RU2423413C2 - Method of producing sulphur-containing additive - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to synthesis of sulphur-containing additives. Described is a method of producing a sulphur-containing additive by reacting α-olefins with elementary sulphur at high temperature in the presence of a nitrogen-containing catalyst, characterised by that the nitrogen-containing catalyst used is 2-[(hydroxymethyl)amino]-1-ethanol in amount of 0.05-0.10 wt % with respect to the C₁₀-C₁₂ α-olefin fraction.

EFFECT: high output of the sulphur-containing additive and simplification of the process.

1 cl, 4 ex

Description

The invention relates to the field of synthesis of sulfur-containing additives with enhanced anti-seize, anti-wear properties, high thermal and oxidative stability.

These additives are used for the manufacture of technological lubricants, including those applicable for operations of cold forging and metal upsetting.

A known method of producing a sulfur-containing additive by the interaction of α-olefins of the C ₁₆ -C ₁₈ fraction with elemental sulfur and hydrogen sulfide at a ratio of the starting components of 1: 1, 5: 0.5 and a temperature of 171 ° C. Sulfidated α-olefins contain 20.6% sulfur [PCT International Application (WO) No. 88/02771, cl. C10M 135/02, 141/08, 1987].

The disadvantages of this method are:

1. The use as a reagent and catalyst of highly toxic hydrogen sulfide, which requires special conditions for safe process.

2. The formation in the presence of hydrogen sulfide of mercaptans, giving the resulting sulfur-containing additive difficult to tolerate smell.

3. The need to remove hydrogen sulfide and the resulting mercaptans from the obtained sulfur-containing additives in order to give the latter the required organoleptic properties.

4. The presence of a significant amount of gas emissions containing hydrogen sulfide and mercaptans.

A known method of producing disulfides by oxidation of the corresponding alkylthiomagnesium bromides with 2,3-dibromotetrahydrofuran or the reaction of alkylthiocyanates with methylmagnesium iodide in ether [Yu.N. Polivin, T.S. Sheveleva, A.A. Bienko, R.A. Karakhanov. New methods for the synthesis of disulfides - promising antiwear additives to oils // Neftekhimiya. 1992.V.32. Number 3. S.260]. The implementation of this method on an industrial scale is in great doubt due to the lack of raw materials and the low technological level of the process as a whole.

The closest in technical essence and the obtained results is a method of producing extreme pressure additives OTP [A. M. Ravikovich, E. I. Petyakina, I. D. Maslova, P. P. Bagryantseva. Anti-seize additive OTP for gear oils // Chemistry and technology of fuels and oils. 1968. No. 1. S.50].

The additive OTP is obtained by sulfidation of a fraction of propylene polymers containing mainly tetramers and pentamers of propylene at a temperature of 150-160 ° C and a duration of 10-15 hours. The resulting additive is treated with a 25-30% aqueous solution of sodium sulfide at a temperature of 85-95 ° C in order to remove hydrogen sulfide and low molecular weight mercaptans.

The purified additive after settling at 70-80 ° C is distilled under vacuum at a residual pressure of 5-10 mm Hg. and a temperature of 120-140 ° C to remove unreacted raw materials. The remainder of the vacuum distillation is mixed with 5% of bleaching earth and 1% zinc oxide at 110-120 ° C for 0.5 h and then filtered. The yield of additives is 50-60 wt.% For raw materials.

The disadvantages of this method are:

1. Low yield of sulfur-containing additives - 50-60%.

2. The insufficiently high sulfur content in the sulphidized additive is 20-25 wt.%.

3. The multi-stage method.

The aim of the invention is to increase the yield of sulfur-containing additives and the simplification of process technology.

To this end, a method for producing a sulfur-containing additive by reacting α-olefins of the C ₁₀ -C ₁₂ fraction with S _{8 is} carried out in the presence of catalytic amounts of 0.05-0.10 wt.% 2 - [(hydroxymethyl) amino] -1-ethanol at a lower temperature 130-140 ° C for 6 hours. The output of sulfur-containing additives is 90-94 wt.%; the sulfur content in the additive reaches 42 wt.%.

The synthesized sulfur-containing additive without any subsequent processing and separation of the catalyst can be used to obtain various technological lubricants, including for cold die stamping and metal upsetting.

The method is as follows.

The α-olefins of the fraction C ₁₀ -C ₁₂ , 0.05-0.10 wt.% With respect to the α-olefins of the catalyst 2 - [(hydroxymethyl) amino] -1 are loaded into a thermostated reactor equipped with an efficient stirrer, refrigerator and thermometer. ethanol and temperature are increased to 130 ° C. Upon reaching a temperature of 130 ° C, powdered or liquid sulfur is supplied to the reactor. Then the temperature is increased to 140 ° C and within 6 hours carry out the synthesis of sulfur-containing additives.

The reaction mass is cooled to 40 ° C and the unconverted sulfur is separated by filtration.

The method is illustrated by the following examples.

Example 1. In a thermostatic glass reactor equipped with an effective stirrer, thermometer, reflux condenser, load 600 g of α-olefins fraction C ₁₀ -C ₁₂ , 0.05 wt.% 2 - [(hydroxymethyl) amino] -1-ethanol and temperature increase to 130 ° C. 450 g of powdered sulfur are fed into the reactor within 1 hour, after which the temperature is increased to 140 ° C and the reaction of sulfur with α-olefins is carried out for 6 hours. The reaction mass is cooled to 40 ° C and separated from unconverted sulfur by filtration. Received 945.5 g of additives with a sulfur content of 40.8 wt.%.

Example 2. 600 g of α-olefins of the fraction C ₁₀ -C ₁₂ , 0.07 wt.% 2 - [(hydroxymethyl) amino] -1-ethanol are charged into the reactor, and the temperature is increased to 130 ° C. 450 g of sulfur are fed into the reactor within 1 hour, then the temperature is increased to 140 ° C and the reaction of sulfur with α-olefins is carried out for 6 hours. After cooling the reaction mass to 40 ° C and filtering, 965.2 g of an additive with a sulfur content of 41.9 wt.% Were obtained.

Example 3 is carried out analogously to example 1, but 0.1 wt.% Of α-olefins are used in the catalyst. Received 987.4 g of additives with a sulfur content of 42.1 wt.%.

Example 4 is carried out analogously to example 1, but the catalyst is used 0.15 wt.% On the taken α-olefins. Received 987.2 g of additives with a sulfur content of 42.2 wt.%.

Thus, the proposed method for producing sulfur-containing additives in comparison with the prototype has the following advantages:

1. The reaction of elemental sulfur with α-olefins of fraction C ₁₀ -C _{12 is} carried out in the presence of catalytic amounts of 0.05-0.10 wt.% On raw materials 2 - [(hydroxymethyl) amino] -1-ethanol and at a lower temperature 130-140 ° C.

2. The sulfur content in the additive is 15-20 wt.% Higher than in the prototype.

3. The output of sulfur-containing additives is 90-94 wt.%; in the prototype - 50-60 wt.%.

4. The method is single-stage and simple technology.

5. The process does not generate wastewater and industrial waste.

6. The resulting additive does not require additional purification from the used catalyst.

Claims (1)

A method of producing a sulfur-containing additive by reacting α-olefins with elemental sulfur at an elevated temperature in the presence of a nitrogen-containing catalyst, characterized in that 2 - [(hydroxymethyl) amino] -1-ethanol in an amount of 0.05-0.10 is used as a nitrogen-containing catalyst wt.% in relation to the α-olefin fraction C ₁₀ -C ₁₂ .