CN106925071B - Hydrofluorination process tail gas processing method - Google Patents

Hydrofluorination process tail gas processing method Download PDF

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Publication number
CN106925071B
CN106925071B CN201511017468.2A CN201511017468A CN106925071B CN 106925071 B CN106925071 B CN 106925071B CN 201511017468 A CN201511017468 A CN 201511017468A CN 106925071 B CN106925071 B CN 106925071B
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tail gas
condenser
cooling water
temperature
process tail
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CN106925071A (en
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陈建勇
刘宾
魏刚
张慧忠
朱坤
向锡洪
周文涛
包国强
王俊
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404 Co Ltd China National Nuclear Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0003—Condensation of vapours; Recovering volatile solvents by condensation by using heat-exchange surfaces for indirect contact between gases or vapours and the cooling medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0051—Regulation processes; Control systems, e.g. valves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention belongs to natural uranium dioxide hydrofluorinations to generate green salt process tail gas processing technology field, and in particular to a kind of hydrofluorination process tail gas processing method.Lead to cooling water to cooling down in condenser, condenser is cut into production system after cooling, hydrofluorination process tail gas is condensed；Condenser liquid is sampled once per hour, hydrogen fluoride content in condensate liquid is analyzed, until being maintained between 5%-15%；If cooling water outlet temperature is greater than 35 DEG C, temperature is every to increase by 5 DEG C, adjusts cooling water flow and increases 5m3/ h, by 5 DEG C of processing when temperature rises less than 5 DEG C；The temporary storage tank exits and entrances valve above condenser is opened, hydrofluoric acid is received；Incoagulable gas acidity is analyzed, value should be less than 2%；Moment observes process tail gas changes in flow rate；The variation of temporary storage tank hydrofluoric acid liquid level is monitored, when reaching volume 70%, starts canned motor pump for hydrofluoric acid and is pumped into hydrofluoric acid storage tank, be recycled.The present invention can complete treatment system tail gas, effect on environment ignores.

