SU973521A1 - Process for producing secondary butanol - Google Patents

Description

Technical and recycled butylenes are used as raw materials, and n-butane is used for dilution. Technical butylenes from the tank, after mixing with a return pump, have a pressure of 8.0-8.5 atm. And are fed to the first one, where they are mixed with sulfuric acid coming from the second sulfonation stage, n-butane. Reaction products containing butyl sulfuric and sulfuric acids, Butane and unreacted butylenes, after cooling in a refrigerator, are sent to the second reactor where they are mixed with fresh butylenes and butane fed to the second reactor. The reaction products from the second reactor are cooled and fed to a settling tank, where they are divided into two sections. The lower acid layer, which is a mixture of butyl sulfuric and unreacted sulfuric acids, is fed to the hydrolysis. The upper hydrocarbon layer, which is a mixture of butane mixed with butylated polymer and dibutyl sulfate, formed during the sulfonation process, is sent to the second sulfonation stage in the third reactor, where it is mixed with fresh sulfuric acid. The reaction products are cooled and fed to the fourth reactor, where the remaining butylenes are recovered as a result of the additional mixing. After cooling, the reaction products are fed to a settling tank, where they are separated into two layers. The upper hydrocarbon layer, which is a mixture of unreacted butylenes, butane, polymers and dibutyl sulfates formed during the sulfonation process, is removed from the system. The lower acid layer, which is a mixture of butylsulfuric and sulfuric acids, directed to :; to the first sulfonation stage The lower acid layer obtained after separation of the sulfonation products in the first stage, which is a mixture of butyl-sulfur and unreacted sulfuric acid, is mixed with water in a volume ratio of 1: 3 and sent to the hydrolyzer, where the hydrolysis is carried out and polymers are byproducts of sulfonation of olefins and; hydrolysis (butyl sulfuric acid. The lower acid layer, which is a mixture of VVS and sulfuric acid solution with a concentration of 30–35 wt.%, enters the stripping column, where raw alcohol is distilled off raw alcohol. Raw alcohol from the distant column, mixed with butylenes, separated during the hydrolysis of butyl sulfuric acid and crude alcohol stripped, is washed off from sulfuric acid. Subsequently, the raw alcohol is directed to the azeotrope for the purification of the azeotrope Air Force with Water. The boilers released after aqueous OTNBJBKH as wet gas are compressed before addition of 7.5-8.0 atm and condensed. Liquefied butylene is fed to the sulfonation reactor in the first step. neither 73-75% sulfuric acid in terms of monohydrate is used as sulphating agent. the conversion of n-butylenes at the stage of sulfonation and hydrolysis of 97.0 and 100% with a selectivity of 94.8 and 89.3%, respectively. The amount of leached hydrocarbons is 6.7% of the initial butylenes; raw materials hydrolysis of 7.3 wt.%. Example 2. Fresh sulfuric acid is pumped into the Venturi tube. Due to the high-speed acid pressure, returnable butylenes, which have undergone preliminary washing with water from the traces of alcohol and drying, are sucked into the Venturi pipe, where they are mixed and react with sulfuric acid. Formed with a mixture of butyl sulfuric acid and sulfuric acid. Enters the refrigerator. Acid for sulfonation of the returned butylenes is fed to the secret of the amount that is necessary for absorption. of all butylenes, mainly the process of sulfatizing liquid butylenes, while maintaining in the process of the butylenes: sulfuric acid molar ratio, equal to 1: 1.1. The mixture of butyl-sulfur and sulfuric sulfur enters the second-stage sulfonation reactor. According to this method, technical butylenes are processed in the amount of 3505.4 kg, returnable butylenes 200 kg in the form of butyl sulfuric acid in the amount of 521.4 kg (and-butylenes content is 189.6 kg). For dilution, n-butane was supplied in an amount of 2,297 kg. 73-75% sulfuric acid in the amount of 5924.1 kg in terms of monohydrate is used for sulfonation. For the hydrolysis of the resulting butylsulfuric acid, 866 kg of ode are fed. . as a result of the reaction of sulfonation of butylenes and hydrolysis of butyl sulfuric acid, followed by stripping of the crude alcohol, kg are obtained: secondary butyl alcohol 3572.2; polymers 127.5; return butylenes 200.0 (including + “- butylenes 189.6), waste butane 3003.5 (including residual butane 79.6; polymers 241.8; dibutylsulphate 74.6; free sulfuric acid 6221.1 ) The conversion of butylenes at the stage of sulfonation and hydrolysis is 97.4 and 100% with a selectivity of 95.1 and 88.0%, respectively. The amount of butylenes released to the starting butylenes is 6.2%.

