CN105819515A

CN105819515A - Preparation method of tungsten hexafluoride

Info

Publication number: CN105819515A
Application number: CN201610223777.3A
Authority: CN
Inventors: 王琪宇; 王新
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-04-05
Filing date: 2016-04-05
Publication date: 2016-08-03

Abstract

The invention relates to a preparation method of tungsten hexafluoride. The method comprises the steps of preparing a tungsten composition; feeding fluorine gas into a reactor filled with the tungsten composition to be subjected to reaction with the tungsten composition, so as to prepare a tungsten hexafluoride crude product under a specific molar ratio of tungsten to fluorine and proper reaction conditions; performing known extracting technology on tungsten hexafluoride gas, so as to obtain high-purity tungsten hexafluoride gas.

Description

A kind of preparation method of tungsten hexafluoride

Technical field

The present invention relates to the preparation method of a kind of fluoro-gas, the preparation method of a kind of tungsten hexafluoride.

Background technology

WF₆Being at room temperature a kind of colourless gas, its density is maximum in known gas.WF₆Relative molecular mass be 297.84, its molecule has the regular octahedron structure of symmetry at normal temperatures, and has diamagnetism.Current industrial main employing tungsten and fluorine gas or NF₃The method of direct reaction prepares WF₆, reaction is generally carried out under conditions of higher than 350 DEG C.For reducing the generation of by-product, tungsten should first carry out being dehydrated and deoxidation treatment before use.

CN102951684A discloses the preparation method of a kind of tungsten hexafluoride, relates to the fluoride of a kind of tungsten.Being passed through in electrolysis bath by fluohydric acid gas and carry out being electrolysed fluorine processed, the low-purity fluorine gas of generation is passed sequentially through purification column, the 1st deep cooling tank and the 2nd deep cooling tank and purifies, the fluorine gas after purification is passed through response system and reacts, and generates crude product tungsten hexafluoride；Fluorine gas after purifying is passed through the 1st horizontal type fixed bed reactor equipped with useless tungsten crop again and the 2nd horizontal type fixed bed reactor reacts, prepared tungsten hexafluoride passes sequentially through primary condenser, middle rank condenser and senior condenser are collected, thaw respectively and flow to the 1st storage tank, 2nd storage tank and the 3rd storage tank are collected, it is not condensed or unreacted foreign gas carries out alkali liquor absorption by afterbody discharge of pipes to eluting column, by the 1st storage tank, the crude product tungsten hexafluoride that 2nd storage tank and the 3rd storage tank are collected heats up, rectification and purification is carried out to rectifying column through filter distillation.Utilizing useless tungsten crop, technological operation safety, purity is higher.

CN101070189 discloses the preparation method of a kind of tungsten hexafluoride, by fluorine gas (F₂) and High Purity Nitrogen (N₂) be passed through in cracker in 1: 0.5～20 ratio mixing, preheating temperature is 10 DEG C～100 DEG C, pressure is 0～0.6MPA, time is 1MIN～20MIN, rear entrance reactor, has 5～15KG raw material tungsten (W) in reactor, in reactor, fluorine gas is 20 DEG C～400 DEG C with the reaction temperature of raw material tungsten, response time is 1MIN～20MIN, prepared tungsten hexafluoride (WF₆) gas by low-temperature collectors liquefaction collect, remove fluorine gas therein, nitrogen and Nitrogen trifluoride low boiling impurity by evacuation, in low-temperature collectors collect 10KG～50KG WF₆After gas, stop collecting and heating up WF₆Gas press-in steel cylinder preserves, and is connected by pipeline between described cracker, reactor and low-temperature collectors.

It is by making fluorine gas flow through the fluid bed containing tungsten or fixed bed completes that existing patent and technical literature are reacted.For promoting the good contact of Gas-solid phase, generally tungsten is processed into powder.After reaction terminates, collect WF in liquid form₆.Above-mentioned technique is fluorine gas and the problem such as tungsten powder is insufficient contact, reactor efficiency is low in practical operation.

Summary of the invention

The technical problem to be solved is to overcome the deficiencies in the prior art, it is provided that the preparation method of a kind of tungsten hexafluoride.

In order to solve above technical problem, present invention employs following technical scheme: the preparation method of a kind of tungsten hexafluoride, comprise the following steps:

Step (1): the preparation of tungsten compositions

By tungsten powder, account for the stearic acid that tungsten powder mass percentage content is 5～10, account for the acrylic resin that tungsten powder mass percentage content is 100-200, stirring 0.5-2h at 100-130 DEG C, extruding pelletization, at 50-80 DEG C, 20-60h is soaked in accounting for the acetone that tungsten powder mass percentage content is 5～10, by stearic acid dissolution, at 60-100 DEG C of dry 5-10h, obtain forming the granule with microcellular structure；Add and account for the amine propyl group-3-Methylimidazole. hexafluorophosphate that tungsten powder mass percentage content is 0.1～1, account for the hydrogen fluoride pyridine complex that tungsten powder mass percentage content is 5～15, react 5-10h at 25-60 DEG C, then through 100-200 DEG C of dry 5-10h.Obtain tungsten compositions.

