KR100698461B1 - A method for preparating triisobutylmercaptan by using zeolite catalyst, and a zeolite catalyst used for the method - Google Patents

Abstract

The present invention relates to a method for preparing triisobutyl mercaptan using a zeolite catalyst and a zeolite catalyst used therein, and more particularly, to triisobutyl mercaptan reacting triisobutylene with hydrogen sulfide using a zeolite catalyst (TIBM). , triisobutylmercaptan) and a zeolite catalyst used therein.

The method for producing triisobutyl mercaptan of the present invention has the advantage of using a zeolite catalyst to produce high conversion and high yield of triisobutyl mercaptan from triisobutylene and hydrogen sulfide.

Zeolite, Triisobutylmercaptan, Triisobutylene, Hydrogen Sulfide, Bottom-up Flow

Description

A method for producing triisobutyl mercaptan using a zeolite catalyst and a zeolite catalyst used therein {A METHOD FOR PREPARATING TRIISOBUTYLMERCAPTAN BY USING ZEOLITE CATALYST, AND A ZEOLITE CATALYST USED FOR THE METHOD}

[Industrial use]

The present invention relates to a method for preparing triisobutyl mercaptan (TIBM, triisobutylmercaptan) using a zeolite catalyst, and to a zeolite catalyst used therein, and more particularly, to high conversion and high yield of triisobutyl from triisobutylene and hydrogen sulfide. A method for producing triisobutyl mercaptan capable of producing mercaptans, and a zeolite catalyst used therein.

[Private Technology]

Alkyl mercaptan is used for the use of molecular weight modifiers such as ABS resin, and can be prepared from hydrogen sulfide and olefins. The process for producing alkylmercaptans from hydrogen sulfide and olefins has long been known for its Markownikoff addition and has been widely used. This method has generally been carried out using a variety of catalysts such as acid catalysts or clay catalysts, for example, homogeneous catalysts such as Lewis acid catalysts, or heterogeneous catalysts such as montmorillonite catalysts, polymer organic sulfonic acid catalysts, etc. Catalysts have been used. However, when a Lewis acid catalyst, which is a homogeneous catalyst, is used, the catalyst has a great solubility in reactants and products, and also has a big problem in corrosion of the device. Therefore, montmorillonite catalysts or polymer organic sulfonic acid catalysts (for example, Amberlyst®: Rohm Haas), which are heterogeneous catalysts, have been mainly used in recent years.

For example, U.S. Patent No. 3,534,106 proposes a method for preparing mercaptans by reacting olefins and hydrogen sulfide in the presence of a montmorillonite clay catalyst. In the examples of this patent, Filtrol 25, 62 is used as a montmorillonite clay catalyst. And 71 were actually used. However, these filtrol catalysts must be activated at a high temperature of 202 ° C., the reaction must be carried out at a high pressure of 54 kg / cm 2 (800 psig), and methanol should be used to reduce side reaction products. In addition, when the reaction was performed using only such a catalyst, boron trifluoride (BF 3) or the like was used as a cocatalyst because the yield of the target product was low.

In addition, in the case of US Patent No. 4,891,445 and French Patent No. 2,531,426, a method of carrying out the reaction using an amberlist, which is a high molecular organic sulfonic acid catalyst, is proposed. In order to make the water content of the catalyst less than 0.5% to be activated for 6 hours at 80 ℃, inactivation occurs at 140 ℃ or more because the catalyst is an organic polymer form, the conversion and yield falls when reacted at low temperatures. In addition, the polymer organic sulfonic acid catalyst is not only limited to the moisture of the catalyst, but also has a disadvantage that the catalyst activity is frequently regenerated unless the hydrogen content of the hydrogen sulfide or olefin as the reactant is strictly regulated.

The present invention is to solve the above problems, an object of the present invention by using a zeolite catalyst from triisobutylene (TIB, triisobutylene) and hydrogen sulfide (H ₂ S) of high conversion and high yield of triisobutylmer It is to provide a production method capable of producing captan.