Description

Hydrofluorination process tail gas processing method
Technical field
The invention belongs to natural uranium dioxide hydrofluorinations to generate green salt process tail gas processing technology field, and in particular to A kind of hydrofluorination process tail gas processing method.
Background technique
In natural green salt production process, process tail gas has larger harm to personal safety and ambient enviroment.Tetrafluoro Change in uranium production and handle hydrofluorination process tail gas, especially HF is an important technology in processing tail gas.
Currently, there are two main classes for the processing method of external hydrofluorination process tail gas: first is that directly use in lye and hydrogen fluoride, Multi-purpose lye KOH, NaOH solution, can also be using ammonium hydroxide, milk of lime etc..Second is that recycling hydrogen fluoride so that the hydrogen of various concentration is made Fluoric acid is used.Neutralisation is mainly used for the lower process tail gas processing of HF concentration, and majority carries out lye in eluting column and follows Ring pump completes neutralization reaction by entering at the top of eluting column, with the tail gas entered by tower bottom.As [F-] reach a certain concentration after, conveying To other process, wherein NaF, NH are recycled4F, the elements such as KF.Mainly using spray liquid is used water as, majority is fluorinated absorption method Hydrogen, water vapour eluted, cool down after enter in leacheate, after eluting liquid acidity and reaching certain value, carry out distillation processing；Or Acid solution is delivered to Calcified pond neutralisation treatment by person.However, according to HF-H2The relationship of O system boiling point and composition, upper azeotropic point temperature Degree is 112 DEG C, and corresponding gas phase fluorination hydrogen content is about 38%, therefore the hydrogen fluorine of high concentration can not be only produced by distillating method Acid.And double salt method is utilized (NaHF can be formed with hydrogen fluoride using NaF, KF etc.2、KHF2、KHF3, then decompose under certain condition Double salt recycles HF) it recycles, the method for the preparation high concentration of hydrofluoric acid precedent that worldwide engineering useless is applied.
Both the above method haves the defects that different degrees of.Neutralisation, which makees leacheate according to lye, can generate a large amount of leaching Washing lotion needs subsequent handling and is handled, can recovery section utility, but treatment process technology is complicated, operation It is complicated.The hydrofluoric acid concentration that absorption method is produced is only capable of reaching 38%, and needs to build a distillation production line, and operating process is more It is complicated；If generating a large amount of waste liquids without distillation and if being neutralized, after acid solution is delivered to Calcified pond neutralisation treatment, handle Efficiency is lower, can not be handled completely acid solution using the method according to investigation, to cause to lime pool environment, soil, underground water etc. Pollution.Also, low concentration hydrofluoric acid has extremely strong corrosivity, and in the presence of having oxygen, hydrofluoric acid corrosive nature is extremely strong, to setting Standby structural material and pipeline, valve require very high.
Optimal method is French " L.C " furnace hydrofluorination vent gas treatment processing technique, without the process tail gas of processing " L.C " furnace is directlyed adopt to recycle, specifically: UO is additionally arranged between reduction section and hydrofluorination section2Cooling section and excess HF Absorber portion, the high temperature UO that will be moved down from reduction section2200 DEG C are cooled to, is allowed to and the excess that is excluded from vertical hydrofluorination reaction area HF gas reaction, is converted into UF4.Root can make HF content in self tail gas be down to 0 according to data, using this method.However it should Method needs more stringent control condition, including biggish HF concentration etc..
Summary of the invention
The purpose of the present invention is to provide a kind of safe and efficient hydrofluorination process tail gas processing methods, can handle completely System tail gas, effect on environment are ignored.
In order to achieve the above objectives, the technical solution used in the present invention are as follows:
A kind of hydrofluorination process tail gas processing method, includes the following steps:
Step 1: logical cooling water in condenser to cooling down, and in temperature-fall period, control cooling water inlet temperature is 10-25 DEG C, Outlet temperature is 25-45 DEG C, temperature fall time 30min；Condenser is cut into production system after cooling, to hydrofluorination process tail gas It is condensed；
Step 2: being sampled once per hour condenser liquid, analyzes hydrogen fluoride content in condensate liquid, until being maintained at Between 5%-15%；
Step 3: if cooling water outlet temperature is lower than 35 DEG C, illustrate that cooling water flow control is suitable；If cooling water outlet temperature Degree is greater than 35 DEG C, and temperature is every to increase by 5 DEG C, adjusts cooling water flow and increases 5m3/ h, by 5 DEG C of processing when temperature rises less than 5 DEG C；
Step 4: opening the temporary storage tank exits and entrances valve above condenser, receives hydrofluoric acid；
Step 5: incoagulable gas acidity is analyzed, value should be less than 2%；If being higher than 2%, tied according to feedback Fruit adjusts condenser temperature, and acidity is higher than controlling value 1%, by 1% processing, cooling water flow when acidity is higher than controlling value less than 1% Amount increase accordingly 2m3/h；
Step 6: the moment observes process tail gas changes in flow rate, if exhaust flow variation is greater than 5%, cooling water flow increases Add 1m3/h；It is not adjusted when less than 5%；
Step 7: monitoring temporary storage tank hydrofluoric acid liquid level variation, when reaching volume 70%, hydrofluoric acid is pumped by starting canned motor pump Hydrofluoric acid storage tank, is recycled.
The condenser selects graphite as inner lining material, and surface uses carbon steel.
The condenser coolant is using upper water is produced, and coolant-temperature gage is 15 DEG C in production.
The condenser draw ratio is in (5~8): in 1 range, condenser absorbing reaction device internal diameter is 530mm, and length is 2860mm。
The condenser heat exchange area is 30m2。
It is obtained by the present invention to have the beneficial effect that
