catalyst, which is commonly used in absorption tower type reactor to improve the gas-liquid contact efficiency, promote the rapid diffusion of hydrogen sulfide by increasing the specific surface area of the catalyst, thereby improving the reaction rate. However, this type of catalyst is easily affected by reaction conditions (such as temperature, pressure), and has a significant carbon deposition problem, resulting in a decrease in selectivity.
[0004] In summary, although the existing catalysts have made some progress in the synthesis of tertiary dodecyl mercaptan, they still have problems such as low selectivity, and therefore, further optimization of the catalyst is needed. SUMMARY
[0005] The technical problem to be solved by the present application is to overcome the shortcomings of the prior art, and to provide a catalyst for synthesizing tertiary dodecyl mercaptan and a preparation method and application thereof. The present application can prepare the catalyst under mild conditions, and when used for synthesizing tertiary dodecyl mercaptan, the selectivity is above 95%, and the synthesized tertiary dodecyl mercaptan product is suitable for high molecular polymerization process of ABS, SBR and nitrile rubber latex products.
[0006] The technical scheme of the present application is as follows: In a first aspect, the present application provides a preparation method of a catalyst for synthesizing tertiary dodecyl mercaptan, comprising the following steps: S1: adding an aromatic hydrocarbon additive into a reaction kettle, and adding anhydrous aluminum chloride and ferric chloride in batches while stirring, and mixing uniformly; S2: the reaction kettle is sealed with nitrogen, and anisole or anisole homologues are added dropwise under the condition of temperature control and stirring, the dropwise adding time is 0.5-1h, after the dropwise adding is completed, the reaction is continued under the condition of temperature control and stirring for 0.1-0.5h under the condition of nitrogen sealing, and then the temperature is restored to room temperature, thereby obtaining the catalyst for synthesizing tert-dodecyl mercaptan.
[0007] Preferably, the molar ratio of the anhydrous aluminum chloride, the ferric chloride, the aromatic hydrocarbon auxiliary agent, the anisole or the anisole homologues is 1:0.01:(0.5-7):(0.1-5).
[0008] Preferably, the molar ratio of the anhydrous aluminum chloride, the ferric chloride, the aromatic hydrocarbon auxiliary agent, the anisole or the anisole homologues is 1:0.01:(0.5-5):(0.1-1).
[0009] Preferably, in step S1, the aromatic hydrocarbon auxiliary agent is benzene, toluene, ethylbenzene, xylene or nitrobenzene.
[0010] Preferably, in step S2, the anisole homologues is anisole, p-methyl anisole or 2-methyl anisole.
[0011] Preferably, in step S2, the temperature of temperature control and stirring is 20-50℃, and the stirring speed is 100-300r / min.
[0012] In a second aspect, the present application provides a catalyst for synthesizing tert-dodecyl mercaptan, which is prepared by the above-mentioned method for preparing the catalyst for synthesizing tert-dodecyl mercaptan.
[0013] In a third aspect, the present application provides the application of the above-mentioned catalyst for synthesizing tert-dodecyl mercaptan, which is used in the synthesis reaction of tert-dodecyl mercaptan.
[0014] Preferably, the catalyst for synthesizing tert-dodecyl mercaptan is used to catalyze the synthesis reaction of tert-dodecyl mercaptan prepared from tetramerization of propylene and hydrogen sulfide.
[0015] Compared with the prior art, the present application has the following beneficial effects: The present application can prepare the catalyst under mild conditions, and when used in the synthesis of tert-dodecyl mercaptan, the selectivity is above 95%, and the synthesized tert-dodecyl mercaptan product is suitable for the high molecular polymerization process of ABS, SBR and nitrile rubber latex products. DETAILED DESCRIPTION
[0016] In order to enable the personnel in the technical field to better understand the technical solutions in the present application, the technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application.
[0017] Embodiment 1 The method for preparing the catalyst for synthesizing tert-dodecyl mercaptan of the present embodiment comprises the following steps: S1: Take anhydrous aluminum chloride, ferric chloride, toluene, anisole by molar ratio 1:0.01:5:1, then add the weighed toluene in the reaction kettle, add anhydrous aluminum chloride, ferric chloride in batches while stirring, and mix uniformly; S2: Seal the reaction kettle with nitrogen, under the condition of temperature control stirring (30℃, 150r / min), use the metering pump to drop anisole, the drop time is 0.5h, after the drop is completed, continue to control temperature stirring under the condition of nitrogen sealing for 0.5h, restore to room temperature, then the acidic liquid tertiary dodecyl mercaptan synthesis catalyst is obtained.
