RU2707362C1 - Method of producing titanium trichloride - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of titanium trichloride used as a component of an anode active coating, a catalyst in organic synthesis, as well as in water purification processes. Method of producing titanium trichloride involves reducing titanium tetrachloride with a metal while heating. Initial solution used is 15–55 wt% aqueous solutions of titanium tetrachloride. Amount of metal varies from 10 to 100 % from stoichiometric. Recovery process is carried out at temperature of 30–110 °C. Metal used is aluminum, iron or a mixture of metal wastes from the process of thermal recycling solid municipal wastes.

EFFECT: reduced power consumption, simplified hardware scheme and improved environmental and production safety.

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Description

The invention relates to the production of titanium trichloride used as a component of the active coating of anodes, a catalyst in organic synthesis, as well as in water purification processes.

Known methods for producing titanium trichloride, including the interaction of metallic titanium with an aqueous solution of hydrochloric acid concentration by heating [US Pat. RF 2316475 02.02.2008; JP 080208227, publ. 08/13/1996].

The disadvantages of the known methods are the technological difficulties of the process, the complexity and high cost of hardware design, expensive raw materials.

Known methods for producing titanium chlorides (II and III) (art. Lower titanium chlorides, their properties, production and use (review of literature and patents). - VG Gopienko, GN Gopienko. - J. Non-ferrous metallurgy. - 1964.-№4, p. 26-29; article Development of the technology for producing and refining titanium-containing melts using mechanical stirring - R.A. Sandler, A.I. Gulyakin, D.S. Abramov, E.N. Pinaev , E.I. Yaskelyainen, L.M. Berdnikova, G.S. Lukashenko, B.A. Karpov. - Works of YOU - Production of Magnesium and Titanium, No. 83, Leningrad, 1972, pp. 94-98; st. Development technological foundations the process of obtaining lower titanium chlorides. - S.V. Aleksandrovsky, L.M. Berdnikova, A.I. Gulyakin, E.N. Pinaev, D.S. Abramov. - J. Non-ferrous metallurgy, No. 12, 1977, - p. . 29-31; Pat. RF No.: 2370445 dated 10/20/2009), which includes supplying metal chlorides, titanium metal (waste) to the sealed reactor, and feeding titanium tetrachloride to the reactor. The process is conducted in an inert atmosphere, titanium chloride is recovered from the reactor by settling or filtration.

The disadvantage of these methods is the high cost of raw materials, the complexity of the hardware scheme, high energy costs (molten salts) and significant amounts of hard to utilize residue (dumping).

Known methods for producing a catalyst based on titanium trichloride (USSR Patent 504496, CL C08F 10/14, 1972; US Patent 4,235,745, CL C08F 4/64, 1980; US Patent 4,199,474, CL C08F 4/64, 1980; RF Patent 2053841, CL B01J 37/00, 1993), including the reduction of titanium tetrachloride with organic compounds.

The disadvantages of these methods are: the long duration of the synthesis process; low stability of the catalyst during storage (storage temperature), high cost of the starting reagents.

The closest in technical essence (prototype) and the achieved result is a method for producing titanium trichloride, including the processing of concentrated titanium tetrachloride with a metal (aluminum, magnesium, titanium) at a temperature of from 200 to 900 ° C (G. Luchinsky, Chemistry of titanium. - M. : Publishing house "Chemistry", 1971. - 471 p.):

The disadvantages of this method are the complex instrumentation of the process and the high energy consumption for heating the reaction mixture. In addition, concentrated titanium tetrachloride does not react with metallic iron even at an incandescent temperature.

A significant disadvantage of the prototype is the work with concentrated anhydrous titanium tetrachloride, which upon contact with air hydrolyzes with the formation of hydrochloric acid vapor (white smoke). The formation of volatile toxic fumes with high corrosivity requires the use of pressurized reactors, as well as additional personnel safety measures.

The objective of the invention is to develop a technology for the production of titanium trichloride with reduced energy consumption, a simplified hardware scheme and increased environmental and industrial safety, which can be used in wastewater treatment processes.

The problem is solved by the method of producing titanium trichloride, including the reduction of titanium tetrachloride by metal when heated, while the initial solution is taken 15-55 wt.% Aqueous solutions of titanium tetrachloride, the amount of metal varies from 10 to 100% of the stoichiometric, and the recovery process is carried out at temperature from 30 to 110 ° C, and the metal used is aluminum or iron, or a mixture of metal waste from the process of thermal utilization of municipal solid waste.

The main advantages of the proposed method include lower temperatures of the recovery process, reduction of energy consumption for heating the reaction mixture, as well as a significant simplification of the hardware circuit of the process, due to the rejection of sealed vessels operating under high pressure and at high temperature. In addition, it becomes possible to use metal waste from solid waste incineration processes. Aqueous solutions of titanium tetrachloride are less susceptible to hydrolysis, and the amount of emitted hydrochloric acid vapor decreases by a factor of 100 or more.

