The method of preparation of the catalyst acid hydrolysis

 

(57) Abstract:

The invention relates to the production of liquid catalysts on the basis of aromatic sulfonic acids for the hydrolysis of fats. Method for obtaining a catalyst for acid hydrolysis of fats and vegetable oils, which 90-98% sulfuric acid or a corresponding mixture of sulfuric acid of a lower concentration of the oleum is introduced into intensive contact with taken 10-20% stoichiometric excess of aromatic hydrocarbon in a bead mill, vertical type at 100 C in the presence of stimulating supplements based on a mixture of acetates of iron (II) and potassium in a molar ratio of 3:2-1:1 in the form of a solution in acetic acid with a salt concentration of iron of 0.1-0.15 mol/kg in the amount of dry catalyst 0,028-to 0.055 wt.% for 45-120 min, followed by settling, separation and return to re-process the hydrocarbon layer. Technical result: the liquid catalyst hydrolysis without specially organized water separation, simplified the process of sulphonation and its instrumentation. 2 C.p. f-crystals, 4 PL.

The invention relates to the production of liquid water-containing catalysts on the basis of aromatic sulfonic acids for hydrolysis W is slag industry.

Know the use as catalyst for the hydrolysis of vegetable oils and fats p-toluenesulfonic acid or its sodium salt with an equivalent amount of hydrochloric acid (patent RF №2166534). p-Toluensulfonate was obtained by the reaction of sulfonation by boiling with water separation of a mixture of sulfuric acid (concentration of 96%) and toluene in excess of the latter. From the reaction mixture the desired product was isolated in the form of hydrated, washed his Hcl conc. to negative reactions on sulfate ions, dried and then were dosed out in the reactor for hydrolysis. Performed in further studies showed the absence of a justified necessity in the selection of individual sulfonic acids in solid form and it thoroughly cleaned from sulfate ions and, moreover, revealed a number of significant disadvantages of the use of the hydrolysis catalyst in solid form.

A method of obtaining aromatic sulfonic acids (as the USSR №835104), in which additional chemical reaction excluded odonatoptera during the interaction of aromatic hydrocarbons with sulfuric acid. To implement this pre-prepared complex formed of 100% sulfuric acid and acetic anhydride, which Yes is Noah mixture are mixed with acetic acid.

Closest to the claimed is a method of producing a liquid anhydrous catalyst on the basis of aromatic sulfonic acids (as the USSR №952319), including sulfonation of aromatic hydrocarbons with sulfuric acid at a temperature of 110-120C, the azeotropic distillation of the water and the extract sulfatase at 180-200C for 2-3 hours, further transmission of the aromatic hydrocarbon with simultaneous azeotropic distillation of the water.

The disadvantages of this method are:

- two-three-fold excess of sulfuric acid, not any, and 98%;

- the need for a fairly long time (2-3 hours) and high temperature (180-200C) endurance to complete the process of sulfonation and removal of the reaction water;

the necessity of passing the aromatic hydrocarbon, which requires not only additional quantities of hydrocarbon, additional inputs, but also additional equipment to receive vapors and condensing them in the form of an azeotropic mixture with water, for water separation, drying and purification of hydrocarbon and so on;

in General, high-intensity, multi-stage and a large assortment of used equipment.

Izvestnaia, sulphate of mercury, cadmium, aluminum, lead, arsenic, bismuth, iron (preparative organic chemistry /Ed. by N. With.Wolfson. - M.: Goskomizdat, 1959. S. 242-244).

The drawback of such solid catalysts is the poor solubility and prolonged dissolution process, which causes inconvenience in use and leads to non-stationary mode of catalysis. Direct experiment has shown that the effectiveness of such additives in high-speed sulfonation in the bead mill is very small.

The objective of the proposed solutions is to obtain liquid catalyst in the hydrolysis of vegetable oils and fats in the form of a reaction mass of sulfonation of aromatic hydrocarbons or their mixtures of concentrated sulfuric acid in the absence of specially organized water separation made with raw material and produced in the course of the process water, promotion of sulfonation of the liquid additive, the reduction of the stages and simplify the process of sulfonation and its hardware design.

This object is achieved in that 90-98% sulfuric acid or the corresponding mixture of sulfuric acid of a lower concentration of the oleum is put into intensive contact with taken with 10-20% excess what about the free discharge gas space of the reactor to the atmosphere at 100 C in the presence of stimulating supplements based on a mixture of acetates of iron (II) and cadmium in a molar ratio of 3:2-1:1 in the form of a solution in acetic acid with a salt concentration of iron of 0.1-0.15 mol/kg in the amount of dry catalyst 0,028-to 0.055 wt.% for 45-120 min, followed by settling and separation of hydrocarbons.