Dp of absorption of the separated butyenes 200 KI- (including n-butylenes 189.6 kg) 3 Venturi reactor filed for sulfuric acid 6255.9 kg; As a result of the reaction of sulfonation of butylenes, butyl sulfuric acid of 521.4 kg is obtained; dissolved butane 10.4 kg and free sulfuric acid 5924.1 kg. These products, in the form of a mixture, are sent to the second stage as a sulphating agent. The molar saturation level of sulfuric acid is 0.05. At the same time, complete conversion of butylenes was achieved without the latter being lost to the formation of dibutyl sulfates due to the high excess of the sulphating agent.

Example 3, Secondary butyl alcohol is obtained using the M method as described in Example 2, Otychie consists only in the fact that the amount of sulfuric acid supplied to the l of sulfonation of return butylenes is 44% of the amount needed for complete absorption of butylenes in the main process. sulfonation of liquid butylenes, at a molar ratio of butylenes: sulfuric acid, equal to 1: 1.1.

Thus, technical butylenes are processed in the amount of 3515.0 kg, including n-butylenes 3114.3 kg and butyl sulfuric acid formed during the absorption of butylenes released during the hydrolysis and stripping of alcohol (ryder, 651.8 kg). To dilute technical butylenes 2250 kg of technical butane are fed in. 5640 kg of sulfuric acid are used as a sulphating agent, 886.9 cg of water are supplied for hydrolysis, 3625.4 kg of secondary butyl alcohol, polymers 115.5, recycled butylenes 250 | butan waste are obtained as a result of the reactions. 2905.2 (including residual e butylenes 105.9; polymers 209.8; dibutyl sulfates (58.3).

Dp of absorbing butylenes released in an amount of 250 kg serves 2763.6 kg of sulfuric acid. The result of the sulfonation reaction is: kg: butyl sulfuric acid 651.8; dissolved butane 13.0; sulfuric acid free 2348.3. The molar saturation level of sulfuric acid is 0.15.

With such a degree of saturation of sulfuric acid, complete conversion of gaseous butylenes is obtained.

The conversion of n-butylenes at the stages of sulfonation and hydrolysis is 96.6 with a selectivity of 96.0 and 87.8 S, respectively. The yield of reusable butylenes on the initial n-butylenes 7.6 ° C. % EXAMPLE 4. The VVS is prepared according to the proposed method, as described in Example 2. The only difference is that the amount of sulfuric acid supplied for the sulphation of gaseous butylene gas is 29.0% by weight of the amount acid, necessary for complete absorption of butylenes in the main process of sulfonation of liquid butylenes, at a molar ratio of butylenes: sulfuric acid, equal to 1: 1.1.

With such an acid supply, the molar saturation of the latter is achieved.

5 butylene, equal to 0.20.

Under these conditions, 3508 kg of technical butylenes are processed; 581.9 kg of butyl-sulfuric acid with 11.7 kg of butane and 3.2 kg of dibutyl sulfate dissolved in it.

0

As a result of the reactions of sulfonation of butylenes and hydrolysis of the resulting butyl sulfuric acid, kg are obtained: secondary butyl alcohol 3555.4; polymers 124.0; return butylenes 225.0; free sulfuric acid 6498.0 and spent butane 2994.7 (including polymers 237.9; residual butylenes 125.6; dibutyl sulfates 51.7),

0

The transformation of butylenes at the stage of sulfonation and hydrolysis is 97.0 and 100% with a selectivity of 94.8 and 88.0%, respectively.

The amount of isolated butilenes

5 is 7.0% of the starting butylenes. The circulation of butyl sulfuric acid from the first stage to the second stage of sulfatization is not carried out. 225 kg of butylenes recovered from the hydrolysis stage are absorbed by sulfuric acid supplied in an amount of 1,871.8 kg. As a result of the sulfonation reaction, butyl sulfuric acid is obtained in an amount of 581.9 kg; dissolved butane 11.7 kg and dibutyl sulfate 3.2 kg. The degree of molar saturation of the acid with butylenes is 0.20. With this saturation of the acid, dibutyl sulfates are formed during gas-phase sulfation, which are extremely undesirable KoivmoHeHTOB (the formation of which is associated not only with direct losses of butylenes due to the weak hydrolysis ability of dibutyl sulfates, but also

5 with strong corrosion, caused by forming at high temperatures with weak sulfuric and sulphurous acids.

