Method of producing alkylmercaptans

专利摘要:

公开号:SU1220569A3
申请号:SU833632061
申请日:1983-08-04
公开日:1986-03-23
发明作者:Аррет Эмманюэль；Мирассу Альфред；Ландусси Клод；Ож Патрик
申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
IPC主号:

专利说明:

I
The invention relates to a method for producing alkyl mercaptans of the general formula
RSH,
where R is normal or ramified C, j -C, g-alkyl, which are used in various organic syntheses.
The purpose of the invention is to increase the selectivity of the process.
Example 1. In a tubular reactor 135 mm long and with an internal diameter of 20 ml or with a capacity of 420 ml, 200 ml of dry sulfonated resin, which is a copolymer of styrene with divinylbayol, are placed. at the same time 73 g / h of gaseous gas is injected into it. | The environment is maintained at 60 ± 2 ° C. The reagents are thoroughly mixed before being fed into the reactor. The liquid continuously flowing from the reactor is collected and the remaining sulfide is degassed.
The resulting product in the form of a liquid contains 8% unreacted tetrapropylene, the rest is tert. -Dodecylmercaptan and the conversion degree of olefin is 92%, the selectivity is 100%. A similar operation takes place, with the difference that the catalyst contains 1.6% moisture. Conversion of tetrapropylene in this case does not exceed 80%.
Example 2. The method according to example 1 is carried out, but with smaller amounts of reagents: 60 g / h of tetrapropylene and 36.7 g / h of hydrogen sulfide are injected under a pressure of 10 bar. Conversion of tetrapropylene 96% tert-o-dodecylmercaptan selectivity 100%. Production capacity for mercaptan is 69.25 g / h per 1 m catalytic surface. In this way, I get a product with a very good yield and unreacted tetrapropylene is easily recycled.