Another object of the present invention is to provide a zeolite catalyst used in the above production method.

The present invention provides a method for producing triisobutyl mercaptan by reacting triisobutylene and hydrogen sulfide by using a zeolite catalyst.

The present invention also provides a zeolite catalyst which is a catalyst for producing triisobutyl mercaptan from triisobutylene and hydrogen sulfide.

Hereinafter, the present invention will be described in more detail.

Catalysts used in the production of conventional alkyl mercaptans have poor reaction efficiency with respect to triisobutylene and hydrogen sulfide.

The present inventors used various types of catalysts to find a catalyst that can be efficiently used in the reaction of reacting triisobutylene with hydrogen sulfide to produce a desired triisobutyl mercaptan, and also by improving the reaction process, Intensive research was conducted to find ways to operate more efficiently. As a result, surprisingly, by using a specific type of zeolite catalyst different from the montmorillonite catalyst or cation exchange resin catalyst actually used in the prior art, the tree can be produced at a higher conversion rate and higher yield than the conventional montmorillonite or cation exchange resin under the same conditions. The present invention has been completed by confirming that isobutyl mercaptan can be prepared.

The present invention produces triisobutyl mercaptan having high conversion and yield by reacting triisobutylene with hydrogen sulfide using a zeolite catalyst.

The kind of the zeolite catalyst used in the production of the triisobutyl mercaptan is not particularly limited, but it is preferable to use a zeolite Y type catalyst. An example of the zeolite Y type catalyst is CP-766, which is currently commercialized, which is a product of Zeolite, contains about 40% by weight of alumina, contains about 0.2% by weight of alkali metal oxide, and has a surface area of about 560 m ² / g. Or LZY-64 (a product of UOP, which contains about 5% by weight of silica and alumina, contains about 2% by weight of alkali metal oxide, and has a surface area of about 720 m ² / g). . However, the zeolite catalyst of the present invention is not limited to the commercialized product.

The zeolite catalyst is preferably used after a sufficient drying process, and more preferably used after activating the catalyst by drying at a high temperature for a sufficient time to remove water contained in the catalyst. At this time, the drying temperature is preferably maintained at 240 ℃ or more.

In the method for producing triisobutyl mercaptan using the catalyst, the reaction temperature of the triisobutylene and hydrogen sulfide is preferably 10 to 90 ° C, more preferably 10 to 45 ° C. Since the reaction is exothermic, it is difficult to control the temperature when the reaction temperature is less than 10 ℃, the reactivity may be lowered when it exceeds 90 ℃.

In addition, in the method for producing triisobutyl mercaptan using the catalyst, the reaction pressure of the triisobutylene and hydrogen sulfide is preferably 1 to 50 bar, more preferably 5 to 15 bar. When the reaction pressure is less than 1 bar, solubility of hydrogen sulfide in triisobutylene decreases, so that the reactivity decreases. When the reaction pressure exceeds 50 bar, the manufacturing cost according to the reactor fabrication and process control increases.

In the reaction, the hydrogen sulfide is generally added in an excessive amount with respect to triisobutylene, and the reaction is preferably performed in an amount of 1.2 to 12 mol with respect to 1 mol of the triisobutylene in terms of conversion and yield, It is more preferable to make it react by input in the ratio of 2-5 mol.

The method for producing triisobutyl mercaptan from triisobutylene and hydrogen sulfide using the catalyst can be carried out discontinuously or continuously, and more preferably continuously.

The reactor used for the reaction may use a conventional batch (discontinuous) reactor or a continuous reactor, but it is preferable that an intercooler for controlling the heat of reaction and maintaining a constant temperature inside the reactor.

Discontinuous manufacturing method of the production method comprises the steps of adding triisobutylene and a dry zeolite catalyst to the reactor; Replacing the inside of the reactor with an inert atmosphere and stirring; Adding hydrogen sulfide into the reactor to react; And discharging hydrogen sulfide in the reactor and filtering the reactants.

