Synthesis method of butyl zirconate and butyl hafnate

Abstract

The invention discloses a method for synthesizing butyl zirconate and butyl hafnate, and relates to the technical field of material synthesis, and the method comprises the following steps: mixing and stirring: putting a solvent n-heptane into a reaction kettle, putting a certain amount of hafnium tetrachloride (or zirconium tetrachloride) solid into the reaction kettle, putting a certain amount of n-butyl alcohol into the reaction kettle, and stirring for 30-60 minutes; finally, stirring; organic synthesis: introducing ammonia gas in the stirring process in the step S1, and setting the reaction temperature to be 45 DEG C or below and the reaction pressure to be normal pressure; performing solid-liquid separation; organic distillation; compared with the existing process, the preparation method has the advantages that the preparation cost of the product is greatly reduced through an organic synthesis and secondary distillation treatment mode; and secondly, in the preparation process, the generation of pollutants, especially triethylamine hydrochloric acid, is reduced, the generation of hazardous wastes is avoided, only deacidification and ammonium chloride removal treatment are needed, and compared with the existing process, the cost is greatly reduced, and the environmental protection benefit is relatively obvious.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material synthesis, in particular to a synthesis method of butyl zirconate and butyl hafnate. BACKGROUND

[0002] Zirconium and hafnium are widely used in aerospace, military, electronic information, and atomic energy fields, and are important strategic metal resources. Efficient utilization of zirconium and hafnium resources and preparation of high-end products are national major strategies. Organic zirconium and hafnium materials are of various types and are essential precursor materials in the field of integrated circuits and chips. At present, several amine-based zirconium and hafnium products, such as tetra(dimethylamino) zirconium and hafnium and tetra(methyl ethyl amino) zirconium and hafnium, have been prepared in China. Butyl zirconate and butyl hafnate are new types of organic zirconium and hafnium products. Due to their characteristics of high efficiency, high performance conversion products, and multifunctional applications as metal organic compound precursors, they have unique advantages in the field of high-end materials.

[0003] The existing mixed esterification process for preparing butyl zirconate and butyl hafnate is as follows: first, n-heptane and hafnium tetrachloride (or zirconium tetrachloride) powder are mixed in an ice bath, then an excess of n-butanol and triethylamine (which emits smoke in air and is toxic) are added, then the solution is subjected to oil bath to obtain a milky white suspension, the triethylamine hydrochloride generated during the reaction is removed by a filtration device, a light yellow clear solution is obtained, and finally butyl hafnate (or butyl zirconate) in the form of a light yellow viscous substance is obtained by distillation.

[0004] The above preparation method has the problems of relatively low production efficiency, difficulty in processing byproducts, and high production cost. In addition, the generation of triethylamine hydrochloride, which is an organic amine salt (belonging to hazardous waste), has a high processing cost. SUMMARY

[0005] Therefore, in order to solve the above problems and deficiencies, the present application provides a synthesis method of butyl zirconate and butyl hafnate, which comprises the following steps: S1, mixing and stirring, first put the solvent n-heptane into the reaction kettle, then put a certain amount of hafnium tetrachloride (or zirconium tetrachloride) solid into the reaction kettle, then put a certain amount of n-butanol into the reaction kettle, and finally stir; S2, organic synthesis, during the stirring process of S1, ammonia gas is introduced, the reaction temperature is set to be below 45℃, and the reaction pressure is normal pressure; S3, solid-liquid separation, the product after the reaction in S2 is subjected to solid-liquid separation by a centrifuge, the separated butyl hafnate (or butyl zirconate) liquid and solvent are reserved for use, and the separated solid ammonium chloride is used as a byproduct; S4, organic distillation, the liquid separated in S3 is subjected to distillation treatment, and the distillation temperature is controlled to be 125±5℃.

[0006] S5, spray filtering, the distillation waste gas in S4 is treated by acid spray through an acid mist absorption tower, and then is discharged after being passed into a secondary activated carbon adsorption.

