CN108057330A - A kind of PTA oxidized tail gas purification and bromine retracting device and technique - Google Patents

A kind of PTA oxidized tail gas purification and bromine retracting device and technique Download PDF

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Publication number
CN108057330A
CN108057330A CN201711415474.2A CN201711415474A CN108057330A CN 108057330 A CN108057330 A CN 108057330A CN 201711415474 A CN201711415474 A CN 201711415474A CN 108057330 A CN108057330 A CN 108057330A
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tail gas
bromine
heat accumulating
accumulating type
oxidation reactor
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Inventor
施文博
江鸿宾
李付兰
马海
杨柳
徐美荣
赵旭东
姚艳艳
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Ningxia Highway Survey And Design Institute Co Ltd
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Ningxia Highway Survey And Design Institute Co Ltd
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/096—Bromine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/16—Halides of ammonium
    • C01C1/166—Ammonium bromide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/10—Bromides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2062—Bromine compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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Abstract

The embodiment of the present application shows a kind of PTA oxidized tail gas purification and bromine retracting device and technique, to the volatile organic matter catalysis oxidation in PTA oxidized tail gas in heat accumulating type catalyst oxidation reactor, and heat accumulating type catalyst oxidation reactor itself can realize the heat recovery of tail gas after reaction.Tail gas after reaction removes the HBr and Br in tail gas after expanding machine does work, into exhaust gas washing tower2, then the cleaning solution of adsorption saturation is transported in bromine recovery tower and carries out bromine recycling.A kind of purification of PTA oxidized tail gas and bromine retracting device and technique shown in the embodiment of the present application, operating cost is low, treatment effeciency is high, non-secondary pollution, and can realize the recycling of bromine in pollutant simultaneously.

