RU2672262C1 - Method for production of calcium-zinc stabilizer - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to petrochemical synthesis, in particular to a method for the production of calcium-zinc stabilizer for the production of hard and plasticized PVC compositions, and can be used as a heat stabilizer for the production of rigid and plasticized PVC compositions: profiles, pipes, wallpaper, hoses, containers, artificial leather, linoleum, as well as products made from them, for example, when casting under pressure, opaque and translucent wire insulation etc. Described is a method for the production of calcium-zinc stabilizer for the production of rigid and plasticized PVC compositions including the preparation of raw materials, the precipitation of calcium stearate and zinc stearate, mixing of calcium stearate with zinc stearate, filtering the calcium zinc stabilizer suspension, drying, packing and packaging the product, with the precipitation of calcium stearate and zinc stearate separately produced in the respective reactors, moreover, the process for obtaining calcium stearate involves the interaction of stearic acid and calcium hydroxide by heating and intensive mixing, followed by heat treatment, while the interaction of stearic acid and calcium hydroxide is carried out in an aqueous medium, and the emulsion is heated to 60–65 °C, transferred to a state of stable emulsion, maintained at this temperature for 110–120 minutes, heat treatment is carried out to aggregate particles, with constant stirring of the suspension, while the temperature is raised to 80–85 °C, maintained at a predetermined temperature for 10–15 minutes to pH 8.5–9.0 of the mother solution of the basic substance and acid number, followed by injection into the apparatus for mixing calcium stearate and zinc stearate, and the precipitation of zinc stearate involves pouring water into the reactor, mixing, then the concentrated hydrochloric acid at pH of 2.8–3.5 is poured in, zinc oxide is added, the temperature is raised to 90–92 °C using live steam, solid stearic acid is added, the temperature of the reaction mass is raised to 96–98 °C, the suspension circulation with the possibility of dissolving precipitated zinc oxide is performed for 110–120 minutes at a temperature of 96–98 °C, the suspension of zinc stearate is transferred to a stable emulsion to 4.5–5.0 pH of the mother solution, the acid number of 5.0 mg KOH/g and the content of the basic substance 10–11 wt.%, followed by pouring chemically purified water, mixing and pumping of stearate and zinc stearate into the apparatus for mixing calcium, and then a suspension of calcium stearate and zinc stearate is discharged, mixed for 20–30 minutes to obtain the basic substances of calcium stearate within 3.5–5 wt.% and zinc stearate within 2.5–3.5 wt. %.EFFECT: simplifying the process and increasing the activity and stability of the stabilizer for the production of rigid and plasticized PVC compositions.1 cl, 2 dwg

Description

FIELD OF THE INVENTION

The invention relates to petrochemical synthesis, in particular, to a method for the production of calcium - zinc stabilizer for the production of rigid and plasticized PVC compositions and can be used as a heat stabilizer for the production of rigid and plasticized PVC compositions: profiles, pipes, wallpaper, hoses, containers, artificial leather, linoleum, as well as products from them, for example, when injection molding, opaque and translucent insulation of wires and so on.

State of the art

A known method of producing salts of organic acids by the interaction of metal oxides with organic acids, including stearic acid, at a temperature of 200-240 C, the process is as follows: to acids heated to the above temperature, gradually, in portions, to avoid strong foaming, metal oxides are introduced in the form of pastes in dehydrated linseed oil, and the introduction of metal oxides in the form of pastes prevents their aggregation, while the process is carried out until a homogeneous reaction mass is obtained (see Forty n M.F.i al Chemistry and technology of film-forming substances -.. M .: Chemistry, 1981, pp 399-400)..

The disadvantage of this method is the high temperature of the process and, as a result, the contamination of salts of organic acids by products of thermal degradation and deterioration in quality.

A known method of preparing a catalyst for the synthesis of methanol by sequential precipitation of an aluminum-containing stabilizing filler and an active copper-zinc composition in the presence of this filler from the corresponding nitric acid solutions by adding sodium carbonate, followed by separation of the resulting catalyst mass, drying, calcining and molding, while the precipitation of the aluminum-containing filler is carried out from nitric acid solutions of zinc and aluminum and the deposition of copper-zinc-containing Compositions - from nitric solution of copper and zinc, including aluminum nitrate.

