CN108383085A - A kind of continuity method hydrochloric acid full stripping produces the device and method of hydrogen chloride gas - Google Patents

A kind of continuity method hydrochloric acid full stripping produces the device and method of hydrogen chloride gas Download PDF

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CN108383085A
CN108383085A CN201810462163.XA CN201810462163A CN108383085A CN 108383085 A CN108383085 A CN 108383085A CN 201810462163 A CN201810462163 A CN 201810462163A CN 108383085 A CN108383085 A CN 108383085A
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sulfuric acid
level
acid
hydrochloric acid
tower
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CN108383085B (en
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童新洋
仇晓丰
邱树锋
徐林波
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Hangzhou East Energy Saving Technology Co Ltd
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Hangzhou East Energy Saving Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/07Purification ; Separation
    • C01B7/0706Purification ; Separation of hydrogen chloride
    • C01B7/0731Purification ; Separation of hydrogen chloride by extraction
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

The present invention relates to the device and methods that a kind of continuity method hydrochloric acid full stripping produces hydrogen chloride gas, including resolution system and dilute sulfuric acid vacuum concentration system, resolution system includes resolving hydrochloric acid tower, level-one hydrogen chloride cooler, secondary chlorination hydrogen cooler, concentrated sulfuric acid drying tower, acid mist separator, and dilute sulfuric acid vacuum concentration system includes dilute sulfuric acid flash tank, the sour heat exchanger of acid, level-one sulphuric acid concentration slot, two level sulphuric acid concentration slot, first grade scrubber, level-one steam condenser, secondary scrubber, two level steam condenser, waste water tank, concentrated sulfuric acid medial launder.The present invention is extractant using the sulfuric acid of high concentration, makes full use of the heat of dilution of the concentrated sulfuric acid, while the concentrated sulfuric acid is continuously added to from resolving hydrochloric acid tower top, resolving hydrochloric acid overhead reflux ratio can be made to minimize, saved energy consumption to greatest extent;Using staged vacuum concentration technology, the waste heat of back segment acid is made full use of, heating steam consumption is saved to greatest extent, technical guarantee is provided for device long period continuous work.

Description

A kind of continuity method hydrochloric acid full stripping produces the device and method of hydrogen chloride gas
Technical field
The present invention relates to a kind of dilute hydrochloric acid complete solution analysis apparatus, and chlorination is produced more particularly, to a kind of continuity method hydrochloric acid full stripping The device and method of hydrogen.
Background technology
It is well known that HCl and H2There are higher boiling azeotrope, (i.e. its boiling point is higher than simple H to the dilute hydrochloric acid that O is formed2O And HCl), constant boiling point and azeotropic composition change with pressure.So to handle dilute hydrochloric acid makes HCl and H2O is separated, with simple Distillation or gas stripping process be not all right.Currently, the method for having industrialized the analysis of dilute hydrochloric acid complete solution has following two kinds:
1, Calcium Chloride Method
CaCl2Aqueous solution extraction breaks azeotropic and recycles HCl, i.e., the limit that calcium chloride breaks its azeotropic point is added in dilute hydrochloric acid System, comes out HCl separation.Its essence is saline extraction, combined by a saline extraction stripper and a water flash column and At can cause operation difficult containing sulfate radical or containing larger molecular organics in hydrochloric acid;It is steamed since Er Taita is required to heating Hair, so steam consumption is high, about 10.5 tons of left sides of HCl per ton (folding 100%) consumption steam are recycled in typical 20% dilute hydrochloric acid parsing It is right.
Calcium Chloride Method deeply parsing industrialized unit there is currently the problem of:
(1), due to high calcium chloride concentration aqueous solution the characteristics of, it is easy the fouling at reboiler hole wall, leads to its heat transfer efficiency Decline, acid content is exceeded in waste water;The chloride especially formed into system dilute hydrochloric acid band by metal ions such as iron, zinc, to chlorine Changing calcium solution has flocculation, can directly result in calcium chloride solution Crystallization Plugging equipment and pipeline;The tools such as silicon powder and micropowder There is thixotropic micro mist, there is thickening power, gradually cause calcium chloride solution in the gradual fouling of reboiler tube side, can cause to give up first Acid content is exceeded in water, eventually leads to reboiler cisco unity malfunction.So in actual industrialization operation, the use of reboiler Service life about at 1~2 year or so, needs overhaul to handle (returning factory's redrilling).