Step (2): synthetic reaction

Fluorine gas enters and reacts equipped with in the reactor of this tungsten compositions, and fluorine gas is 3～5: 1 with the mol ratio of tungsten, and reaction temperature is 300～500 DEG C, air speed 1～5BV/h, prepares tungsten hexafluoride crude product.

Step (3): refined

Tungsten hexafluoride is through known purification technique, including rectification isolation technics, removes low-boiling-point substance, then removes high-boiling components, enter back into the adsorption tower equipped with adsorbent, temperature-40～-10 DEG C, flow velocity 1～5BV/h；High-purity tungsten hexafluoride is obtained after absorption.

Hydrogen fluoride pyridine complex described in step (1), HF content more than 70%, for commercially available prod, such as Guangzhou and the product that produces for Chemical Co., Ltd.；Described amine propyl group-3-Methylimidazole. hexafluorophosphate is commercially available prod, the product produced such as Chinese Academy of Sciences's Lanzhou Chemical Physics institute.Described tungsten powder, stearic acid, acrylic resin is commercially available prod.

Adsorbent described in step (3) includes X-type molecular sieve, A type molecular sieve, activated carbon, and adsorbent can be before use through pretreatment, such as acid treatment, and heat treatment and steam process.

Compared with prior art, the method have the advantages that

Through this patent tungsten compositions as graininess, there is microcellular structure, can be deposited in fixed bed, big with fluorine gas area, amine propyl group-3-Methylimidazole. hexafluorophosphate, the addition of hydrogen fluoride pyridine complex makes tungsten compositions and fluorine gas be more easy to reaction, and product can obtain electron level tungsten hexafluoride after refining further.

Detailed description of the invention

Below in conjunction with specific embodiment, it is further elucidated with the present invention, but these embodiments are only used for explaining the present invention rather than for limiting the scope of the present invention.

Tungsten powder is commercially available prod, and as above sea valley grinds the product that Science and Technology Ltd. produces, and fluorine gas is commercially available prod, such as the product of Zhengzhou Xing Dao Chemical Manufacture.

Embodiment 1

Step (1): the preparation of tungsten compositions

Add 100Kg tungsten powder in the reactor, 800Kg stearic acid, 150Kg acrylic resin, stirring 1.5h at 120 DEG C, extruding pelletization, under the conditions of 60 DEG C, tungsten powder after processing soaks 40h in the acetone of 800Kg, by stearic acid dissolution, under the conditions of 80 DEG C, it is dried 7h, obtains forming the granule with microcellular structure；Add the amine propyl group-3-Methylimidazole. hexafluorophosphate of 0.5Kg, the hydrogen fluoride pyridine complex of 1000Kg, under the conditions of 40 DEG C, react 7h, then at a temperature of 150 DEG C, be dried 8h.Obtain tungsten compositions.

Step (2): synthetic reaction

Being entered by fluorine gas and react equipped with in the reactor of this tungsten compositions, fluorine gas is 4: 1 with the mol ratio of tungsten, and reaction temperature is 400 DEG C, air speed 3BV/h, prepares tungsten hexafluoride crude product.

Step (3): refined

Tungsten hexafluoride is through known purification technique, including rectification isolation technics, removes low-boiling-point substance, then removes high-boiling components, enter back into the adsorption tower equipped with adsorbent, temperature-20 DEG C, flow velocity 3BV/h；High-purity tungsten hexafluoride is obtained after absorption.In product, the content of tungsten hexafluoride is shown in Table 1.

Embodiment 2

Step (1): the preparation of tungsten compositions

Add 100Kg tungsten powder in the reactor, 500Kg stearic acid, 100Kg acrylic resin, stirring 0.5h at 100 DEG C, extruding pelletization, under the conditions of 50 DEG C, tungsten powder after processing soaks 20h in the acetone of 500Kg, by stearic acid dissolution, under the conditions of 60 DEG C, it is dried 5h, obtains forming the granule with microcellular structure；Add the amine propyl group-3-Methylimidazole. hexafluorophosphate of 0.1Kg, the hydrogen fluoride pyridine complex of 500Kg, under the conditions of 25 DEG C, react 5h, then at a temperature of 100 DEG C, be dried 5h.Obtain tungsten compositions.