[0018] The catalyst prepared in this example is used to catalyze the synthesis reaction of preparing tertiary dodecyl mercaptan from tetrameric propylene and hydrogen sulfide, and the specific steps are as follows: Add 400g tetrameric propylene in a 1L reaction kettle, drop 36g catalyst prepared in example 1-3 under stirring, control the hydrogen sulfide inlet pressure at 37kPa, control the reaction liquid temperature in the reaction kettle within the range of 20-25℃; stop the hydrogen sulfide inlet after 1.5h, continue stirring for 30min, and 500g reaction liquid is obtained.
[0019] Sample analysis, the weight composition of the reaction liquid is: dodecene accounts for 12.01wt.%, tertiary dodecyl mercaptan accounts for 78.16wt.%, dodecanethiol accounts for 1.38wt.%, and the rest 8.45wt.% is mainly catalyst components and dissolved hydrogen sulfide; the selectivity of tertiary dodecyl mercaptan is 98%.
[0020] Example 2 The preparation method of the tertiary dodecyl mercaptan synthesis catalyst in this example includes the following steps: S1: Take anhydrous aluminum chloride, ferric chloride, ethylbenzene, phenetole by molar ratio 1:0.01:0.5:0.1, then add the weighed ethylbenzene in the reaction kettle, add anhydrous aluminum chloride, ferric chloride in batches while stirring, and mix uniformly; S2: Seal the reaction kettle with nitrogen, under the condition of temperature control stirring (20℃, 300r / min), use the metering pump to drop phenetole, the drop time is 0.6h, after the drop is completed, continue to control temperature stirring under the condition of nitrogen sealing for 0.1h, restore to room temperature, then the acidic liquid tertiary dodecyl mercaptan synthesis catalyst is obtained.
[0021] The catalyst prepared in this example is used to catalyze the synthesis reaction of preparing tertiary dodecyl mercaptan from tetrameric propylene and hydrogen sulfide, and the specific steps are as follows: Sample analysis, the weight composition of the reaction liquid is: dodecene accounts for 11.31wt.%, tertiary dodecyl mercaptan accounts for 77.25wt.%, dodecanethiol accounts for 1.68wt.%, and the rest 9.76wt.% is mainly catalyst components and dissolved hydrogen sulfide; the selectivity of tertiary dodecyl mercaptan is 98%.
[0022] Example 3 The preparation method of the tertiary dodecyl mercaptan synthesis catalyst in this example comprises the following steps: S1: weigh anhydrous aluminum chloride, iron chloride, dimethylbenzene, and p-methyl anisole according to a molar ratio of 1:0.01:7:5, then add the weighed dimethylbenzene into a reaction kettle, and add the anhydrous aluminum chloride and iron chloride in batches while stirring, and mix uniformly; S2: seal the reaction kettle with nitrogen, and drop the p-methyl anisole by using a metering pump under the condition of temperature control stirring (50°C, 100 r / min), the dropping time is 1 h, after the dropping is completed, continue to control the temperature and stir under the condition of nitrogen sealing for 0.5 h, and then restore to room temperature, thereby obtaining the acidic liquid tertiary dodecyl mercaptan synthesis catalyst.
[0023] The catalyst prepared in this example is used for catalyzing the synthesis reaction of preparing tertiary dodecyl mercaptan from tetrameric propylene and hydrogen sulfide, and the specific steps are the same as those in Example 1. Sampling analysis shows that the weight composition of the reaction liquid is as follows: 10.31 wt.% of dodecene, 79.82 wt.% of tertiary dodecyl mercaptan, 1.66 wt.% of dodecanethiol, and the remaining 8.21 wt.% is mainly the catalyst components and dissolved hydrogen sulfide; the selectivity of the tertiary dodecyl mercaptan is 98%.
[0024] Comparative Example 1 The difference from Example 1 is that the molar ratio of anhydrous aluminum chloride, iron chloride, toluene, and anisole is 1:0.01:10:1.
[0025] The catalyst prepared in this example is used for catalyzing the synthesis reaction of preparing tertiary dodecyl mercaptan from tetrameric propylene and hydrogen sulfide, and the specific steps are the same as those in Example 1. Sampling analysis shows that the weight composition of the reaction liquid is as follows: 12.34 wt.% of dodecene, 55.21 wt.% of tertiary dodecyl mercaptan, 22.25 wt.% of dodecanethiol, and the remaining 10.2 wt.% is mainly the catalyst components and dissolved hydrogen sulfide; the selectivity of the tertiary dodecyl mercaptan is 71%.
[0026] Comparative Example 2 The difference from Example 1 is that the molar ratio of anhydrous aluminum chloride, iron chloride, toluene, and anisole is 1:0.01:5:7.