As the aromatic hydrocarbon take toluene, o-xylene, m-xylene, p-xylene, mixtures of xylene isomers and ethylbenzene. And stimulating Supplement for the sulfonation of aromatic hydrocarbons with sulfuric acid to obtain a concentration in the refining process with delegacia reaction mixtures formed in the quantitative oxidation of potassium iodide is taken in the stoichiometric ratio of iron oxide Fe3O4or Fe2ABOUT3in glacial acetic acid at a temperature of 75-85C in a bead mill.

Characteristics of the raw materials used

Toluene GOST 5789-78

o-Xylene THE 6-09-3825-78

m-Xylene THE 6-09-2438-82

p-Xylene THE 6-09-3780-78

Givental THE 6-09-2786-73

The mixture of xylene isomers THAT 6-09-3829-74

Sulfuric acid GOST 4204-77 (90% and above)

Oleum TU 6-09-3881-75

Acetate of iron (II), 4-water THAT 6-09-08-1287-78

Potassium acetate GOST 5820-78

Acetic acid GOST 61-75

Iodine GOST 4159-79

The process of preparation of the catalyst of the hydrolysis of the inventive method consists in the following. In ball mill vertical type load sulfuric acid or a mixture of sulfuric acid with oleum stirring and heating, open the output of the gas space into the atmosphere, bring the temperature to the preset value and stabilize it. In this mode, continue the stirring for the desired time. Then turn off the heating, mechanical stop stirring and allow the reaction mass to settle and decompose. Then discharged through the drain pipe by gravity first bottom layer of concentrated solution of sulfonic acids and then the upper hydrocarbon layer. A solution of sulfonic acids suitable for direct use as catalyst for the hydrolysis of vegetable oils and fats. The hydrocarbon layer (very diluted solution of sulfonic acids in the hydrocarbon) return repeated the process.

Getting stimulant supplements for sulfonation is conducted as follows. In ball mill vertical type heating glass beads as pereirago means enter the appropriate quantity of glacial acetic acid, potassium iodide. When mixing this download is heated to operating temperature, then enter the appropriate amount of iron oxide Fe2ABOUT3or Fe3O4. Include again the mechanical stirring and lead okishio obtained reaction mixture was subjected to simple distillation with delegacia, controlling the salt content of iron in Cuba. As soon as the latter will be in the range of 0.1 to 0.15 mol/kg, the process of distillation ceased, cubic liquid is drained and used for these purposes.

Example 1.

In ball mill vertical type with case and blade stirrer of stainless steel with a capacity of 6.5 liters, with the boot nozzle and nozzle with shutoff valve as free access to the atmosphere, located in the top cover, an electrical heating element on the side walls and the bottom drain pipe with a metal grid with dimensions of 11 mm, slightly spherical bottom, containing constantly 2,75 kg of glass beads with a diameter of 2-3 mm, enter 2,18 kg of 90% sulfuric acid (20 mol), 2.44 kg o-xylene (23 mol; stoichiometric excess of 15%) and 50 g of stimulating supplements in the form of a solution of acetate of iron (II) and potassium in a molar ratio of 1:1 acetic acid with the concentration of iron salts 0,1442 mol/kg (1,962 g anhydrous salts, i.e. 0,042% by weight of the initial reaction mixture, and the share acetate anhydrous iron (II) have 1,2546 g and at a fraction of potassium acetate 0,7077 g). Include mechanical stirring and heating for 17 min deduce the temperature at 115S. Stabilize the temperature at this level is clucalc heating for 30 min to give the mixture to flow from the walls to settle. During this time the temperature dropped to S. Open the bottom drain pipe and is collected containing killswitches layer number 4280 g, and then 360 g of the hydrocarbon layer; loss of 30, a Full material balance showed that the degree of conversion of sulfuric acid was 97%. The hydrocarbon layer without any processing returns to repeat sulfonation.