Description

A kind of PTA oxidized tail gas purification and bromine retracting device and technique
Technical field
This application involves chemical industry tail gas Recovery Purifying technical fields more particularly to a kind of purification of PTA oxidized tail gas and bromine to return Receiving apparatus and technique.
Background technology
P-phthalic acid (Purified terephthalic acid, abbreviation PTA) is that petrochemical industry downstream is important One of large organic products, more than 90% PTA are used to produce polyethylene terephthalate (Polyethylene Terephthalate, abbreviation PET), and PET is then the important source material of chemical fibre industry.PTA mainly uses paraxylene (P- at present Xylene, abbreviation PX) air oxidation process production, typical production technology mainly includes PX oxidation units and crude terephthalic acid adds Hydrogen refined unit.Raw material PX is dissolved in Acetic Acid-Water solvent, and using cobalt acetate/manganese acetate/hydrogen bromide as catalyst, PX is through in air Dioxygen oxidation, be made crude terephthalic acid.Then hydrofining crude terephthalic acid, removal impurity, then crystallized, separation, It is dry, PTA finished products are made.
PTA oxidation gaseous effluents are the organic exhaust gas containing multiple pollutant discharged by oxidation reactor, are PTA device discharge capacitys Maximum pernicious gas.Gas main component N2Volume fraction account for 94%, O2Volume fraction be about 4%, organic matter is dirty Contaminating object includes acetic acid, methyl acetate, paraxylene, bromomethane etc., and total mass concentration is more than 1000mg/m3, wherein bromide Mass concentration about 100mg/m3, in addition, the mass concentration of CO about 5000mg/m3, serious is more than national discharge standard.
At present, a variety of PTA oxidized tail gas purification techniques, such as absorption method, condensation method, direct combustion method are had reported, this A little methods can generate that secondary pollution, energy consumption be big, clean-up effect is easily by organic exhaust gas concentration and temperature limiting, and for heat The mode that recycling link is combined usually using heat exchanger and catalytic oxidizing equipment, heat recovery rate are relatively low.PTA oxidations simultaneously are useless The bromos organic matter such as bromomethane in gas is after catalytic oxidation, and bromine mainly exists with hydrogen bromide and a small amount of bromine simple substance, so It is discharged afterwards by waste water formation, causes the significant wastage of bromine product.
The content of the invention
The embodiment of the present application provides a kind of purification of PTA oxidized tail gas and bromine retracting device and technique, the process operation into This low, non-secondary pollution, vent gas treatment is efficient and realizes the recycling of bromine.
The embodiment of the present application first aspect provides a kind of purification of PTA oxidized tail gas and bromine retracting device, including wind turbine, automatically Intake valve, heat accumulating type catalyst oxidation reactor, expanding machine, tail gas washing tower, bromine recovery tower and PTA tail gas intake valves；
The heat accumulating type catalyst oxidation reactor is provided with the import of heat accumulating type catalyst oxidation reactor and heat accumulating type catalysis oxygen Change reactor outlet；
The heat accumulating type catalyst oxidation reactor is provided with the first regenerative chamber, the second regenerative chamber, thermal oxidizer and automatic control Device processed；
The expanding machine is provided with expander inlet and expander outlet；
The bottom of towe side wall of the tail gas washing tower is provided with tail gas washing tower import, and the bottom of towe of the tail gas washing tower is set There is tail gas washing tower outlet, the tower top of the tail gas washing tower is exported equipped with cleaning of off-gas, the tower top side of the tail gas washing tower Wall is equipped with alkali liquor inlet；
The bromine recovery tower is provided with the import of bromine recovery tower and the outlet of bromine recovery tower；
The wind turbine is connected by the automatic admission valve with the heat accumulating type catalyst oxidation reactor import；
The PTA tail gas intake valve is connected with the heat accumulating type catalyst oxidation reactor import；
The heat accumulating type catalyst oxidation reactor outlet is connected with the expander inlet；
The expander outlet is connected with the tail gas washing tower import；
The tail gas washing tower outlet is connected with the bromine recovery tower import.
Optionally, the heat accumulating type catalyst oxidation reactor is double bed type heat heat accumulating type catalyst oxidation reactor.
Optionally, the catalyst in the heat accumulating type catalyst oxidation reactor uses ruthenium base honeycomb catalyst.
Optionally, the automaton of the heat accumulating type catalyst oxidation reactor uses PLC automatons.
Optionally, the quantity of the heat accumulating type catalyst oxidation reactor is two, and two heat accumulating type catalysis oxidations are anti- Device is answered to be arranged in parallel.
The embodiment of the present application second aspect, which provides a kind of PTA oxidized tail gas purification and bromine recovery process, the technique, to be included Following steps：
Step 1：Using fresh air auxiliary fuel effect under pre-heating heat accumulation type catalyst oxidation reactor (3)；
Step 2：After PTA oxidized tail gas is preheated into the first regenerative chamber, into thermal oxidizer catalyst effect Lower carry out catalytic oxidation；
Step 3：The substance obtained in the step 2 is transmitted to the second regenerative chamber and carries out heat recovery, heat accumulating type is urged Oxidation device (3) exports tail gas and does work by expanding machine (4)；
Step 4：The substance obtained in the step 3 is transmitted in exhaust gas washing tower (5) and utilizes lye absorption tail gas In HBr and Br2, the lye of adsorption saturation enters bromine recovery tower (6), obtains NaBr, NH4Br or Br2Bromine recycles product.
Optionally, the heat accumulating type catalyst oxidation reactor inlet temperature is 300-350 DEG C, and outlet temperature is 50-80 DEG C, Operating pressure is 0.8-1.2MPa.
Optionally, the inlet pressure of the expanding machine is 0.8-1.2MPa, outlet pressure 0.1MPa.