In addition, the continuous production method of the production method is a method of reacting while flowing triisobutylene and hydrogen sulfide into the reactor filled with zeolite catalyst, preferably the triisobutylene and hydrogen sulfide upflow (upward flowing) There is a method of reacting by flowing from the bottom to the conditions and a method of reacting the triisobutylene and hydrogen sulfide by flowing from the top to the bottom in an upward flowing condition. It is more preferable to manufacture under the bottom-up flow conditions of the former of the two continuous manufacturing methods.

In the continuous reaction, the weight hourly space velocity (WHSV) of the triisobutylene to be added is preferably 0.3 hr ⁻¹ or more, and more preferably 0.3 to 1 hr ⁻¹ . If the medium space velocity is less than 0.3 hr ^-1, triisobutylene has a low supply rate per unit time, and the production rate of triisobutyl mercaptan is low, and if it exceeds 1 hr ^-1 , the reaction time is insufficient and triisobutyl is not sufficient. The yield of mercaptans can be lowered.

The WHSV represents the amount of triisobutylene supplied per unit weight of the catalyst present in the reactor for a unit time, when 100 g of catalyst is present in the reactor and 100 g of triisobutylene is flowed for 1 hour. WHSV value is 1. The WHSV range may be applied to both a bottom-up flow condition and a top-down flow condition.

The triisobutyl mercaptan prepared by the above method may be used as a molecular weight regulator for preparing a polymer resin, and is particularly suitable as a molecular weight regulator for nitrile-butadiene rubber (NBR).

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

EXAMPLE

Example 1 (discontinuous manufacturing method)

80 g of triisobutylene (TIB) and 16 g of a dry zeolite catalyst (CP-766, manufactured by Zeolyst) were added to a 250 ml reactor. After the inside of the reactor was replaced with nitrogen, the mixture was stirred at 200 rpm, and hydrogen sulfide (H ₂ S) was added to the inside of the reactor in an excessive amount while maintaining the temperature of the reactor at 15 ° C. such that the internal pressure was 10 bar. After the reaction was performed for 2 hours in this state, triisobutyl mercaptan (TIBM) was prepared by discharging hydrogen sulfide gas and filtering to remove the catalyst.

Example 2 (discontinuous manufacturing method)

Triisobutyl mercaptan was prepared in the same manner as in Example 1, except that LZY-64 of UOP Corp. was used as the zeolite catalyst.

Comparative Example 1 (Discontinuous Manufacturing Method)

Triisobutyl mercaptan was prepared in the same manner as in Example 1 except that a sulfonated styrene-divinylbenzene copolymer (Amberlyst-15 (Dry), manufactured by Rohm Haas), which was a cation exchange resin, was used as a catalyst.

Comparative Example 2 (Discontinuous Production Method)

Triisobutyl mercaptan was prepared in the same manner as in Comparative Example 1 except that the reaction pressure was maintained at 5 bar.

Comparative Example 3 (Discontinuous Production Method)

Triisobutyl mercaptan was prepared in the same manner as in Example 1 except that the montmorillonite catalyst (Filtrol-24, manufactured by Engelhard) was used as the catalyst.

Comparative Example 4 (Discontinuous Manufacturing Method)

Triisobutyl mercaptan was prepared in the same manner as in Comparative Example 3 except that the reaction temperature was 90 ° C.

Example 3 (Discontinuous Production Method Using Regenerated Triisobutylene)

The reaction product obtained in Example 1 was distilled to obtain unreacted triisobutylene having a purity of 99.4%, and triisobutyl mercaptan was prepared in the same manner as in Example 1.

Comparative Example 5 (Discontinuous Production Method Using Regenerated Triisobutylene)

The reaction product obtained in Example 1 was distilled to obtain 99.4% unreacted triisobutylene, and triisobutyl mercaptan was prepared in the same manner as in Comparative Example 1.