Step (2): synthetic reaction

Being entered by fluorine gas and react equipped with in the reactor of this tungsten compositions, fluorine gas is 3: 1 with the mol ratio of tungsten, and reaction temperature is 300 DEG C, air speed 1BV/h, prepares tungsten hexafluoride crude product.

Step (3): refined

Tungsten hexafluoride is through known purification technique, including rectification isolation technics, removes low-boiling-point substance, then removes high-boiling components, enter back into the adsorption tower equipped with adsorbent, temperature-40 DEG C, flow velocity 1BV/h；High-purity tungsten hexafluoride is obtained after absorption.In product, the content of tungsten hexafluoride is shown in Table 1.

Embodiment 3

Step (1): the preparation of tungsten compositions

Add 100Kg tungsten powder in the reactor, 1000Kg stearic acid, 200Kg acrylic resin, stirring 2h at 130 DEG C, extruding pelletization, under the conditions of 80 DEG C, tungsten powder after processing soaks 60h in the acetone of 1000Kg, by stearic acid dissolution, under the conditions of 100 DEG C, it is dried 10h, obtains forming the granule with microcellular structure；Add the amine propyl group-3-Methylimidazole. hexafluorophosphate of 1Kg, the hydrogen fluoride pyridine complex of 1500Kg, under the conditions of 25 DEG C, react 5h, then at a temperature of 200 DEG C, be dried 10h.Obtain tungsten compositions.

Step (2): synthetic reaction

Being entered by fluorine gas and react equipped with in the reactor of this tungsten compositions, fluorine gas is 5: 1 with the mol ratio of tungsten, and reaction temperature is 500 DEG C, air speed 5BV/h, prepares tungsten hexafluoride crude product.

Step (3): refined

Tungsten hexafluoride is through known purification technique, including rectification isolation technics, removes low-boiling-point substance, then removes high-boiling components, enter back into the adsorption tower equipped with adsorbent, temperature-10 DEG C, flow velocity 5BV/h；High-purity tungsten hexafluoride is obtained after absorption.In product, the content of tungsten hexafluoride is shown in Table 1.

Comparative example 1

Step (1) is added without amine propyl group-3-Methylimidazole. hexafluorophosphate, the other the same as in Example 1.In product, the content of tungsten hexafluoride is shown in Table 1.

Comparative example 2

Step (2) is added without hydrogen fluoride pyridine complex, the other the same as in Example 1.In product, the content of tungsten hexafluoride is shown in Table 1.

Comparative example 3

Step (1) is cancelled, and step (2) uses tungsten powder to replace tungsten compositions, the other the same as in Example 1.In product, the content of tungsten hexafluoride is shown in Table 1.

Table 1: in the product of embodiment 1-3 and comparative example 1-3, the content of tungsten hexafluoride is shown in Table 1.

Embodiment	Product purity volume fraction %
		1	99.999
2	99.999
		3	99.999
Comparative example 1	99.994
		Comparative example 2	99.991
Comparative example 3	99.922

These are only the specific embodiment of the present invention, but the technical characteristic of the present invention is not limited thereto.Any based on the present invention, for solving essentially identical technical problem, it is achieved essentially identical technique effect, done simple change, equivalent or modification etc., all it is covered by among protection scope of the present invention.

Claims

1. the preparation method of a tungsten hexafluoride, it is characterised in that comprise the following steps:

The preparation of step (1) tungsten compositions

By tungsten powder, account for the stearic acid that tungsten powder mass percentage content is 5～10, account for the acrylic resin that tungsten powder mass percentage content is 100-200, stirring 0.5-2h at 100-130 DEG C, extruding pelletization, at 50-80 DEG C, 20-60h is soaked in accounting for the acetone that tungsten powder mass percentage content is 5～10, by stearic acid dissolution, at 60-100 DEG C of dry 5-10h, obtain forming the granule with microcellular structure；Add and account for the amine propyl group-3-Methylimidazole. hexafluorophosphate that tungsten powder mass percentage content is 0.1～1, account for the hydrogen fluoride pyridine complex that tungsten powder mass percentage content is 5～15, react 5-10h at 25-60 DEG C, then through 100-200 DEG C of dry 5-10h, obtain tungsten compositions；

Step (2) synthetic reaction

Fluorine gas enters and reacts equipped with in the reactor of this tungsten compositions, and fluorine gas is 3～5: 1 with the mol ratio of tungsten, and reaction temperature is 300～500 DEG C, prepares tungsten hexafluoride crude product；

Step (3) refines

Tungsten hexafluoride is through known purification technique, including rectification isolation technics, removes low-boiling-point substance, then removes high-boiling components, enter back into the adsorption tower equipped with adsorbent, temperature-40～-10 DEG C, flow velocity 1～5BV/h, obtain high-purity tungsten hexafluoride after absorption.