In the method, aluminum nitrate is taken in an amount ensuring its content in the filler in terms of aluminum 20-80 wt. % of the total aluminum content in the catalyst (see US Pat. RU No. 1750094, IPC B01J 37/03, B01J 23/80, publ. March 20, 1995).

The disadvantage of this method is the complexity of the process, high energy intensity.

A known method of preparing a catalyst by precipitation of nitric salts of copper, zinc and aluminum with sodium carbonate at 50-80 ° C, a pH of 6.0-8.0 and a precipitation time of 3 to 60 minutes, while the deposition of copper - zinc or copper - zinc - the aluminum compound is carried out on pre-precipitated zinc - aluminum stabilizer, and the deposition is carried out by continuously supplying solutions to the reactor system consisting of one or more reactors, and continuously withdrawing the suspension from the system, while the average residence time of copper - zinc - lyuminievogo compound in the reaction zone is no more than 60 minutes. (see Pat. RU No. 2100069, IPC B01J 23/80, B01J 37/03, publ. 12/27/1997).

The disadvantage of this method is the complexity of the process, high energy intensity.

A known method of producing thermal stabilizers of chlorinated hydrocarbons by the interaction of stearic acid and oxides or hydroxides of calcium, zinc, barium, magnesium or lead in the form of individual or mixed salts of stearic acid in the solid phase with vigorous stirring, the process is carried out in the presence of caustic soda or caustic potassium 0, 05-0.15% by weight of stearic acid and propylene carbonate, or dimethylformamide, or hexametapol, or sulfolane, or dimethyl sulfoxide in an amount of 0.005-0.05% by weight of stearic acid lots at a temperature of 40-95 ° C in a twin-screw reactor.

In the method, the interaction of stearic acid is carried out with oxides of Mg, Pb (see US Pat. RU No. 2391360, IPC С08К 5/098, С07С 51/41, С08К 5/5399, С08К 5/1565, С08К 5/20, С08К 5/45 , С08К 5/42, published on October 27, 2009).

The disadvantage of this method is the complexity of the process, the process in excess of hydroxides, which leads to a rise in the cost of the process.

The closest in technical essence and the achieved positive effect and adopted by the authors for the prototype is a method for the production of calcium - zinc complex stabilizer Vigostab KC-24, including the preparation of raw materials, precipitation of calcium stearate and zinc stearate, mixing calcium stearate with zinc stearate, filtering a suspension of calcium - zinc stabilizer, drying, packing and packaging of the product (see "Method for the production of calcium - zinc complex stabilizer Vigostab KTs-24", TU 2492-481-04872688-2006 "Vigostab KTs-24". Tech NIICHIMPOLIMER OJSC, Tambov, 3 Montazhnikov St.).

The disadvantage of this method is the complexity of the process, low activity and stability of the stabilizer.

Disclosure of invention

The objective of the invention is to develop a method for the production of calcium - zinc stabilizer for the production of rigid and plasticized PVC - compositions, which has a simplification of the process, increasing the activity and stability of the stabilizer.

The technical result, which can be obtained using the present invention, is to simplify the process and increase the activity and stability of the stabilizer for the production of rigid and plasticized PVC compositions.