(2), hydrogen chloride content is high in waste water, and in order to extend the cycle of operation, chlor-alkali enterprises running gear uses reduction hydrochloric acid The technological measure of middle calcium chloride concentration, Calcium Chloride Method device discharge waste water in HCl concentration be much larger than normal process desired value 1%;HCl concentration actual value is 2~3% or so in waste water;Its main cause has two, when caused by Analytic Tower design defect, Mass and heat transfer is insufficient.Analytically (mostly using packed tower now) is analyzed on tower structure or tower diameter type selecting is excessive;Or filler It is improper to select;Or liquid distribution trough, redistributor design selection are improper.Second is that influence of the reboiler due to fouling, heat transfer effect Rate declines.
(3), block in order to prevent, Calcium Chloride Method resolving hydrochloric acid device needs the calcium chloride hydrochloric acid in regular exchange system molten Liquid prevents harmful ion from accumulating;Such as Tian Ye groups dilute hydrochloric acid Calcium Chloride Method depth resolver when first quarter exchange system in Calcium chloride is primary, and year replaces 4 times;Calcium chloride is primary in northern member 2 months exchange systems of chemical industry, and year replaces 6 times.
2, variable-pressure rectification method (or pressure differential method)
It is to form to change with pressure using azeotropic hydrochloric acid that variable-pressure rectification, which breaks azeotropic recycling HCl basic principles, relative to H2O And HCl, the characteristics of azeotropic hydrochloric acid is high boiling component always, make H to reach2The purpose of O and HCl separation.In absolute pressure When 33.33kPa, azeotropic composition is about 22%HCl, and constant boiling point temperature is 81.2 DEG C, and the boiling temperature of water is 70.8 DEG C;
When pressure is 0.20~0.30MPa (A), hydrochloric acid azeotropic composition mutually should be 19%~18.20%HCl.Dilute hydrochloric acid Rectification under vacuum is carried out into vacuum rectifying tower, tower top steams partial reflux after water condensation, remaining is as waste water discharge system;Tower Bottom is the barostat control after enrichment, and into pressing and desorption tower, tower top desorbs HCl, through B-grade condensation cooling except the acid mist of deentrainment Afterwards, it then obtains dry hydrogen chloride through the further dehydration of low temperature demisting and send user.
Transformation distills dilute hydrochloric acid analytic technique adaptability ratio CaCl2The broken azeotropic method of aqueous solution extraction is good, to most in hydrochloric acid Number impurity is insensitive, but cannot can lead to liquid foam like that containing the organic matter of macromolecular in acid, to destroy the biography of filler Matter.It is typical high energy consumption technique that azeotropic technique is broken in transformation distillation, and the parsing of 20% dilute hydrochloric acid recycles HCl per ton (folding 100%) and disappears Consume about 14 tons or so of steam.
Invention content
In order to overcome the shortcomings of the prior art, the present invention provides a kind of economic value higher, purposes is recycled more Extensive continuity method hydrochloric acid full stripping produces the device and method of hydrogen chloride gas.The present invention utilizes the sulfuric acid (83% of high concentration ~88%) it is extractant, the hydrogen chloride in continuous extraction hydrochloric acid is produced dry hydrogen chloride gas and recycled.
A kind of continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas, and described device includes interconnected parsing system System and dilute sulfuric acid vacuum concentration system, the resolution system includes resolving hydrochloric acid tower, level-one hydrogen chloride cooler, secondary chlorination hydrogen Cooler, concentrated sulfuric acid drying tower, acid mist separator, the dilute sulfuric acid vacuum concentration system include that dilute sulfuric acid flash tank, sour acid change Hot device, level-one sulphuric acid concentration slot, two level sulphuric acid concentration slot, first grade scrubber, level-one steam condenser, secondary scrubber, two Grade steam condenser, waste water tank, concentrated sulfuric acid medial launder, the resolving hydrochloric acid tower bottom and dilute sulfuric acid reboiler, dilute sulfuric acid Flash tank is connected, and resolving hydrochloric acid top of tower is connected with concentrated sulfuric acid medial launder;Resolving hydrochloric acid column overhead sequentially with level-one chlorination Hydrogen cooler, secondary chlorination hydrogen cooler, concentrated sulfuric acid drying tower, acid mist separator are connected, the level-one hydrogen chloride cooler, Secondary chlorination hydrogen cooler, which is divided into, not to be connected in the middle part of resolving hydrochloric acid tower;
The dilute sulfuric acid flash tank is connected by dilute sulphuric acid delivery pump with sour heat exchanger, the sour heat exchanger and one of acid Grade sulphuric acid concentration slot is connected, and the level-one sulphuric acid concentration slot is connected with two level sulphuric acid concentration slot, the two level sulphuric acid concentration Slot is connected with sour heat exchanger;The level-one sulphuric acid concentration slot is connected with first grade scrubber, the first grade scrubber and one Grade steam condenser is connected, and the two level sulphuric acid concentration slot is connected with secondary scrubber, the secondary scrubber and two Grade steam condenser be connected, the level-one steam condenser, two level steam condenser respectively with Water-ring vacuum pump machine Group is connected;The sour heat exchanger of acid is also connected with concentrated sulfuric acid medial launder.