[0007] S6, secondary distillation, after the organic matter left after the first distillation in S4 is filtered to remove ammonium chloride, secondary distillation is carried out, and the solvent is further evaporated to obtain butyl hafnate / butyl zirconate products.

[0008] Further, the ratio of hafnium tetrachloride, n-butanol, n-heptane and ammonia in S1 and S2 is 4.7:4.3:41:1; in the actual production process, 100KG of butyl hafnate is produced, and the material weight of hafnium tetrachloride, n-butanol, n-heptane and ammonia is 68, 63, 600 and 14.47KG respectively.

[0009] Further, the ratio of the separated solid and liquid in S3 is 1.45:1.

[0010] Further, the distillation in S4 and S6 is carried out in a reaction kettle.

[0011] Further, the organic matter in S6 is filtered by filter cloth.

[0012] The beneficial effects of the present application are: first, the butyl hafnate / butyl zirconate prepared by the present application has a greatly reduced product preparation cost compared with the existing process through organic synthesis+secondary distillation treatment; second, the generation of pollutants, especially triethylamine hydrochloride, is reduced during preparation, avoiding the generation of hazardous waste, only needing to be deacidified and ammonium chloride removed, which greatly reduces the cost compared with the existing process, and the environmental benefits are more obvious. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is the process flow chart of the present application; DETAILED DESCRIPTION

[0014] The present application will be described in detail below with reference to the accompanying drawings. The technical solutions in the embodiments of the present application are clearly and completely described, wherein the same or similar reference signs represent the same or similar elements or elements with the same or similar functions throughout the description; based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application; It should be understood that the ordinal numbers and the orientation descriptions, such as "first", "second", "third", "up", "down", "left", "right", etc., are only used for description purposes, and cannot be understood as indicating or implying relative importance. Meanwhile, in the description of the present application, unless otherwise explicitly specified and limited, the terms "connected", "connected" should be understood in a broad sense, and cannot be understood as a limitation of the present application.

[0015] The technical scheme of the present application will be further described in detail below in combination with the drawings and specific embodiments of the present application. Please refer to Figure 1 As shown in the drawings, the present application provides a synthesis method of butyl zirconate and butyl hafnate, which comprises the following steps: S1, mixing and stirring, first, the solvent n-heptane is put into a reaction kettle, then a certain amount of hafnium tetrachloride solid is put into the reaction kettle, then a certain amount of n-butanol is put into the reaction kettle, and finally stirring is carried out; S2, organic synthesis, ammonia gas is introduced during the stirring process of S1, the reaction temperature is set below 45℃, and the reaction pressure is normal pressure; the introduced ammonia gas reacts with hafnium tetrachloride to displace chlorine ions to form NH4Cl, and organic synthesis is carried out, wherein, according to the difference of hafnium / zirconium chloride, the chemical reaction equations of hafnium / zirconium chloride with n-butanol and ammonia gas are as follows: 4C4H 10 O+4NH3+HfCl4→C 16 H 36 HfO4+4NH4Cl; 4C4H 10 O+4NH3+ZrCl4→C 16 H 36 ZrO4+4NH4Cl.

[0016] S3, solid-liquid separation, the product after the reaction in S2 is subjected to solid-liquid separation by a centrifuge, the separated butyl hafnate liquid and solvent are reserved for use, and the separated solid ammonium chloride is used as a byproduct; S4, organic distillation, the liquid separated in S3 is subjected to distillation treatment, and the distillation temperature is controlled to be 125±5℃; S5, spray filtration, the distillation waste gas in S4 is subjected to acid spray treatment by an acid mist absorption tower, and then is discharged after being subjected to secondary activated carbon adsorption; S6, secondary distillation, the organic matter left after the first distillation in S4 is subjected to a second distillation after being filtered to remove ammonium chloride, and the solvent is further evaporated to obtain butyl hafnate / butyl zirconate finished products.