The technical result is achieved using the method of production of calcium - zinc stabilizer for the production of rigid and plasticized PVC compositions, including the preparation of raw materials, precipitation of calcium stearate and zinc stearate, mixing calcium stearate with zinc stearate, filtering a suspension of calcium-zinc stabilizer, drying, packaging and packaging product, while the precipitation of calcium stearate and zinc stearate, is carried out separately in the respective reactors, and the production of calcium stearate involves the interaction stearic acid and calcium hydroxide by heating and vigorous stirring followed by heat treatment, while the interaction of stearic acid and calcium hydroxide is carried out in an aqueous medium, and the emulsion is heated to 60-65 ° C, transferred to a state of stable emulsion, maintained at this temperature for 110 -120 minutes, heat treatment is carried out to aggregate particles with constant stirring of the suspension, while the temperature is raised to 80-85 ° C, kept at a given temperature for 10-15 minutes to a pH of 8.5-9.0 m an aqueous solution of the basic substance and the acid number, followed by pumping into the apparatus for mixing calcium stearate and zinc stearate, and the precipitation of zinc stearate includes pouring water into the reactor, stirring, then pour concentrated hydrochloric acid at a solution pH of 2.8-3.5, load zinc oxide, raise the temperature to 90-92 ° C with hot steam, load solid stearic acid, raise the temperature of the reaction mass to 96-98 ° C, circulate the suspension with the possibility of dissolving the precipitated zinc oxide for 110-120 minutes at a temperature of 96-98 ° C, the suspension of zinc stearate is transferred to a stable emulsion to a pH of a mother liquor of 4.5-5.0, an acid value of 5.0 mg KOH / g and a basic substance content of 10-11 wt.%, s subsequent pouring of chemically purified water, mixing and pumping into the apparatus for mixing calcium stearate and zinc stearate, and then the suspension of calcium stearate and zinc stearate is drained, mixing them for 20-30 minutes to obtain basic substances of calcium stearate in the range of 3.5-5 wt.% and zinc stearate in the range of 2.5-3.5 wt.%.

Thus, the method of production of calcium - zinc stabilizer for the production of rigid and plasticized PVC compositions by the proposed method allows to simplify the process, increase activity and stability, as well as reduce costs.

The essence of the method of production of calcium - zinc stabilizer for the production of rigid and plasticized PVC compositions, is as follows.

Raw materials are preliminarily prepared, then calcium stearate and zinc stearate are precipitated, calcium stearate is mixed with zinc stearate, the suspension of calcium - zinc stabilizer is filtered, dried, packaged and packaged, while calcium stearate and zinc stearate are precipitated separately in the corresponding reactors, moreover, the production of calcium stearate includes the interaction of stearic acid and calcium hydroxide by heating and vigorous stirring, followed by heat treatment, while the interaction of stearic acid and calcium hydroxide is carried out in an aqueous medium, and the emulsion is heated to 60-65 ° C, transferred to a stable emulsion, maintained at this temperature for 110-120 minutes, heat treatment is carried out to aggregate the particles with constant stirring of the suspension, while the temperature is raised to 80-85 ° C, maintained at a given temperature for 10-15 minutes to a pH of 8.5-9.0 of the mother liquor of the basic substance and acid number, followed by pumping into the apparatus, and the precipitation of zinc stearate, including t pour water into the reactor, stirring, then pour concentrated hydrochloric acid at a solution pH of 2.8-3.5, load zinc oxide, raise the temperature to 90-92 ° C with hot steam, load solid stearic acid, raise the temperature of the reaction mixture to 96 -98 ° C, carry out the circulation of the suspension with the possibility of dissolving the precipitated zinc oxide for 110-120 minutes at a temperature of 96-98 ° C, transfer the zinc stearate suspension to a state of stable emulsion to a pH of the mother liquor 4.5-5.0, acid number 5.0 mg KOH / g and basic substance content 10-11%, followed by pouring chemically purified water, mixing and pumping into the apparatus, then a suspension of calcium stearate and zinc stearate is drained, mixing them for 20-30 minutes to obtain basic calcium substances in stearate in the range of 3.5-5 % and zinc stearate in the range of 2.5-3.5%.

Brief description of drawings and other materials

In FIG. 1, a method for the production of calcium - a zinc stabilizer for the production of rigid and plasticized PVC compositions is given, the characteristics of the feedstock, materials and intermediates table 1.

In FIG. 2, too, physico-chemical indicators of calcium-zinc stabilizer, table 2.

The implementation of the invention

Examples of specific performance of the method of production of calcium-zinc stabilizer for the production of rigid and plasticized PVC compositions.