Preferably, the level-one steam condenser, two level steam condenser are connected with waste water tank respectively, institute Waste water tank is stated by waste water delivery pump to be connected with the water treatment centers outside battery limit (BL).
Preferably, the concentrated sulfuric acid medial launder is connected by concentrated sulfuric acid reflux pump with resolving hydrochloric acid tower.
Preferably, the level-one sulfuric acid heater of level-one sulphuric acid concentration slot is connected with the first steam distribution platform, two level sulphur The two level sulfuric acid heater of sour thickener is connected with the second steam distribution platform.
Preferably, dilute sulfuric acid reboiler is connected with the first steam distribution platform, steam condensate (SC) slot respectively.
Preferably, the concentrated sulfuric acid drying tower bottom is connected by concentrated sulfuric acid circulating pump with concentrated sulfuric acid drying tower top It is logical.
Preferably, being respectively equipped with multiple enriched chambers, adjacent concentration in the level-one sulphuric acid concentration slot, two level sulphuric acid concentration Partition board is equipped between room.Multiple indoor acid solution explosive evaporations at a lower temperature of concentration, concentration improve step by step in thickener, respectively The partition board of grade enriched chamber prevents the reflux of acid solution, ensure that the maximum mean temperature difference between acid solution and heating tube, makes full use of The heating surface (area) (HS of tantalum pipe surface, ensure that treated, sulfuric acid reaches technological requirement.
A kind of method that continuity method hydrochloric acid full stripping produces hydrogen chloride gas, includes the following steps:
(1) it is sent into resolving hydrochloric acid tower after the dilute hydrochloric acid metering from storage tank, with 83%~88% under tower top spray Concentrated vitriol mixes, and concentrated vitriol is absorbed into the dilute sulfuric acid that the water after tower in dilute hydrochloric acid is diluted as 57%~62%, while quilt The heat of dilution heating of itself, under the collective effect that bottom of tower dilute sulfuric acid reboiler inputs heat, dilute sulfuric acid is heated to boiling-like State;Rise water vapour and tower gradually is stripped off in the hydrogen chloride in hydrochloric acid and sulfuric acid mixture liquid, sequentially enters the cooling of level-one hydrogen chloride Device and secondary chlorination hydrogen cooler sub-sectional cooling, sulfuric acid, water vapour in mixed chlorinated hydrogen are condensed and are back to resolving hydrochloric acid Tower;
(2) hydrogen chloride gas for going out secondary chlorination hydrogen cooler is cooled to 10~18 DEG C into concentrated sulfuric acid drying tower, gas Moisture dried and absorb by the concentrated sulfuric acid, go out the hydrogen chloride gas of drying tower after acid mist separator removes sulfuric acid mist, send out battery limit (BL) It is recycled after pressurizeing into hydrogen chloride compressor;
(3) dilute sulfuric acid of resolving hydrochloric acid tower bottom of tower is sent into adiabatic flash in dilute sulfuric acid flash tank by potential difference pressurization, metering, It flashes and the sour heat exchanger of acid is sent by dilute sulphuric acid delivery pump after concentrate, using going out two level dilute sulfuric acid thickener high temperature concentrated vitriol Waste heat preheats dilute sulfuric acid, and subsequently into level-one sulphuric acid concentration slot, dilute sulfuric acid is heated by level-one sulfuric acid heater in slot, sulfuric acid in slot It is gradually concentrated, the water vapour evaporated in the slot is introduced into first grade scrubber, and the water vapour come out with dilute sulfuric acid flash tank Enter level-one steam condenser together, the water vapour in tail gas is largely condensed, after fixed gas and the congregation of a small amount of water vapour Into water-ring vacuum pump assembly, the sour water condensed in tail gas is collected in waste water tank, and battery limit (BL) is pumped out to water by waste water conveying Processing center focuses on;
(4) the dilute sulfuric acid overflow for going out level-one sulphuric acid concentration slot enters two level sulphuric acid concentration slot, is steamed under higher vacuum degree It sends out, sulfuric acid is heated by two level sulfuric acid heater in slot, and sulfuric acid is finally concentrated into technique concentration 83%~88% in slot, concentrates sulphur Sour overflow goes out two level sulphuric acid concentration slot, is introduced into sour acid cooler and is cooled down by charging dilute sulfuric acid, subsequently into concentrated sulfuric acid medial launder, Water in resolving hydrochloric acid tower cycling extraction dilute hydrochloric acid is returned to by concentrated sulfuric acid reflux pump;
(5) water vapour that two level sulphuric acid concentration slot evaporates successively enters two-stage scrubber and two level steam condenser is cold But to technological temperature, tail gas after cooling enters water-ring vacuum pump assembly, and on-condensible gas is discharged through vacuum pump assembly;Steam condenses Water, condensation dilute sulfuric acid collect in waste water tank, by waste water conveying pump out battery limit (BL) to water treatment centers focus on.