: Example 5 (comparative), secondary butyl alcohol is obtained according to the proposed method, as described in Example 2. The difference is that due to the fact that

5 circulation of butylsulfuric acid with

the first to the second step is not carried out, the loading of fresh butylenes was increased by an average of 10%. In addition, sulfuric acid in an amount of 23.3% by weight of the acid required to completely absorb butylenes in the main sulfonation process of liquid butylenes, at a molar ratio of butylenes: sulfuric acid, is 1: 1.1. On the sulfonation serves, kg technical butylenes 3950, including n butylenes 3448.3; butylsulfur acid 586.3; dissolved butane 12.0 and dibutyl sulfate 9.0. To dilute the raw material, n-butane is used in the amount of 2595 kg. 6921.8 kg of sulfuric acid are fed for sulphurization. Water is supplied for hydrolysis in the amount of 966.4 kg. As a result of the reaction of sulfonation of butylenes and hydrolysis of butylsulfuric acid, kg are obtained: secondary butyl alcohol 3986.4; polymers 145,6; butylenes returnable 230; spent butane 3412,6, including: residual n-butylene 110.3; polymers 260.9; dibutyl sulfate 71.1; sulfuric acid free 7271.9.

The degree of conversion of n-butylenes at the stage of sulfonation and hydrolysis is 96j8 and 100% with a selectivity of 94.8 and 88.5%, respectively. The yield of return butylenes 6.3 wt.% In terms of n-butylenes raw materials.

The bilenyses separated during the hydrolysis stage are absorbed by sulfuric acid in the amount of 1,274.0 kg, which is 18.5% of the amount of sulfuric acid used in the basic process of sulfonation of liquid butylenes. All butylene gases are absorbed by sulfuric acid to form butyl sulfuric acid in the amount of 596.3 kg; dissolved butane 12.0 kg; butylsulfa-, comrade 9.0 kg and free sulfuric acid 896.7 kN. The degree of saturation of the sulfuric acid is 0.29. At the molar saturation of sulfuric

acid butylenes, equal to 0.23, the selectivity of hydrolysis is reduced by 2.2% due to the formation of dibutyl sulfates.

Example 6, Secondary butyl alcohol get proposed. the method as described in example 2. ra processing serves technical butylenes in the amount of 3525.0 kg;

butyl sulfuric acid 269.8 kg, containing 5.2 kg of dissolved ff-butane. The sulfonation is carried out with sulfuric acid in the amount of 6250.5 kg. To dilute the original mixture;

5 podaJT 2280 kg of n-butane. For hydrolysis, 882.7 kg of water are supplied. As a result of the reaction of sulfonations of butylenes and hydrolysis of butylsulfuric acid, kg: secondary butyo: lovy alcohol 3641, polymers 111.9, otrotrovannaya butane 2267.6, returnable butylenes 100.0, free sulfuric acid 6392.7 are obtained. The degree of conversion of m-butylenes at the stage of sulfiruvani and hydrolysis, respectively, is 96.2 and 100% with a selectivity of 95.5 and 92.8%, the yield of butylenes.

5833.3 kg of sulfuric acid are supplied to absorb reusable butylenes.

which is 93.8% of the amount

acid used in the main process of sulfonation of butylenes. As a result of the interaction of sulfuric acid and butylenes with the complete transformation of the latter, the butyl-sulfuric acid was obtained.

5 acids 269.8 kg in dissolved in it -butane in the amount of 5.2 kg, free sulfuric acid 5658.3 kg. The degree of saturation of sulfuric acid is 0.03, the material balance of the process of obtaining the air force. method of sulfuric acid hydration of butylenes by the known and. The proposed methods are presented in the table ..

The use of the invention makes it possible to simplify the process of producing secondary butyl alcohol due to the exclusion from the process chain of the liquefaction stage of the side-produced butylenes.

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Claims (2)

m and 1397352 Formula of the Invention The method of recovering the secondary buty-: lovogo alcohol by two-step liquid phase sulfonation of the butane-butylene fraction, hydrolyzing the resulting butyl-sulfuric acid, isolating the target product by water distillation using a recurring blend, using the same pattern. product butylenes at 0 stage of sulfonation, I distinguish. t and with the fact that, in order to simplify the process, the side-formed 114 shys butylenes are absorbed with sulfuric acid up to the molar degree of saturation equal to 0.03-0.2, and the resulting mixture of sulfuric and butyl sulfuric acids is fed to the sulfonation stage. , Taken into account for examination 1. USSR author's certificate W 202912, cl. From 07 to 31/12, 09.09.65 2. Reconstruction of the production of “EC. The engineering project of Lengiproneftekhim, D., 1974, W D-11248, p. 87-95 (prototype).