Example. The raw materials are preliminarily delivered and prepared in accordance with GOST and TU (see Fig. 1, table 1): solid raw materials for the production of calcium - zinc stabilizer: calcium hydroxide, zinc oxide, stearic acid, and in polyethylene canisters: concentrated acetic acid, hydrochloric acid, while household, chemically purified water is supplied through the main pipeline, and compressed air is piped from the compressor unit, then calcium stearate and zinc stearate are precipitated, calcium stearate is mixed with zinc m stearate, filtering a suspension of calcium - zinc stabilizer, drying, packing and packaging of the product, while the precipitation of calcium stearate and zinc stearate is carried out separately in the respective reactors, each of which is equipped with two frame mixers and local ventilation, heating of the reaction mass is carried out with hot steam using a bubbler pipe, the temperature of the reaction mixture is controlled using a device, for example, “PRN-200”, a chemical household chemical is fed to the reactor using a centrifugal pump, using a top-level sensor the searched water or condensate and when the stirrer is turned on, load calcium hydroxide, then stearic acid, and the production of calcium stearate involves the interaction of stearic acid and calcium hydroxide by heating and vigorous stirring, followed by heat treatment, and the interaction of stearic acid and calcium hydroxide is carried out in an aqueous medium, and the emulsion is heated to 60-65 ° C, transferred to a stable emulsion, direct synthesis, then open the bottom drain valve from the reactor, turn on centrifugal the first pump and circulate in order to dissolve the settled and unreacted calcium hydroxide, maintain it, circulate the suspension at a given temperature of 60-65 ° C for 110-120 minutes, and to complete the synthesis of calcium stearate, heat the suspension to aggregate, enlarge the product particles, contributing to the improvement of suspension filtration with constant stirring, while the temperature is raised to 80-85 ° C, kept at a given temperature for 10-15 minutes to a pH of 8.5-9.0 of the mother liquor of the basic substance and acid other substance (see FIG. 2, tab. 2) with subsequent pouring of household water into the reactor, mixing and gravity transfer to the apparatus for mixing calcium stearate and zinc stearate, and precipitation, synthesis of zinc stearate is carried out in a separate reactor, also equipped with two frame mixers, three bubblers for supplying sharp steam and exhaust ventilation for which, using a centrifugal pump, a measuring rod is used to pour household or mother water into the reactor and, with the stirrer turned on, pour concentrated hydrochloric (or acetic) acid at a solution pH in the range of 2.8 -3.5, then load zinc oxide, raise the temperature to 90-92 ° C with hot steam supplied to the reactor through bubblers, load solid stearic acid, raise the temperature of the reaction mixture to 96-98 ° C, then open the bottom drain valve from the reactor, turn on a centrifugal pump and circulate the suspension in order to dissolve the settled and unreacted zinc oxide for 110-120 minutes at a temperature of 96-98 ° C, transferring the zinc stearate suspension to a state of stable emulsion to a mother liquor pH of 4.5-5, 0, acid number 5, 0 mg KOH / g and the content of the basic substance 10-11%, followed by pouring chemically purified water into the reactor with the mixer turned on, mixing with a centrifugal pump and pumping to the apparatus, and then with the mixer turned on and the lower zinc drain valve open, the stearate will gravity drain zinc stearate in the apparatus for mixing a suspension of calcium stearate and zinc stearate, where they are mixed for 20-30 minutes to obtain the basic substances of calcium stearate in the range of 3.5-5% and zinc stearate in the range of 2.5-3.5% (cm. FIG. 2, tab. 2), the filtration of a suspension of calcium - zinc stabilizer is carried out on drum vacuum filters of the type BOK-5 and BOK-3 with a filter surface of 5 and 3 m ² , consisting of perforated metal drums covered with filter cloth and receiving troughs with stirrers for receiving the suspension on filtering, and the filtering drums of vacuum filters are divided into zones of squeezing, blowing and tissue regeneration; during the filtering process, the paste of calcium stearate - zinc stabilizer from the drum web is cut with a special knife into the estrus hopper It is equipped with a vibrator, from where, with the help of twin-screw feeders, it is fed to the drying stage of calcium — a zinc stabilizer — to the grate of the drying unit, and the water obtained during the filtration of vacuum filters is fed through receivers to the industrial water collector for reuse. The drying of calcium stearate paste - zinc stabilizer is carried out in drying units of the type "Fluidized bed (KS)", which is a vertical apparatus - conical in the lower part and cylindrical in the upper, into which the wet product paste from the hopper - agitator is fed to the grate using a twin-screw feeder drying unit located in the lower part, and the drying agent is air using pressure gas blowers passing through steam heaters, heated in them to a temperature of 100-150 ° C and fed under the grates of the drying plants k, the heaters are turned on and off automatically depending on the temperature of the heated air, and the temperature in the fluidized bed of the product is maintained within 70-90 ° C, which is controlled, for example, by the TRM-101 device blocked with the inclusion of a twin-screw feeder, the hot steam used to heat the air in the air heaters has a pressure of 6-8 kg / cm ² , then the dried product from the KS drying plant in the form of a dusty air mixture enters cyclones, type STsL-42, where the dust is separated from the dusty air mixture the new part (85%) of the product, and the product that is not trapped in cyclones, mixed with air, enters the bag filter, where it is retained by the filter cloth of the sleeves, on which automatic machines for pulsed blowing of the bags with compressed air from the product supplied by the main pipeline are installed, then from cyclones and bag filters, the finished product, with the help of gate feeders, is fed into the bunkers of the finished product, and the drying agent, thoroughly cleaned of the product, is thrown into the atmosphere using tail gas blowers. From the finished product bin, the dried calcium-zinc stabilizer is Packed with a sectional feeder into a packaging booth equipped with a local exhaust ventilation system consisting of a sanitary filter bag type - FRKN-60 with a filtration area of 60 m ² and a tail gas blower type TG-150-1, 12 into soft containers or kraft bags with plastic liners. In accordance with GOST 3885 -73, a batch of a finished product is considered to be the mass of the product obtained according to one technological documentation and accompanied by one quality document, which is transported to the finished goods warehouse.