Preferably, level-one sulfuric acid heater makees heat source using low-pressure saturated steam, two level sulfuric acid heater uses low pressure Saturated vapor makees heat source, and the steam condensate (SC) that level-one sulfuric acid heater and two level sulfuric acid heater are discharged is collected in steam condensate (SC) Slot recycles.It is used as power source with factory common 0.6~1.0Mpa (G) low-pressure saturated steam, effectively reduces the concentration of ton acid Cost.
Preferably, 83%~88% concentrated vitriol from the packing layer of resolving hydrochloric acid tower spray under, dilute salt from storage tank Acid is continuously added to from resolving hydrochloric acid tower middle and upper part.
The beneficial effects of the present invention are:
1, it is extractant using the sulfuric acid of high concentration (83%~88%), the hydrogen chloride in continuous extraction hydrochloric acid is produced dry Dry hydrogen chloride gas recycles;
2, it is extractant using the sulfuric acid of high concentration (83%~88%), makes full use of the heat of dilution of the concentrated sulfuric acid, while dense Sulfuric acid is continuously added to from resolving hydrochloric acid tower top, and resolving hydrochloric acid overhead reflux ratio can be made to minimize, saved to greatest extent in this way Energy consumption;Steam consumption is low, and 30% or more steam consumption is saved with Calcium Chloride Method complete solution analysis technics comparing;With variable-pressure rectification Complete solution analyses technics comparing and saves 50% or more steam consumption;
It 3, can be utmostly using staged vacuum concentration technology according to the difference of dilute sulfuric acid various concentration boiling temperature Reduce concentration technology to heat vapor (steam) temperature and process equipment material requirement;And make full use of the remaining of back segment high temperature gelled acid Heat saves heating steam consumption, technology is provided for vacuum concentration technique for dilute sulphuric acid device long period continuous work to greatest extent It ensures;
4, Technological adaptability is good, of less demanding to the impurity content in dilute hydrochloric acid;
5, the HCl contents in waste water are stably controlled≤0.3%, and cost for wastewater treatment is low.
Description of the drawings
Fig. 1 is the structural schematic diagram of resolution system of the present invention;
Fig. 2 is the structural schematic diagram of dilute sulfuric acid vacuum concentration system of the present invention.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments, but invention which is intended to be protected is simultaneously It is without being limited thereto.