Example 4 (Continuous Manufacturing Method-Upward Flow)

37.5 g of a dry zeolite catalyst (CP-766, manufactured by Zeolyst) was charged into a cylindrical reactor having an internal diameter of 2.54 cm and a length of 10.16 cm, equipped with an intercooler, and maintained at 10 bar and a temperature of 10.degree. Triisobutyl mercaptan was prepared by capturing the liquid reactant while flowing hydrogen sulfide at the rate of hr upwardly into the reactor at a rate of 6.8 g / hr.

Example 5 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 4 except that the reaction temperature was 15 ° C.

Example 6 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 4 except that the reaction temperature was 20 ° C.

Example 7 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 4 except that the reaction temperature was 25 ° C.

Example 8 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 4 except that the reaction temperature was 30 ° C.

Example 9 (Continuous Manufacturing Method-Downward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 4 except that triisobutylene and hydrogen sulfide were reacted while flowing downward from the top into the reactor.

Example 10 (Continuous Manufacturing Method-Upward Flow)

37.5 g of a dry zeolite catalyst (CP-766, manufactured by Zeolyst) was charged into a cylindrical reactor having an internal diameter of 2.54 cm and a length of 10.16 cm with an intercooler, and 37.5 g / of triisobutylene while maintaining a pressure of 10 bar and a temperature of 10 ° C. Triisobutyl mercaptan was prepared by capturing the liquid reactant while flowing hydrogen sulfide at the rate of hr upwardly through the reactor at a rate of 22.8 g / hr.

Example 11 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 10 except that the reaction temperature was 15 ° C.

Example 12 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 10 except that the reaction temperature was 20 ° C.

Example 13 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 10 except that the reaction temperature was 25 ° C.

Example 14 (Continuous Manufacturing Method-Upward Flow)

Triisobutyl mercaptan was prepared in the same manner as in Example 10 except that the reaction temperature was 30 ° C.

Example 15 (Continuous Manufacturing Method-Downflow)

Triisobutyl mercaptan was prepared in the same manner as in Example 10 except that triisobutylene and hydrogen sulfide were reacted at 20 ° C. while flowing downward from the top into the reactor.

In the method for preparing tertiary triisobutyl mercaptan according to Examples 1 to 15 and Comparative Examples 1 to 5, the obtained reactant is weighed and titrated with silver nitrate (AgNO ₃ ) to give unreacted triisobutylene and tri The content of isobutyl mercaptan was measured.

The reaction conditions and yields of the final products of Examples 1 to 15 and Comparative Examples 1 to 5 are summarized in Table 1 below.

TABLE 1

TIB (g) H ₂ S (g) Catalyst type Catalyst weight (g) Reaction temperature (℃) Reaction pressure (bar) TIB (%) TIBM (%) Example 1 80 Overdose CP-766 16 15 10 54 44 Example 2 80 Overdose LZY-64 16 15 10 55 43 Comparative Example 1 80 Overdose Amberlyst-15 16 15 10 57 40 Comparative Example 2 80 Overdose Amberlyst-15 16 15 5 59 39 Comparative Example 3 80 Overdose Filtrol-24 16 15 10 99 0.2 Comparative Example 4 80 Overdose Filtrol-24 16 90 10 73 24 Example 3 80 (playback) Overdose CP-766 16 15 10 67 31 Comparative Example 5 80 (playback) Overdose Amberlyst-15 16 15 10 71 29 Example 4 11.25 g / hr ↑ 6.8g / hr ↑ CP-766 37.5 10 10 27 73 Example 5 11.25 g / hr ↑ 6.8g / hr ↑ CP-766 37.5 15 10 31 68 Example 6 11.25 g / hr ↑ 6.8g / hr ↑ CP-766 37.5 20 10 36 63 Example 7 11.25 g / hr ↑ 6.8g / hr ↑ CP-766 37.5 25 10 50 49 Example 8 11.25 g / hr ↑ 6.8g / hr ↑ CP-766 37.5 30 10 53 46 Example 9 11.25 g / hr ↓ 6.8g / hr ↓ CP-766 37.5 10 10 32 67 Example 10 37.5g / hr ↑ 22.8g / hr ↑ CP-766 37.5 10 10 42 58 Example 11 37.5g / hr ↑ 22.8g / hr ↑ CP-766 37.5 15 10 43 56 Example 12 37.5g / hr ↑ 22.8g / hr ↑ CP-766 37.5 20 10 47 52 Example 13 37.5g / hr ↑ 22.8g / hr ↑ CP-766 37.5 25 10 52 47 Example 14 37.5g / hr ↑ 22.8g / hr ↑ CP-766 37.5 30 10 56 43 Example 15 37.5g / hr ↓ 22.8g / hr ↓ CP-766 37.5 20 10 49 50