The essence of the proposed method and the achieved results can be more clearly illustrated by the following examples

The content of titanium trichloride is determined according to the titration of the resulting solution with ammonium sulfate in the presence of an indicator of thiocyanate or methylene blue (GP Luchinsky. Chemistry of titanium. - M .: Publishing house "Chemistry", 1971. - 471 p. P. 397).

EXAMPLE No. 1

Into an aqueous solution of titanium tetrachloride (15 wt.%) Weighing 50 grams, 0.355 grams of aluminum is introduced in the form of granules (100% of stoichiometry). The reaction mixture is heated to 90 ° C, with constant stirring and the recovery process is carried out for 100 minutes. The content of titanium trichloride in the resulting solution is 12.1%.

EXAMPLE No. 2

Into an aqueous solution of titanium tetrachloride (55 wt.%) Weighing 50 grams, 1.3 grams of aluminum is introduced in the form of chips (100% of stoichiometry). The recovery process is carried out with constant alteration for 120 minutes at a temperature of 30 ° C. The content of titanium trichloride in the resulting solution is 44.7%.

EXAMPLE No. 3

Into an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, 0.71 grams of aluminum in the form of a powder (100% of stoichiometry) is introduced. The reaction mixture is heated to 80 ° C, with constant stirring and the recovery process is carried out for 60 minutes. The content of titanium trichloride in the resulting solution is 24.4%.

EXAMPLE No. 4

In an aqueous solution of titanium tetrachloride (25 wt.%) Weighing 50 grams, enter 0.59 grams of aluminum in the form of electrical scrap (100% of stoichiometry). The reaction mixture is heated to 100 ° C, with constant stirring and the recovery process is carried out for 30 minutes. The content of titanium trichloride in the resulting solution is 20.3%.

EXAMPLE No. 5

In an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, 2.21 grams of iron in the form of scrap (100% of stoichiometry) is introduced. The reaction mixture is heated to 110 ° C, with constant stirring and the recovery process is carried out for 45 minutes. The content of titanium trichloride in the resulting solution is 40.6%.

0.25 ml of the resulting solution is introduced into the wastewater of galvanic production with a volume of 1 liter and a content of chromium (VI) compounds of 3.2 mg / l. The removal efficiency of chromium compounds (VI) is 99.9%.

EXAMPLE No. 5 (a)

Into an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, 0.95 grams of magnesium is introduced in the form of chips or scrap (100% of stoichiometry). The recovery process is carried out with constant alteration for 120 minutes at a temperature of 70 ° C. The content of titanium trichloride in the resulting solution is 40.6%.

0.55 ml of the resulting solution is introduced into the wastewater of galvanic production with a volume of 2 liters and a content of chromium (VI) compounds of 2.3 mg / L. The removal efficiency of chromium compounds (VI) is 99.4%.

EXAMPLE No. 6

In an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, injected 0.071 grams of aluminum in the form of a powder (10% of stoichiometry). The reaction mixture is heated to 110 ° C, with constant stirring and the recovery process is carried out for 5 minutes. The content of titanium trichloride in the resulting solution is 2.44%.

EXAMPLE No. 7

In an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, enter 0.355 grams of aluminum in the form of a powder (50% of stoichiometry).

The reaction mixture is heated to 100 ° C, with constant stirring and the recovery process is carried out for 15 minutes. The content of titanium trichloride in the resulting solution is 12.2%.

2.0 ml of the resulting solution is introduced into the wastewater of galvanic production with a volume of 1 liter and a content of chromium (VI) compounds of 19.2 mg / l. The removal efficiency of chromium compounds (VI) is 99.9%.

EXAMPLE No. 8

Into an aqueous solution of titanium tetrachloride (30 wt.%) Weighing 50 grams, 0.75 metal mixtures (waste) of thermal utilization of municipal solid waste (100% of stoichiometry) are introduced. The reaction mixture is heated to 80 ° C, with constant stirring and the recovery process is carried out for 60 minutes. The content of titanium trichloride in the resulting solution is 24.2%.

1.0 ml of the resulting solution is introduced into the wastewater of galvanic production with a volume of 1 liter and a content of chromium (VI) compounds of 12.7 mg / l. The removal efficiency of chromium compounds (VI) is 99.8%.

As can be seen from the examples, the technical result of the above is a decrease in the temperature of the process, simplification of the hardware scheme and the possibility of using cheap metal raw materials and increasing environmental and industrial safety through the use of diluted solutions. Using the present invention, it is possible to obtain a wide range of reagents for organic synthesis processes and wastewater treatment processes of various origins (including electroplating).

In addition, it was found that iron can be used to reduce titanium tetrachloride, which also distinguishes the proposed method from the prototype.

Claims (2)

1. A method of producing titanium trichloride, including the recovery of titanium tetrachloride by metal by heating, characterized in that 15-55 wt.% Aqueous solutions of titanium tetrachloride are taken as the initial solution, the amount of metal varies from 10 to 100% of the stoichiometric, and the reduction process at a temperature of 30 to 110 ° C. 2. A method of producing titanium trichloride according to claim 1, characterized in that aluminum or iron or a mixture of metal waste from the process of thermal utilization of municipal solid waste is used as the metal.