Referring to Fig.1, Fig. 2, a kind of continuity method hydrochloric acid full stripping produce the device of hydrogen chloride gas, and described device includes parsing System and dilute sulfuric acid vacuum concentration system, the resolution system include resolving hydrochloric acid tower 1, level-one hydrogen chloride cooler 2, two level chlorine Change hydrogen cooler 3, concentrated sulfuric acid drying tower 4, acid mist separator 6, dilute sulfuric acid reboiler 7, the dilute sulfuric acid vacuum concentration system packet Include dilute sulfuric acid flash tank 8, the sour heat exchanger 10 of acid, level-one sulphuric acid concentration slot 11, two level sulphuric acid concentration slot 14, first grade scrubber 12, Level-one steam condenser 13, secondary scrubber 15, two level steam condenser 16, waste water tank 18, concentrated sulfuric acid medial launder 19, 1 bottom of resolving hydrochloric acid tower is connected with dilute sulfuric acid reboiler 7, and 1 top of resolving hydrochloric acid tower is connected with concentrated sulfuric acid medial launder 19 It is logical;1 tower top of resolving hydrochloric acid tower sequentially with level-one hydrogen chloride cooler 2, secondary chlorination hydrogen cooler 3, concentrated sulfuric acid drying tower 4, acid Mist separator 6 is connected, the level-one hydrogen chloride cooler 2, secondary chlorination hydrogen cooler 3 be divided into not in resolving hydrochloric acid tower 1 Portion is connected;
1 bottom of resolving hydrochloric acid tower is communicated with dilute sulfuric acid flash tank 8, and the dilute sulfuric acid flash tank 8 is changed with sour respectively Hot device 10 is connected with level-one steam condenser 13, and the acid acid heat exchanger 10 is connected with level-one sulphuric acid concentration slot 11, institute It states level-one sulphuric acid concentration slot 11 with two level sulphuric acid concentration slot 14 to be connected, the two level sulphuric acid concentration slot 14 and acid acid heat exchanger 10 It is connected;The level-one sulphuric acid concentration slot 11 is connected with first grade scrubber 12, the first grade scrubber 12 and level-one water vapour Condenser 13 is connected, and the two level sulphuric acid concentration slot 14 is connected with secondary scrubber 15, the secondary scrubber 15 and two Grade steam condenser 16 is connected, and the level-one steam condenser 13, two level steam condenser 16 are true with water ring respectively Empty pump assembly 27 is connected;The acid acid heat exchanger 10 is also connected with concentrated sulfuric acid medial launder 19.
The level-one steam condenser 13, two level steam condenser 16 are connected with waste water tank 18 respectively, described Waste water tank 18 is connected by waste water delivery pump 17 with the water treatment centers outside battery limit (BL).The concentrated sulfuric acid medial launder 19 is by dense Sulfuric acid reflux pump 20 is connected with resolving hydrochloric acid tower 1.The dilute sulfuric acid flash tank 8 is exchanged heat by dilute sulphuric acid delivery pump 9 and acid acid Device 10 is connected.
The level-one sulfuric acid heater of level-one sulphuric acid concentration slot is connected with the first steam distribution platform 23, two level sulphuric acid concentration slot Two level sulfuric acid heater and the second steam distribution platform 25 be connected;The level-one sulfuric acid heater, two level sulfuric acid heater point It is not connected with steam condensate (SC) slot 24.Dilute sulfuric acid reboiler 7 distributes platform 23,24 phase of steam condensate (SC) slot with the first steam respectively Connection.4 bottom of concentrated sulfuric acid drying tower is connected by concentrated sulfuric acid circulating pump 5 with 4 top of concentrated sulfuric acid drying tower, and the concentrated sulfuric acid is dry 4 top of dry tower is connected with 98% sulfuric acid supplemental tank 25.
Multiple enriched chambers are respectively equipped in the level-one sulphuric acid concentration slot, two level sulphuric acid concentration, are set between adjacent enriched chamber There is partition board 21.Multiple indoor acid solution explosive evaporations at a lower temperature of concentration, concentration improve step by step in thickener, concentrations at different levels The partition board of room prevents the reflux of acid solution, ensure that the maximum mean temperature difference between acid solution and heating tube, takes full advantage of tantalum pipe The heating surface (area) (HS on surface, ensure that treated, sulfuric acid reaches technological requirement.