The invention in comparison with the prototype and other known technical solutions has the following advantages:

- simplification of the technological process of the method of production of calcium - zinc stabilizer;

- reducing the cost of the method for producing lead stabilizer of polyvinyl chloride stabilizer;

- increase the activity and stability of the stabilizer;

- reducing the cost of the method of obtaining a stabilizer;

- improving the environmental cleanliness of the drying agent emitted into the atmosphere, due to the purification of the product in several stages;

- the exclusion of the explosion of a dusty mixture of calcium - zinc stabilizer and the destruction of equipment.

Claims (1)

A method of producing a calcium-zinc stabilizer for the production of rigid and plasticized PVC compositions, including preparing raw materials, precipitating calcium stearate and zinc stearate, mixing calcium stearate with zinc stearate, filtering a suspension of calcium-zinc stabilizer, drying, packaging and packaging of the product, characterized in that the precipitation of calcium stearate and zinc stearate is carried out separately in the respective reactors, moreover, the production of calcium stearate involves the interaction of stearic acid and hydroxide to water by heating and vigorous stirring, followed by heat treatment, while the interaction of stearic acid and calcium hydroxide is carried out in an aqueous medium, and the emulsion is heated to 60-65 ° C, transferred to a stable emulsion, kept at this temperature for 110-120 minutes, conduct heat treatment to aggregate particles, with constant stirring of the suspension, while the temperature is raised to 80-85 ° C, kept at a given temperature for 10-15 minutes to a pH of 8.5-9.0 of the mother liquor of the main substance VA and acid number, followed by injection into the apparatus for mixing calcium stearate and zinc stearate, and the precipitation of zinc stearate involves pouring water into the reactor, stirring, then pour concentrated hydrochloric acid at a pH of a solution of 2.8-3.5, load zinc oxide , raise the temperature to 90-92 ° C with hot steam, load solid stearic acid, raise the temperature of the reaction mass to 96-98 ° C, circulate the suspension with the possibility of dissolving the precipitated zinc oxide for 110-120 minutes at a temperature of 96-98 ° C translating t a suspension of zinc stearate in a state of stable emulsion to a pH of a mother liquor of 4.5-5.0, an acid number of 5.0 mg KOH / g and a basic substance content of 10-11 wt.%, followed by pouring chemically purified water, stirring and pumping into an apparatus for mixing calcium stearate and zinc stearate, and then the suspension of calcium stearate and zinc stearate is drained, mixing them for 20-30 minutes to obtain basic substances of calcium stearate in the range of 3.5-5 wt.% and zinc stearate in the range of 2 5-3.5 wt.%.

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