[0027] The catalyst prepared in this example is used for catalyzing the synthesis reaction of preparing tertiary dodecyl mercaptan from tetrameric propylene and hydrogen sulfide, and the specific steps are the same as those in Example 1. Sampling analysis shows that the weight composition of the reaction liquid is as follows: 13.76 wt.% of dodecene, 54.32 wt.% of tertiary dodecyl mercaptan, 23.41 wt.% of dodecanethiol, and the remaining 8.51 wt.% is mainly the catalyst components and dissolved hydrogen sulfide; the selectivity of the tertiary dodecyl mercaptan is 70%.
[0028] The physical and chemical properties of the tertiary dodecyl mercaptan synthesized in Example 1 and the tertiary dodecyl mercaptan product produced by Phillips are shown in Table 1: Table 1 Physical and chemical properties of the tertiary dodecyl mercaptan synthesized in Example 1 and the tertiary dodecyl mercaptan product produced by Phillips
[0029] The tertiary dodecyl mercaptan synthesized in Example 1 and the tertiary dodecyl mercaptan product produced by Phillips were used to prepare emulsion polymerization ABS products, and the specific preparation process used the existing preparation method. The performance of the ABS products was tested, and the test results are shown in Table 2: Table 2 Performance test results of two emulsion polymerization ABS products
[0030] The tertiary dodecyl mercaptan synthesized in Example 1 and the tertiary dodecyl mercaptan product produced by Arkema were used to prepare SBR products, and the specific preparation process used the existing preparation method. The performance of the SBR products was tested, and the test results are shown in Table 3: Table 3 Performance test results of two SBR products
[0031] The tertiary dodecyl mercaptan synthesized in Example 1 and the tertiary dodecyl mercaptan product produced by Phillips were used to prepare nitrile rubber latex products, and the specific preparation process used the existing preparation method. The performance of the nitrile rubber latex products was tested, and the test results are shown in Table 4: Table 4 Performance test results of two nitrile rubber latex products
Claims
1. A method for preparing a catalyst for synthesizing tert-dodecyl mercaptan, characterized in that: The following steps are involved: S1: Add aromatic additives to the reactor, add anhydrous aluminum chloride and ferric chloride in batches while stirring, and mix well; S2: Seal the reactor with nitrogen, add anisole or anisole homologue dropwise under temperature-controlled stirring for 0.5-1 h. After the addition is completed, continue to control the temperature and stir for 0.1-0.5 h under nitrogen sealing, and return to room temperature to obtain a catalyst for the synthesis of tert-dodecyl mercaptan.
2. The method for preparing a catalyst for synthesizing tert-dodecyl mercaptan according to claim 1, wherein The molar ratio of the anhydrous aluminum chloride, ferric chloride, aromatic hydrocarbon auxiliary agent, anisole or anisole homologue is 1:0.01:(0.5-7):(0.1-5).
3. The method for preparing a catalyst for synthesizing tert-dodecyl mercaptan according to claim 2, wherein: The molar ratio of the anhydrous aluminum chloride, ferric chloride, aromatic hydrocarbon auxiliary agent, anisole or anisole homologue is 1:0.01:(0.5-5):(0.1-1).
4. The method for preparing a catalyst for synthesizing tert-dodecyl mercaptan according to claim 1, wherein In step S1, the aromatic hydrocarbon auxiliary agent is benzene, toluene, ethylbenzene, xylene or nitrobenzene.
5. The method for preparing a catalyst for synthesizing tert-dodecyl mercaptan according to claim 1, wherein In step S2, the anisole homologue is phenethyl ether, p-methyl anisole or 2-methyl anisole.
6. The method for preparing a catalyst for synthesizing tert-dodecyl mercaptan according to claim 1, wherein In step S2, the temperature of the temperature-controlled stirring is 20-50° C., and the stirring speed is 100-300 r / min.
7. A catalyst for synthesizing tert-dodecyl mercaptan, characterized in that: The catalyst is prepared by the method for preparing the catalyst for synthesizing tert-dodecyl mercaptan according to any one of claims 1 to 6.
8. Use of the catalyst for synthesizing tert-dodecyl mercaptan according to claim 7, characterized in that: It was used in the synthesis of tert-dodecyl mercaptan.
9. Use of the catalyst for synthesizing tert-dodecyl mercaptan according to claim 8, characterized in that: The catalyst for synthesizing tert-dodecyl mercaptan is used for catalyzing the synthesis reaction of tetrapropylene and hydrogen sulfide to prepare tert-dodecyl mercaptan.