Above-mentioned apparatus is used for the method that continuity method hydrochloric acid full stripping produces hydrogen chloride gas, includes the following steps:
(1) it is continuously added to resolving hydrochloric acid tower 1 from resolving hydrochloric acid tower middle and upper part after the dilute hydrochloric acid metering from storage tank 22, with 83%~88% concentrated vitriol lower from tower top packing layer spray mixes, and the water that concentrated vitriol is absorbed into after tower in dilute hydrochloric acid is dilute It is interpreted as 57%~62% dilute sulfuric acid, while being heated by the heat of dilution of itself, dilute sulfuric acid reboiler 7 inputs being total to for heat in bottom of tower Under same-action, dilute sulfuric acid is heated to fluidized state;Rise water vapour gradually the hydrogen chloride vapour in hydrochloric acid and sulfuric acid mixture liquid It proposes tower, sequentially enters level-one hydrogen chloride cooler and secondary chlorination hydrogen cooler sub-sectional cooling, the sulphur in mixed chlorinated hydrogen Acid, water vapour are condensed and are back to resolving hydrochloric acid tower;
(2) hydrogen chloride gas for going out secondary chlorination hydrogen cooler is cooled to 15 DEG C into concentrated sulfuric acid drying tower, the water of gas Divide to be dried by the concentrated sulfuric acid and absorb, goes out the hydrogen chloride gas of drying tower after acid mist separator removes sulfuric acid mist, send out battery limit (BL) entrance It is recycled after hydrogen chloride compressor pressurization;
(3) dilute sulfuric acid of resolving hydrochloric acid tower bottom of tower is sent into adiabatic flash in dilute sulfuric acid flash tank by potential difference pressurization, metering, It flashes and the sour heat exchanger of acid is sent by dilute sulphuric acid delivery pump after concentrate, using going out two level dilute sulfuric acid thickener high temperature concentrated vitriol Waste heat preheats dilute sulfuric acid, and subsequently into level-one sulphuric acid concentration slot, dilute sulfuric acid is heated by level-one sulfuric acid heater in slot, sulfuric acid in slot It is gradually concentrated, the water vapour evaporated in the slot is introduced into first grade scrubber, and the water vapour come out with dilute sulfuric acid flash tank Enter level-one steam condenser together, the water vapour in tail gas is largely condensed, after fixed gas and the congregation of a small amount of water vapour Into water-ring vacuum pump assembly, the sour water condensed in tail gas is collected in waste water tank, and battery limit (BL) is pumped out to water by waste water conveying Processing center focuses on;
(4) the dilute sulfuric acid overflow for going out level-one sulphuric acid concentration slot enters two level sulphuric acid concentration slot, is steamed under higher vacuum degree It sends out, sulfuric acid is heated by two level sulfuric acid heater in slot, and sulfuric acid is finally concentrated into technique concentration 83%~88% in slot, concentrates sulphur Sour overflow goes out two level sulphuric acid concentration slot, is introduced into sour acid cooler and is cooled down by charging dilute sulfuric acid, subsequently into concentrated sulfuric acid medial launder, Water in resolving hydrochloric acid tower cycling extraction dilute hydrochloric acid is returned to by concentrated sulfuric acid reflux pump;
(5) water vapour that two level sulphuric acid concentration slot evaporates successively enters two-stage scrubber and two level steam condenser is cold But to technological temperature, tail gas after cooling enters water-ring vacuum pump assembly, and on-condensible gas is discharged through vacuum pump assembly;Steam condenses Water, condensation dilute sulfuric acid collect in waste water tank, by waste water conveying pump out battery limit (BL) to water treatment centers focus on.
Level-one sulfuric acid heater makees heat source using low-pressure saturated steam, and two level sulfuric acid heater is made using low-pressure saturated steam The steam condensate (SC) of heat source, level-one sulfuric acid heater and the discharge of two level sulfuric acid heater is collected recycles profit in steam condensate (SC) slot With.It is used as power source with factory common 0.6~1.0Mpa (G) low-pressure saturated steam, effectively reduces the concentrated cost of ton acid;This hair Bright hydrochloric acid full stripping technological principle is:
Using the water imbibition of the concentrated sulfuric acid, azeotropic distillation is broken in dilute hydrochloric acid, tower top obtains hydrogen chloride gas, and bottom of tower obtains dilute Sulfuric acid.The concentrated sulfuric acid is continuously added to from resolving hydrochloric acid top of tower, and the dilute hydrochloric acid from storage tank continuously adds from resolving hydrochloric acid tower middle and upper part Enter, the concentrated sulfuric acid is mixed with hydrochloric acid in packing layer, and in the case where diluting concentrated sulfuric acid heat and tower reactor rise water vapour collective effect, mixing is molten Liquid azeotropic distillation in packing layer, hydrogen chloride and part water vapour in hydrochloric acid rise, mixed by hydrogen chloride when tower top packing layer The most of water vapor closed in gas is continuously absorbed into the concentrated sulfuric acid of tower, and the hydrogen chloride gas containing a small amount of water vapour escapes tower top, Into in hydrogen chloride gas cooler, anhydrous hydrogen chloride gas is cooled and is dried to obtain.
It has been diluted as dilute sulfuric acid when the concentrated sulfuric acid of moisture flow to resolving hydrochloric acid bottom of tower in absorption hydrochloric acid, has been arranged by bottom of tower Reboiler be heated to boiling with saturated vapor, the water vapour of rising in packing layer with the defluent sulfuric acid of gravity with Hydrochloric acid mixed solution conducts heat, and the hydrogen chloride in mixed liquor is stripped out liquid under the promotion of partial pressure difference;Extra dilute sulphur in tower reactor Sour automatic overflow goes out tower reactor, is concentrated into dilute sulfuric acid vacuum concentration system.