In the same operating conditions, but with
From tab. 3 it follows that
using a wet resin convert to a favorable pressure effect.
tetrapropylene drops to 85%.
Example 3. In the same reactor as in Example 1, 100 g of perfluorosulfonic acid-based dry resin are operated. At a pressure of 10 bar, 60 g / h of tetrapropylene and 36.7 g / h of hydrogen sulfide are introduced. At the exit of the reactor get the conversion of tetrapropylene
the gain in yield at a pressure of 50 b is not large enough to cover the cost of increasing the duration from 25 to 50 bar, 55 Examples 15 and 16. The change in the ratio H 3 / olefin,
In examples 1 and 2, which give good results, the molar ratio
five
five
with a tert-dodecyl mercaptan selectivity of almost 100%,
Example 4. Work with 120 g of a resin based on a copolymer of alcohol with divinylbenzene, 40 g / h of isobutylene and 73 g / h of hydrogen sulfide are introduced into the reactor at a pressure of 10 bar. Temperatures of the reaction are 70 ° C. 63 g / h of tert-butylmercaptan are obtained, i.e. The conversion to this product is 98%.
Example 5. The resin was operated as in Example 1 with a dry resin and with loads of 121 g / h of tetrapropylene and 73 g / h of hydrogen sulfide, at 60 ° C. The experience continued for 700 hours without changing the conversion of tetrapropylene, which was maintained at 91- 92%.
Examples 6 and 7, Temperature effect.
The operation is carried out according to the procedure of examples 1 and 2, but the reaction is carried out at 45 and 73 ° C. The amount of introduced tetrapropylene is the same and amounts to 121 g, but it is introduced in 3 hours at 45 ° C and in 0.5 hours at 75 C. Others The working conditions are the same as in Examples 1 and 2. The catalyst has a moisture content of 0.05%.
In tab. 1, the results obtained are compared with the results of examples 1 and 2.
From tab. 1 shows that the optimum process temperature is about 60 C.
Examples 8-11, Effect of catalyst moisture.
Example 1 is repeated with the same cation-exchange resin, but with a different moisture content. Get the outputs of the product are presented in table. 2
From the data table. 2 that the yield remains acceptable at a humidity of about 0, 5% j, but outside of this value falls.
Examples 12-14. The effect of pressure.
The test was carried out according to Example 1, but was carried out under different pressure. The results are presented in table. 3
From tab. 3 it follows that despite
0
five
0
five
 on the beneficial effect of pressure.
the gain in the outlet at a pressure of 50 bar is not large enough to cover the cost of increasing the pressure from 25 to 50 bar, 55 Examples 15 and 16. The change in the ratio H 3 / olefin,
In examples 1 and 2, which give good results, the molar ratio is 3
HjS / olefin is adjusted to its optimum value, i.e. to 2.98. The same experiment was carried out, but with limiting values of this ratio, respectively 1.2 and 10.
The results of the experiments are presented in table. four.
From tab. It follows that the lower limit of the ratio H B / olefin of 1.2 gives a lower but acceptable yield. With an upper limit of 10, the yield of the target products increases slightly, i.e. an increase in the ratio H 3 / olefin to the specified limit is not economically feasible.
I
Examples 17-19. Use of various cation exchange resins
Work according to example 1, but using three different types of sulfonated resin with a moisture content of 0.05%.
The results are shown in the table. five.
20569
Thus, based on the data of tabLo 5, it can be seen that the sulfonated resins used in examples 17-19 allow to obtain results 5 of the same order as when using the resin based on copolymers of sulfonated styrene with divinylbenzene (examples 1, 2 , 4 and 5) or with a polyfluoric sulfone resin (Example 3). 10 Examples 20-24. Application of the method to various olefins.
The tetrapropylene of example 1 is replaced each time with a different olefin, and the reaction conditions remain the same, fj The weight of olefin used is 121 g
Table 6 gives the results of experiments,
Given the data table. 6, the proposed method can be used to obtain any liquid mercaptan-20 nova at 45-75 ° C, obtained from olefins, which can be in the form at 45-75 ° C and pressure of 1-50 bar, t . olefins with the content of carbon atoms With -Cig.
Table 1
table 2
Example
Pressure bar
12 13 14
one
25
50
Lignsulfonov 128
Sulfonated Phenol / Formaldehyde Resin 123
Sulfonated phenylpoly krils a
resin 126,6
20 Isoamylene (CdNc) 70 Isoamyl mercaptan 174
(,, SH) 104
21 Diisobutylene
(CgH ,,) 112
22
Tripropylene
(SdN, c) 126
 Table 3
The resulting mercaptan, g
Output, %
126 137 138
87 94 95
88
85
87
Table 6
97
tert.-Octylmer-captan (CgH, SH) 146152.7
97
Rubs-Nonilmercaptan (C, H ,, SH) 160 147
96
Editor V. Petrash
Order 1337/62 Circulation 379 Subscription
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab, 4/5
Branch mm Patent, Uzhgorod, 4 Project St.
Compiled by O. Safonov
Tehred N. Bonkalo Corrjoctor A.Zimokosov

权利要求:
Claims (4)
[1]
1. METHOD FOR PRODUCING ALKYL MERCAPTANES of the general formula
RSH, where R is straight or branched C 3 -C ₁₈ alkyl, by reacting the corresponding Olefin with hydrogen sulfide while heating the reaction medium to
45-75 ° C and in the presence of an organic cation exchange resin as a catalyst, characterized in that, in order to increase the selectivity of the process, said resin with a moisture content of not more than 0.5% is used as a catalyst.
[2]
2. The method according to p. ^ Characterized in that the catalyst is a copolymer of sulfonated alcohol with divinylbenzene or a copolymer of tetrafluoro-thylene with perfluorosulfonic acid.
[3]
3. The method according to claims 1 and 2, wherein the process is carried out at a pressure of 1-50 bar.
[4]
4. The method according to PP. 1 and 3, characterized in that the process is carried out at a water content in the reaction medium of 0.01-0.2%.

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引用文献:

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US4102931A|1977-05-17|1978-07-25|Pennwalt Corporation|Manufacture of tertiary mercaptans using zeolite catalysts|

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FR2627182B1|1988-02-17|1991-03-22|Elf Aquitaine|IMPROVEMENT IN SYNTHESIS OF SECONDARY MERCAPTANS FROM LINEAR OLEFINS|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8213689A|FR2531426B1|1982-08-05|1982-08-05|

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