Stimulating Supplement for this example, get so. In ball mill vertical type load 393,8 g of glacial acetic acid and 4,16 g KJ. Include mixing and heating, and heat the mixture up to 80C. Upon reaching this temperature, administer 2 g Fe2ABOUT3(hematite) and lead the process to practically complete consumption of the oxidant and reductant. Control is carried out on the kinetics of excretion of molecular iodine. To achieve a 97% degree of conversion of the oxide in this case, it took 37 minutes

By filtration through a grid with dimensions 0,50,5 mm the reaction mass is separated from the glass beads and transferred into a cube for the distillation of volatile with delegacia carried out to achieve the concentration of iron salts 0,1442 mol/kg (salt content of iron in the original mass to concentration was ~0,062 mol/kg).I get stimulating for the sulfonation supplements the concentration of sulfuric acid, the procedure and the amount of downloads of sulfuric acid and hydrocarbons, as well as reagents for stimulating additives, temperature and other characteristics of the methods of sulfonation is similar to that described in example 1. Different dosage of stimulating additives, the amount, calculated on the anhydrous salt, the salt concentration of iron in stimulating additive nature of the iron oxide and the temperature upon receipt stimulating supplements. Here are examples of carrying out the sulphonation in the absence of stimulating additives, using only as a last acetic acid, as well as with model stimulating additive in the form of a specially prepared solution of acetate of iron (II) and potassium acetate in acetic acid. Characteristics of the process of sulfonation and receive stimulating supplements for these examples are summarized in table.1

Examples 11-14

Sulfiram hydrocarbon, installation for carrying out the process of sulfonation and receive stimulating for the sulfonation of the additive, the concentration of sulfuric acid, the order and magnitude of loads of sulfuric acid and hydrocarbons, as well as reagents for stimulating additives, temperature, etc is in the process of obtaining a stimulating supplements, lower molar ratio of acetate of iron and potassium in a stimulating addition, the salt concentration of iron in the additive and the mass content of the dry catalyst in the initial download on sulfonation.

In particular, to obtain stimulating additives load 395,3 g of glacial acetic acid and 2,80 g KJ. The specified weight is heated to 80C and enter 1,95 g Fe3O4. 54 min the process bead mill, the degree of conversion of iron oxide Fe3O4reached 98%. And after concentration by distillation of volatile salt concentration of iron in Cuba was 0.147 mol/kg, the Ratio of the concentrations of iron acetate and potassium acetate 3:2.

Characteristics of the process of sulfonation are given in table.2

Examples 15-24

Download sulfonamide hydrocarbons, sulfuric acid and stimulating supplements, as well as the initial concentration of sulfuric acid and salt in a stimulating addition, the molar ratio of acetate of iron and potassium in addition, as well as getting stimulating additives similar to those described in example 1. Similar to example 1 and the procedure of the process of sulfonation. Different temperature and nature sulfonamide hydrocarbon. Characteristics of the conduct of sulfonation is similar to that described in example 16. Different concentration of sulfuric acid, a method of obtaining a concentration of the excess and nature sulfonamide hydrocarbon, characteristics and dosage used stimulating supplements. Characteristics of such processes are given in table.4.

As can be seen from the data presented above, all processes of sulfonation of aromatic hydrocarbons in a bead mill were almost quantitatively without specially organized sanitation, helped by intensive mechanical mixing and the use of effective stimulating supplements. The process of sulfonation was almost single-stage, passing under easily achieved moderate temperatures, and fast. Simplified and instrumentation. Pretty easy and getting stimulating supplements. The latter can be performed in the same bead mill and the process of sulfonation. Get sulfatase after separation of the hydrocarbon layer is used as the catalyst for hydrolysis without any treatment.

1. The method of producing acid hydrolysis catalyst, characterized in that 90-98% sulfuric acid or a corresponding mixture of sulfuric Ki is the number of aromatic hydrocarbon in a bead mill, vertical type with easy access to the gas space of the reactor to the atmosphere at 100 C in the presence of stimulating supplements based on a mixture of acetates of iron (II) and potassium in a molar ratio of 3:CH:1 in the form of a solution in acetic acid with a salt concentration of iron of 0.1-0.15 mol/kg in the amount of dry catalyst 0,028-to 0.055 wt.% for 45-120 min, followed by settling, branch and return to repeat the process of hydrocarbons.

2. The method according to p. 1, characterized in that the aromatic hydrocarbon take toluene, o-xylene, m-xylene, p-xylene, mixture of isomers of xylene, and ethylbenzene.

3. The method according to p. 1, wherein the stimulating additive for the sulfonation of aromatic hydrocarbons with sulfuric acid to obtain a concentration in the refining process with delegacia reaction mixtures formed in the quantitative oxidation of potassium iodide is taken in the stoichiometric ratio of iron oxide Fe3O4or Fe2O3in glacial acetic acid at a temperature of 75-85C in a bead mill.

 

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