Its technological principle of vacuum concentration technique for dilute sulphuric acid is:
Utilize H in sulfuric acid solution under adiabatic flash and identical temperature2O and H2SO4Different vapour pressures, steams in sulfuric acid Water and improve the concentration of sulfuric acid;The process carries out under vacuum, is mainly manifested in and greatly reduces concentrated sulfuric acid solution Boiling point, meanwhile, it, in this way can be maximum using staged vacuum concentration technology according to the difference of dilute sulfuric acid various concentration boiling temperature Degree reduces requirement of the concentration technology to heating vapor (steam) temperature and process equipment material;And make full use of back segment high temperature gelled acid Waste heat, to greatest extent save heating steam consumption;It is provided for vacuum concentration technique for dilute sulphuric acid device long period continuous work Technical guarantee.
The present invention saves 30% or more steam consumption with Calcium Chloride Method complete solution analysis technics comparing, and work is analysed with variable-pressure rectification complete solution Skill, which compares, saves 50% or more steam consumption;The HCl contents in waste water are stably controlled≤0.3% simultaneously, wastewater treatment at This is low.

Claims (10)

1. a kind of continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas, it is characterised in that:Described device includes mutually interconnecting Logical resolution system and dilute sulfuric acid vacuum concentration system, the resolution system include resolving hydrochloric acid tower, level-one hydrogen chloride cooler, Secondary chlorination hydrogen cooler, concentrated sulfuric acid drying tower, acid mist separator, the dilute sulfuric acid vacuum concentration system include dilute sulfuric acid flash distillation The sour heat exchanger of slot, acid, level-one sulphuric acid concentration slot, two level sulphuric acid concentration slot, first grade scrubber, level-one steam condenser, two level Scrubbing tower, two level steam condenser, waste water tank, concentrated sulfuric acid medial launder, the resolving hydrochloric acid tower bottom boil again with dilute sulfuric acid Device, dilute sulfuric acid flash tank are connected, and resolving hydrochloric acid top of tower is connected with concentrated sulfuric acid medial launder;Resolving hydrochloric acid column overhead sequentially with Level-one hydrogen chloride cooler, secondary chlorination hydrogen cooler, concentrated sulfuric acid drying tower, acid mist separator are connected, the level-one chlorination Hydrogen cooler, secondary chlorination hydrogen cooler, which are divided into, not to be connected in the middle part of resolving hydrochloric acid tower;
The dilute sulfuric acid flash tank is connected by dilute sulphuric acid delivery pump with sour heat exchanger, the sour heat exchanger of acid and level-one sulphur Sour thickener is connected, and the level-one sulphuric acid concentration slot is connected with two level sulphuric acid concentration slot, the two level sulphuric acid concentration slot with Sour heat exchanger is connected;The level-one sulphuric acid concentration slot is connected with first grade scrubber, the first grade scrubber and level-one water Steam condenser is connected, and the two level sulphuric acid concentration slot is connected with secondary scrubber, the secondary scrubber and two level water Steam condenser is connected, the level-one steam condenser, two level steam condenser respectively with water-ring vacuum pump assembly phase Connection;The sour heat exchanger of acid is also connected with concentrated sulfuric acid medial launder.
2. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:Described one Grade steam condenser, two level steam condenser are connected with waste water tank respectively, and the waste water tank is conveyed by waste water Pump is connected with the water treatment centers outside battery limit (BL).
3. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:It is described dense Sulfuric acid medial launder is connected by concentrated sulfuric acid reflux pump with resolving hydrochloric acid tower.
4. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:Level-one sulphur The level-one sulfuric acid heater of sour thickener is connected with the first steam distribution platform, the two level sulfuric acid heater of two level sulphuric acid concentration slot It is connected with the second steam distribution platform;The level-one sulfuric acid heater, two level sulfuric acid heater respectively with steam condensate (SC) slot phase Connection.
5. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:Dilute sulfuric acid Reboiler is connected with the first steam distribution platform, steam condensate (SC) slot respectively.
6. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:It is described dense Sulfuric acid drying tower bottom is connected by concentrated sulfuric acid circulating pump with concentrated sulfuric acid drying tower top, concentrated sulfuric acid drying tower top and 98% Sulfuric acid supplemental tank is connected.
