CN-122006631-A - Device for preparing hydrogen fluoride by molecular recognition complexation method and application thereof

CN122006631ACN 122006631 ACN122006631 ACN 122006631ACN-122006631-A

Abstract

The invention discloses a device for preparing hydrogen fluoride by a molecular identification complexation method and application thereof. The device comprises an integrated partition reactor, a dryer and a double-tower circulation type thermal decomposition system which are sequentially connected, wherein the integrated partition reactor comprises a complexation reaction-in-situ filtration area and a cross-linking reaction area, a spiral pushing type stirrer and a filter are sequentially arranged in the complexation reaction-in-situ filtration area from front to back, the filter is vertically arranged, the filtering surface of the filter is perpendicular to the material flow direction pushed by the spiral pushing type stirrer, a discharging baffle with adjustable switch state and switch degree is arranged at the bottom of the complexation reaction-in-situ filtration area, the other side of the discharging baffle is communicated with the top of the cross-linking reaction area, the vertical section of the cross-linking reaction area is of a trapezoid structure with wide upper part and narrow lower part, the dryer is connected with the bottom of the cross-linking reaction area, and the double-tower circulation type thermal decomposition system is used for fluidizing solid complex dried by the circulation type thermal decomposition dryer and discharging gas containing hydrogen fluoride.

Inventors

BAO ZONGBI
YANG XIUNA
SHEN FUXING
LI JINE
LI ZHENGTAO
REN QILONG

Assignees

浙江大学衢州研究院

Dates

Publication Date: 20260512
Application Date: 20251224

Claims (10)

1. The device for preparing the hydrogen fluoride by the molecular recognition complexation method is characterized by comprising an integrated partition reactor, a dryer and a double-tower circulation type thermal decomposition system which are connected in sequence; the integrated zoned reactor integrates the functions of complexation reaction, in-situ filtration and crosslinking reaction, and comprises a complexation reaction-in-situ filtration zone and a crosslinking reaction zone, wherein a spiral pushing stirrer and a filter are sequentially arranged in the complexation reaction-in-situ filtration zone from front to back; the dryer is connected with the bottom of the crosslinking reaction zone and is used for drying the solid complex crosslinked in the crosslinking reaction zone; the double tower loop thermal decomposition system is used to fluidize the solid complex dried by the loop thermal decomposition dryer and to discharge the hydrogen fluoride containing gas.
2. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 1, wherein the aspect ratio of the complexation reaction-in-situ filtration area is 1-15:1, preferably 3-8:1.
3. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 1, wherein the rotation speed of the spiral pushing type stirrer is 50-500 rpm, preferably 80-200 rpm.
4. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 1, wherein an included angle between two sides of the trapezoid structure and a vertical direction is 5 ° -80 °, preferably 15 ° -45 °.
5. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 1, wherein the double-tower circulation thermal decomposition system comprises a first circulation thermal decomposition tower and a second circulation thermal decomposition tower, an upper circulation channel, a middle circulation channel and a lower circulation channel are arranged between the first circulation thermal decomposition tower and the second circulation thermal decomposition tower, the material flow direction in the upper circulation channel is from the first circulation thermal decomposition tower to the second circulation thermal decomposition tower, the material flow direction in the middle circulation channel is from the first circulation thermal decomposition tower to the second circulation thermal decomposition tower or from the second circulation thermal decomposition tower to the first circulation thermal decomposition tower, and the material flow direction in the lower circulation channel is from the second circulation thermal decomposition tower to the first circulation thermal decomposition tower; the dryer is connected with the first circulating thermal decomposition tower, and the connection part is positioned between the middle circulating channel and the lower circulating channel; The top of the first circulating thermal decomposition tower and the top of the second circulating thermal decomposition tower are provided with gas outlets, a carrier gas inlet is arranged below the lower circulating channel, and a molecular identification complexing system discharge outlet is arranged below the carrier gas inlet; A gas-liquid separation member is disposed in the first and second circulating thermal decomposition towers between the gas discharge port and the upper circulating passage.
6. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 5, wherein the interface position of the upper circulation channel in the first circulation thermal decomposition tower is higher than that in the second circulation thermal decomposition tower, and the included angle between the upper circulation channel and the horizontal direction is 1-60 degrees, preferably 5-30 degrees; The middle circulation channel is horizontal; The interface position of the lower circulation channel at the first circulation thermal decomposition tower is lower than that of the lower circulation thermal decomposition tower, and the included angle between the lower circulation channel and the horizontal direction is 1-60 degrees, preferably 5-30 degrees.
7. The device for preparing hydrogen fluoride by a molecular recognition complexation method according to claim 5, wherein an outlet collector with steady flow and filtering functions is arranged at the front end of a discharge port of the molecular recognition complexation system; The discharge port of the molecular recognition complexing system is connected with the complexing reaction-in-situ filtering area.
8. The device for preparing hydrogen fluoride by the molecular recognition complexation method according to claim 1, wherein the device for preparing hydrogen fluoride by the molecular recognition complexation method further comprises a hydrogen fluoride separation tower and a hydrogen fluoride refining tower, wherein the double-tower circulation thermal decomposition system, the hydrogen fluoride separation tower and the hydrogen fluoride refining tower are connected in sequence; The device for preparing the hydrogen fluoride by the molecular recognition complexation method also comprises a fluosilicic acid raw material tank and solid-liquid separation equipment, wherein the fluosilicic acid raw material tank, the solid-liquid separation equipment and a complexation reaction-in-situ filtration area are connected in sequence, and a hydrogen fluoride separation tower is connected with the fluosilicic acid raw material tank.
9. The use of a device for preparing hydrogen fluoride by a molecular recognition complexation method according to any one of claims 1 to 8 for preparing hydrogen fluoride.
10. A method for preparing hydrogen fluoride by a molecular recognition complexation method, which is characterized in that the device for preparing hydrogen fluoride by the molecular recognition complexation method according to any one of claims 1 to 8 is adopted; the method for preparing the hydrogen fluoride by the molecular recognition complexation method comprises the following steps: The fluosilicic acid solution and the molecular recognition complexing system enter an integrated zoned reactor, the complexing reaction and the in-situ filtration are completed under the action of a spiral pushing type stirrer in a complexing reaction-in-situ filtration zone, filtrate is discharged through a filter, a primary complex generated by the complexing reaction is pushed to the rear side of the filter by the spiral pushing type stirrer, a discharging baffle is opened, and the primary complex enters a crosslinking reaction zone to carry out crosslinking reaction to obtain a complex with a stable network structure; the complex with stable network structure is dried by a dryer and then enters a double-tower circulation thermal decomposition system to be subjected to fluidization circulation thermal decomposition and discharge gas containing hydrogen fluoride.