In Table 1, '↑' indicates a bottom-up flow condition, '↓' indicates a top-down flow condition.

As shown in Table 1 above, when triisobutyl mercaptan was prepared using triisobutylene and hydrogen sulfide as starting materials under the same conditions, zeolite catalysts CP-766 and LZY-64 were more active than the other catalysts. It can be seen that this shows high conversion and yield. In addition, since triisobutylene, which is recovered in an unreacted state in the manufacturing method, has a reactivity of about 70% compared to the first use, the manufacturing method also has the advantage of recycling triisobutylene.

In addition, in the case of continuously reacting triisobutylene and hydrogen sulfide, a better yield can be obtained than in the case of the non-continuous reaction. It can be seen that an excellent yield can be obtained.

 The method for producing triisobutyl mercaptan of the present invention has the advantage of using a zeolite catalyst to produce a high conversion and high yield of tertiary triisobutyl mercaptan from triisobutylene and hydrogen sulfide.

Claims (14)

A method for producing triisobutyl mercaptan (TIBM, triisobutylmercaptan) in which triisobutylene is reacted with hydrogen sulfide using a zeolite catalyst. The method for producing triisobutyl mercaptan according to claim 1, wherein the reaction temperature of the triisobutylene and hydrogen sulfide is 10 to 90 ° C. The method for producing triisobutyl mercaptan according to claim 2, wherein the reaction temperature of the triisobutylene and hydrogen sulfide is 10 to 45 ° C. The method for preparing triisobutyl mercaptan according to claim 1, wherein the reaction pressure of triisobutylene and hydrogen sulfide is 1 to 50 bar. The method of claim 4, wherein the reaction pressure of triisobutylene and hydrogen sulfide is 5 to 15 bar. The method for producing triisobutyl mercaptan according to claim 1, wherein the hydrogen sulfide is added at a rate of 1.2 to 12 moles with respect to 1 mole of the triisobutylene. The method for producing triisobutyl mercaptan according to claim 1, wherein the hydrogen sulfide is added and reacted at a ratio of 2 to 5 mol with respect to 1 mol of triisobutylene. The method of claim 1, wherein the method comprises the steps of adding triisobutylene and a dry zeolite catalyst to the reactor; Replacing the inside of the reactor with an inert atmosphere and stirring; Adding hydrogen sulfide into the reactor to react; And Draining hydrogen sulfide in the reactor and filtering the reactants Method for producing a triisobutyl mercaptan comprising a. The method for preparing triisobutyl mercaptan according to claim 1, wherein the manufacturing method is continuously reacted while flowing triisobutylene and hydrogen sulfide into a reactor filled with a zeolite catalyst. The method of claim 9, wherein the weight hourly space velocity (WHSV) of the triisobutylene is 0.3 hr ⁻¹ or more. The method of claim 10, wherein the weight hourly space velocity (WHSV) of the triisobutylene is 0.3 to 1 hr ⁻¹ . 10. The method of claim 9, wherein the method is for reacting the triisobutylene and hydrogen sulfide in an upward flowing condition. The method of claim 9, wherein the reacting comprises reacting the triisobutylene and hydrogen sulfide in a downward flowing condition. delete