The present invention realizes the complete processing of hydrofluorination process tail gas.The lower about 10%-30% of the hydrofluoric acid acidity of condensation, It can be used as byproduct for treatment；It can also be re-used by the methods of distillation；Or it is thoroughly handled using neutralisation.This hair It is bright there is device structure to be simple and convenient to operate quick, control condition is easily achieved, safety coefficient is higher, good economy performance, while HF The advantages that recovery processing.It is specific as follows:
(1) system structure is simple.The sampling system mainly includes condenser, HF storage tank, canned motor pump and corresponding pipeline, valve Deng.(2) easy to operate.It under production conditions, only need to be by unlatching/closed state of control cooling water control valve, i.e., The achievable processing to hydrogen fluoride process tail gas.(3) control condition is easily achieved.Without complicated control system in treatment process System, wherein temperature controls, and can be carried out by adjusting cooling water flow；Pressure is normal pressure or tiny structure, in the condensate liquid unit time Limited flow, therefore pressure can be considered normal pressure in condenser.(4) safety coefficient is higher.Vent gas treatment process, to process control condition Without strict demand, process is simple, is not related to thinking to operate substantially.The strong oxidizing property from hydrofluoric acid is lost in the overwhelming majority, but The materials such as graphite, line with rubber, Fluorine-lined are used in selection, and there is high corrosion resistance.(5) good economy performance.It is only needed in the system Cooling water is cooled down (cooling water can be recycled), and without other raw material, (incoagulable gas is relied at exhaust Air Cleaning process Reason).Gained hydrofluoric acid can be used as accessory products sale, can also react neutralisation treatment with quick lime, thoroughly handle.(6) technique tail Gas disposal is complete.It is no other to need treated substance output in the process in addition to generating hydrofluoric acid.Incoagulable gas relies on air draft net Chemical industry sequence is handled, and most in incoagulable gas is nitrogen, air, contains only micro HF, is handled using acid mist eluting column.
Detailed description of the invention
Fig. 1 is hydrofluorination tail gas treatment process flow chart.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
As shown in Figure 1, hydrofluorination process tail gas processing method of the present invention includes the following steps:
Step 1: logical cooling water in condenser to cooling down, and in temperature-fall period, control cooling water inlet temperature is 10-25 DEG C, Outlet temperature is 25-45 DEG C, temperature fall time 30min；Condenser is cut into production system after cooling, to hydrofluorination process tail gas It is condensed；
Step 2: being sampled once per hour condenser liquid, analyzes hydrogen fluoride content in condensate liquid, Ying 5%-15% Between, if being more than limit value, need to carry out corresponding system call interception；
Step 3: if cooling water outlet temperature is lower than 35 DEG C, illustrate that cooling water flow control is suitable；If cooling water outlet temperature Degree is greater than 35 DEG C, and temperature is every to increase by 5 DEG C, adjusts cooling water flow and increases 5m3/ h, temperature rise less than 5 DEG C, handle by 5 DEG C；
Step 4: opening the temporary storage tank exits and entrances valve above condenser, receives hydrofluoric acid；
Step 5: incoagulable gas acidity is analyzed in notice air draft post, and value should be less than 2%, if being higher than 2%, Condenser temperature is then adjusted according to feedback result, acidity is higher than controlling value 1%, and acidity is higher than controlling value less than 1%, at 1% Reason, cooling water flow increase accordingly 2m3/h；
Step 6: the moment observes process tail gas changes in flow rate, if exhaust flow variation is greater than 5%, cooling water flow is answered Increase 1m3/ h, to adjust condenser temperature；It can not be adjusted when less than 5%；
Step 7: monitoring temporary storage tank hydrofluoric acid liquid level variation, when reaching volume 70%, hydrofluoric acid is pumped by starting canned motor pump Hydrofluoric acid storage tank, is recycled.
Condenser selects graphite as inner lining material, and equipment surface uses carbon steel.It is calculated and needs the heat exchange area to be about 24m2, it is contemplated that the uncertain design heat exchange area of production process is 30m2.Draw ratio is determined in (5~8): in 1 range.It is cold Condenser coolant considers that producing upper coolant-temperature gage is 15 DEG C, process tail gas temperature is 160 DEG C, per hour flow using upper water is produced For 3m3, heat exchange area 30m2, bonding apparatus design treatment ability and tail gas density are final to determine condenser absorbing reaction device internal diameter For 530mm, length 2860mm.Condenser cooling water and tail gas use counter current contacting, to guarantee condensation efficiency, condensation-water drain Temperature is analyzed by the specific heat of each component in the specific heat and tail gas of water, is calculated, the stream of condensed water not above 50 DEG C Amount is 3m3/h。
Contain H in hydrofluorination process tail gas2O、HF、N2、O2、NH4And trace meter uranium etc. F,.Wherein tenor is little, It is negligible.HF content is about 5% -15%, and HF boiling point is about 19.5 DEG C under normal temperature and pressure, soluble easily in water, any with water Than dissolving each other.Moisture content accounts for about 60% in tail gas, 100 DEG C of boiling point normal temperature and pressure, starts to condense lower than 100 DEG C, the lower temperature the more sharp It is condensed in moisture content.NH4It is white solid under F normal temperature and pressure, it is 98 DEG C of boiling point, soluble easily in water, and before entering exhaust pipe Processing is crossed, content is less in tail gas.Other gas harmless, without processing.The treatment process of hydrofluorination process tail gas is mainly adopted It is carried out with condensation recycling mode.Hydrofluorination production system process tail gas (removes most of through rubber lined pipe through sedimenting system NH4F condenser condensation) is sent into as water and then absorption HF produces hydrofluoric acid, and hydrofluoric acid enters HF storage tank, incoagulability by flow by gravity Gas is then sent into exhaust Air Cleaning system by pipeline above storage tank and is handled together with gas in workshop.