7. continuity method hydrochloric acid full stripping produces the device of hydrogen chloride gas according to claim 1, it is characterised in that:Described one It is respectively equipped with multiple enriched chambers in grade sulphuric acid concentration slot, two level sulphuric acid concentration, partition board is equipped between adjacent enriched chamber.
8. a kind of claim 1 described device is used for the method that continuity method hydrochloric acid full stripping produces hydrogen chloride gas, feature exists In including the following steps:
(1) it is sent into resolving hydrochloric acid tower after the dilute hydrochloric acid metering from storage tank, with 83%~88% concentration under tower top spray Sulfuric acid mixes, and concentrated vitriol is absorbed into the dilute sulfuric acid that the water after tower in dilute hydrochloric acid is diluted as 57%~62%, while by itself The heat of dilution heating, bottom of tower dilute sulfuric acid reboiler input heat collective effect under, dilute sulfuric acid is heated to fluidized state;On It rises water vapour and tower gradually is stripped off in the hydrogen chloride in hydrochloric acid and sulfuric acid mixture liquid, sequentially enter level-one hydrogen chloride cooler and two Grade hydrogen chloride cooler sub-sectional cooling, sulfuric acid, water vapour in mixed chlorinated hydrogen are condensed and are back to resolving hydrochloric acid tower;
(2) hydrogen chloride gas for going out secondary chlorination hydrogen cooler is cooled to 10~18 DEG C into concentrated sulfuric acid drying tower, the water of gas Divide to be dried by the concentrated sulfuric acid and absorb, goes out the hydrogen chloride gas of drying tower after acid mist separator removes sulfuric acid mist, send out battery limit (BL) entrance It is recycled after hydrogen chloride compressor pressurization;
(3) dilute sulfuric acid of resolving hydrochloric acid tower bottom of tower is sent into adiabatic flash in dilute sulfuric acid flash tank, flash distillation by potential difference pressurization, metering The sour heat exchanger of acid is sent by dilute sulphuric acid delivery pump after concentrate, utilizes the waste heat for two level dilute sulfuric acid thickener high temperature concentrated vitriol Preheat dilute sulfuric acid, subsequently into level-one sulphuric acid concentration slot, dilute sulfuric acid is heated by level-one sulfuric acid heater in slot, in slot sulfuric acid by by Step concentrates, and the water vapour evaporated in the slot is introduced into first grade scrubber, and together with the water vapour that dilute sulfuric acid flash tank comes out Into level-one steam condenser, the water vapour in tail gas is largely condensed, and enters after fixed gas and the congregation of a small amount of water vapour Water-ring vacuum pump assembly, the sour water condensed in tail gas are collected in waste water tank, and battery limit (BL) is pumped out to water process by waste water conveying Center focuses on;
(4) the dilute sulfuric acid overflow for going out level-one sulphuric acid concentration slot enters two level sulphuric acid concentration slot, is evaporated under higher vacuum degree, slot Interior sulfuric acid is heated by two level sulfuric acid heater, and sulfuric acid is finally concentrated into technique concentration 83%~88% in slot, and concentrated vitriol overflows Two level sulphuric acid concentration slot is flowed out, sour acid cooler is introduced into and is cooled down by charging dilute sulfuric acid, subsequently into concentrated sulfuric acid medial launder, by dense Sulfuric acid reflux pump returns to the water in resolving hydrochloric acid tower cycling extraction dilute hydrochloric acid;
(5) water vapour that two level sulphuric acid concentration slot evaporates successively enters two-stage scrubber and two level steam condenser is cooled to Technological temperature, tail gas after cooling enter water-ring vacuum pump assembly, and on-condensible gas is discharged through vacuum pump assembly;Steam condensate (SC), The dilute sulfuric acid of condensation is collected in waste water tank, and pumping out battery limit (BL) to water treatment centers by waste water conveying focuses on.
9. the method that continuity method hydrochloric acid full stripping produces hydrogen chloride gas according to claim 8, it is characterised in that:Level-one sulphur Sour heater makees heat source using low-pressure saturated steam, and two level sulfuric acid heater makees heat source using low-pressure saturated steam.
10. the method that continuity method hydrochloric acid full stripping produces hydrogen chloride gas according to claim 8, it is characterised in that:83% Under the packing layer of resolving hydrochloric acid tower spray, the dilute hydrochloric acid from storage tank connects~88% concentrated vitriol from resolving hydrochloric acid tower middle and upper part It is continuous to be added.
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