Description

Device for preparing hydrogen fluoride by molecular recognition complexation method and application thereof Technical Field The invention relates to the technical field of chemical industry, in particular to a device for preparing hydrogen fluoride by a molecular identification complexation method and application thereof. Background Hydrogen fluoride is used as a basic raw material and is a basic stone in the fluoride industry, and is a key starting point for producing various fluorides, and supports the operation of the whole industrial chain. Along with the development of the fluorine chemical industry to refinement and large scale, the supply stability of anhydrous hydrogen fluoride is important to the healthy development of national strategic emerging industries such as new energy, new materials, semiconductors, medicines and the like. The fluorosilicic acid sulfuric acid decomposition method is an important process route for industrially preparing hydrogen fluoride, and is characterized in that the resource utilization of phosphate fertilizer industrial byproducts is realized, waste is changed into valuable, and the method is a typical circular economy route, but the process brings huge environmental protection pressure based on the generation of a large amount of dilute sulfuric acid, so that whether the problem of dilute sulfuric acid can be solved is the key of reasonable utilization of resources. The sulfuric acid decomposition method in the existing hydrogen fluoride preparation technology has the environmental protection problem that a large amount of dilute sulfuric acid can be generated, and researchers develop some alternative technologies. The following prior art is available after the search: The patent specification with publication number CN116835597A proposes a multistage extraction and concentration process of dilute fluosilicic acid, which adopts alcohol organic matters as extractant to extract and concentrate dilute fluosilicic acid, and adds polar or nonpolar organic matters as auxiliary agent into the extractant, and uses reduced pressure distillation method to recover the extractant. The extraction method has the problems of low extraction efficiency, large loss of extractant, complex process flow and the like. The patent specification with publication number CN113816340A proposes a method for preparing anhydrous hydrogen fluoride and co-producing silicon tetrafluoride by sodium fluosilicate, which is characterized in that sodium fluosilicate and hydrogen chloride gas are subjected to fluidized bed gas-solid reaction, and the obtained crude anhydrous hydrogen fluoride is refined to obtain pure anhydrous hydrogen fluoride. The patent specification with publication number CN106865500A discloses a cyclic production process for preparing hydrogen fluoride by fluosilicic acid, which is to mix fluosilicic acid and alkaline earth metal fluoride or alkali metal fluoride for reaction to obtain mixed solution of hydrogen fluoride and fluosilicate, further obtain hydrogen fluoride gas and fluosilicate solid, and then decompose the fluosilicate solid by heating to obtain fluoride solid and silicon tetrafluoride gas, wherein the silicon tetrafluoride gas is absorbed by fluosilicic acid solution. The patent specification with publication number CN117208912B proposes a process for purifying concentrated dilute fluosilicic acid solution by using a chemical extraction method, wherein organic alkali or modified organic alkali is used as an extractant, inorganic acid is used as a back extractant, dilute fluosilicic acid is concentrated by chemical extraction-chemical back extraction, and an auxiliary agent is recovered by a reduced pressure distillation method and the extractant is recovered by a reduced pressure heating decomposition method. The patent specification with the publication number of CN120646865A proposes a comprehensive utilization method of fluosilicic acid containing hydrogen fluoride, which comprises the following steps of 1) reacting stock solution containing fluosilicic acid with potassium fluoride raw material, obtaining potassium fluosilicate and hydrofluoric acid solution after solid-liquid separation, 2) reacting potassium fluosilicate with sodium hydroxide raw material, obtaining a mixture of potassium fluoride solution, sodium fluoride and silicon dioxide after solid-liquid separation, and returning the potassium fluoride solution to the step 1) to be used as the potassium fluoride raw material for recycling. The main problem of the process is that the gas-solid reaction temperature is high and the process energy consumption cost is high. However, the new process for preparing hydrogen fluoride, which is proposed in the prior art, is difficult to industrialize due to the problems of complex process flow, large amount of solid waste byproducts, low fluorine yield and the like, and under the background, a new process capable of replacing the existing sulfuric acid decomposition