Claims (5)

1. a kind of hydrofluorination process tail gas processing method, characterized by the following steps:
Step 1: logical cooling water in condenser to cooling down, and in temperature-fall period, control cooling water inlet temperature is 10-25 DEG C, outlet Temperature is 25-45 DEG C, temperature fall time 30min；Condenser is cut into production system after cooling, hydrofluorination process tail gas is carried out Condensation；
Step 2: being sampled once per hour condenser liquid, analyzes hydrogen fluoride content in condensate liquid, until being maintained at 5%- Between 15%；
Step 3: if cooling water outlet temperature is lower than 35 DEG C, illustrate that cooling water flow control is suitable；If cooling water outlet temperature is big In 35 DEG C, temperature is every to increase by 5 DEG C, adjusts cooling water flow and increases 5m3/ h, by 5 DEG C of processing when temperature rises less than 5 DEG C；
Step 4: opening the temporary storage tank exits and entrances valve above condenser, receives hydrofluoric acid；
Step 5: incoagulable gas acidity is analyzed, value should be less than 2%；If being higher than 2%, according to feedback result tune Condenser temperature is saved, acidity is higher than controlling value 1%, by 1% processing, cooling water flow phase when acidity is higher than controlling value less than 1% 2m should be increased3/h；
Step 6: the moment observes process tail gas changes in flow rate, if exhaust flow variation is greater than 5%, cooling water flow increases 1m3/ h；It is not adjusted when less than 5%；
Step 7: monitoring temporary storage tank hydrofluoric acid liquid level variation when reaching volume 70%, starts canned motor pump for hydrofluoric acid and is pumped into hydrogen fluorine Acid storage tank is recycled.
2. hydrofluorination process tail gas processing method according to claim 1, it is characterised in that: the condenser selects stone Ink is used as inner lining material, and surface uses carbon steel.
3. hydrofluorination process tail gas processing method according to claim 1, it is characterised in that: the condenser coolant Using upper water is produced, coolant-temperature gage is 15 DEG C in production.
4. hydrofluorination process tail gas processing method according to claim 1, it is characterised in that: the condenser draw ratio In (5~8): in 1 range, condenser absorbing reaction device internal diameter is 530mm, and length is
2860mm。
5. hydrofluorination process tail gas processing method according to claim 1, it is characterised in that: the condenser heat-transfer surface Product is 30m2。
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CN109336213A (en) * 2018-09-27 2019-02-15 中核四0四有限公司 One kind being used for UO2The processing method of hydrofluorination tail gas condensing liquid
CN110559778A (en) * 2019-09-10 2019-12-13 内蒙古中科凯建科技有限公司 Dry-wet combined treatment system for roasting flue gas by rare earth concentrate concentrated sulfuric acid method
CN113154793B (en) * 2021-04-24 2023-03-10 昆明理工大学 Corrosive liquid cooling system

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