[0017] Through the two-stage distillation process, the butyl hafnate liquid and solvent reserved for use after the solid-liquid separation are put into a subsequent reaction kettle for distillation treatment, the distillation temperature reaches 125±5℃, the n-butanol and the solvent n-heptane are condensed and recycled, the distillation waste gas is discharged after being subjected to acid spray+secondary activated carbon adsorption, the organic matter left after the distillation is subjected to a second distillation after being filtered to remove ammonium chloride, and the solvent is further evaporated to obtain butyl hafnate / butyl zirconate finished products, and finally the liquid butyl hafnate / butyl zirconate finished products after the distillation are packed.

[0018] More specifically, the ratio of hafnium tetrachloride, n-butanol, n-heptane and ammonia in S1 and S2 is 4.7:4.3:41:1; in the actual production process, 100KG of butyl zirconate is produced, which requires the material weight of hafnium tetrachloride, n-butanol, n-heptane and ammonia to be 68, 63, 600 and 14.47KG respectively, and ammonia is stored in liquid state, which can be gasified at normal temperature and pressure.

[0019] More specifically, the solid-liquid ratio of the separated solid and liquid in S3 is 1.45:1, the solid phase is ammonium chloride, and the liquid phase is butyl zirconate solution.

[0020] More specifically, the distillation in S4 and S6 is carried out in a reaction kettle, the reaction kettle for secondary distillation is S6, and the organic matter is filtered by filter cloth.

[0021] In summary, the synthesis method of butyl zirconate and butyl hafnate of the present application, compared with the existing process, through organic synthesis + secondary distillation treatment, the product preparation cost is greatly reduced; secondly, in the preparation process, the generation of pollutants, especially triethylamine hydrochloride, is reduced, the generation of hazardous waste is avoided, only deacidification and removal of ammonium chloride treatment is needed, compared with the existing process, the cost is greatly reduced, and the environmental benefit is more obvious.

[0022] The above is only an embodiment of the present application, and the common knowledge of specific structures and properties in the scheme is not described in detail; it should be pointed out that for those skilled in the art, without departing from the structure of the present application, a number of modifications and improvements can be made, which should also be considered as the protection scope of the present application, which will not affect the effect and practicality of the patent; the protection scope claimed in the present application should be subject to the content of its claims, and the specific implementation mode and the like in the specification can be used to explain the content of the claims.

Claims

1. A method for the synthesis of butyl zirconate and butyl hafnate, characterized by: It comprises the following steps: S1, mixing and stirring, first put the solvent n-heptane into the reaction kettle, then put a certain amount of hafnium tetrachloride (or zirconium tetrachloride) solid into the reaction kettle, then put a certain amount of n-butanol into the reaction kettle, and finally stir; S2, organic synthesis, ammonia is introduced during the stirring process described in S1, the reaction temperature is set below 45℃, and the reaction pressure is normal pressure; S3, solid-liquid separation, the product after the reaction in S2 is subjected to solid-liquid separation by a centrifuge, the separated butyl hafnate (or butyl zirconate) liquid and solvent are reserved, and the separated solid ammonium chloride is used as a by-product; S4, organic distillation, the liquid separated in S3 is subjected to distillation treatment, and the distillation temperature is controlled at 125±5℃; S5, spray filtration, the distillation waste gas in S4 is subjected to acid spray treatment by an acid mist absorption tower, and then is introduced into secondary activated carbon adsorption and discharged; S6, secondary distillation, the organic matter left after the first distillation in S4 is subjected to a second distillation after removing ammonium chloride by filtration, and the solvent is further evaporated to obtain butyl hafnate / zirconate finished product.

2. The process for synthesis of butyl zirconate and butyl hafnate as claimed in claim 1 wherein: The ratio of hafnium tetrachloride, n-butanol, n-heptane and ammonia in S1 and S2 is 4.7:4.3:41:

1.

3. The process for synthesis of butyl zirconate and butyl hafnate as claimed in claim 1 wherein: The solid-liquid ratio after separation in S3 is 1.45:

1.

4. The process for synthesis of butyl zirconate and butyl hafnate as claimed in claim 1 wherein: The distillation in S4 and S6 is carried out in a reaction kettle.

5. The process for synthesis of butyl zirconate and butyl hafnate as claimed in claim 1 wherein: The organic matter in S6 is filtered by filter cloth.

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