Optionally, the lye of the exhaust gas washing tower uses the sodium hydrate aqueous solution or ammonium hydroxide of 10-15%, exhaust gas washing Temperature is 45-60 DEG C in tower.
Optionally, the bromine recovery tower passes through concentration, Crystallization Procedure using the lye of exhaust gas washing tower adsorption saturation as raw material Obtain NaBr, NH4Br or by chlorine or hydrogen peroxide oxidation, is oxidized to bromine simple substance by bromide ion, then passes through extraction again Or sky blows bromine simple substance in method separation water.
The embodiment of the present application shows a kind of PTA oxidized tail gas purification and bromine retracting device and technique, and the embodiment of the present application will The volatile organic matter being harmful in PTA oxidized tail gas is converted into CO by catalytic oxidation2、H2O, the inorganic molecules such as HBr Object is closed, the process efficient, low energy consumption, processing procedure are generated without NOx.The heat accumulating type catalytic oxidation that the embodiment of the present application uses Device carries out heat recovery, and organic efficiency is high, while can realize the recycling of bromo element in PTA oxidized tail gas, obtains NaBr, NH4Br Or Br2Bromines product is waited, realizes the recycling of pollutant, with good economic efficiency, social benefit and environmental benefit.
Description of the drawings
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below Singly introduce, it should be apparent that, for those of ordinary skills, without having to pay creative labor, It can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is that a kind of PTA oxidized tail gas purification exemplified is preferably implemented in the application one and the structure of bromine retracting device is shown It is intended to.
In figure, 1- wind turbines；2- automatic admission valves；3- heat accumulating type catalyst oxidation reactors；4- expanding machines；5- washing tail gas Tower；6- bromine recovery towers；7-PTA tail gas intake valves；31- heat accumulating type catalyst oxidation reactor imports；32- heat accumulating type catalysis oxidations are anti- Device is answered to export；41- expander inlets；42- expander outlets；51- tail gas washing tower imports；52- tail gas washing towers export；53- Tail gas washing tower exports；54- alkali liquor inlets；61- bromine recovery tower imports；62- bromines recovery tower exports.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete Whole description, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work Embodiment belongs to the scope of protection of the invention.
Refering to Fig. 1, the embodiment of the present application first aspect shows a kind of PTA oxidized tail gas purification and bromine retracting device, including Wind turbine 1, automatic admission valve 2, heat accumulating type catalyst oxidation reactor 3 (English abbreviation RCO), expanding machine 4, tail gas washing tower 5, bromine return Receive tower 6 and PTA tail gas intake valve 7；
The heat accumulating type catalyst oxidation reactor 3 is provided with heat accumulating type catalyst oxidation reactor import 31 and heat accumulating type catalysis Oxidation reactor outlet 32；
The heat accumulating type catalyst oxidation reactor 3 is provided with the first regenerative chamber, the second regenerative chamber, thermal oxidizer and automatic control Device processed；
The expanding machine 4 is provided with expander inlet 41 and expander outlet 42；
The bottom of towe side wall of the tail gas washing tower 5 is provided with tail gas washing tower import 51, the bottom of towe of the tail gas washing tower 5 Tail gas washing tower outlet 52 is provided with, the tower top of the tail gas washing tower 5 is equipped with cleaning of off-gas and exports 53, the tail gas washing tower 5 tower top side wall is equipped with alkali liquor inlet 54；
The bromine recovery tower 6 is provided with bromine recovery tower import 61 and bromine recovery tower outlet 62；
The wind turbine 1 is connected by the automatic admission valve 2 with the heat accumulating type catalyst oxidation reactor import 31；
The PTA tail gas intake valve 7 is connected with the heat accumulating type catalyst oxidation reactor import 31；
The heat accumulating type catalyst oxidation reactor outlet 32 is connected with the expander inlet 41；
The expander outlet 42 is connected with the tail gas washing tower import 51；
The tail gas washing tower outlet 52 is connected with the bromine recovery tower import 61.
The concrete operating principle of the present apparatus is：Fresh air conveying is catalyzed by wind turbine 1 by automatic admission valve 2 into heat accumulating type Oxidation reactor 3, convey into fresh air auxiliary fuel effect under heat accumulating type catalyst oxidation reactor 3 is preheated, Automaton in subsequent heat accumulating type catalyst oxidation reactor 3 automatically switches valve and is passed through low temperature PTA oxidized tail gas, wherein PTA tail gas intake valve 7 can control PTA oxidized tail gas inlets, and PTA oxidized tail gas passes through in heat accumulating type catalyst oxidation reactor 3 The first regenerative chamber preheated, subsequently into the thermal oxidizer in heat accumulating type catalyst oxidation reactor 3 catalyst effect Lower carry out catalytic oxidation, the high-temperature gas after reaction enter the second regenerative chamber, heat in heat accumulating type catalyst oxidation reactor 3 It is absorbed by the second regenerative chamber, heat accumulating type catalyst oxidation reactor 3 is thereafter let out, wherein the second regenerative chamber temperature after heat is absorbed Rise, and automatically switch valve using automaton, air inlet flow direction is made to take a turn for the worse, the pending PTA oxidations tail of low temperature Gas is preheated into the second regenerative chamber, and the second accumulation of heat room temperature reduces, and is prepared for heat absorption next time.Tail gas after catalysis oxidation It does work into expanding machine 4, subsequently enters exhaust gas washing tower 5, wherein lye is injected to exhaust gas washing tower 5 by alkali liquor inlet 54, Hydrogen bromide, the bromine in tail gas, the cleaning solution circulation absorption in exhaust gas washing tower 5, the cleaning solution of adsorption saturation are removed by alkali cleaning It finally enters bromine recovery tower 6, carries out bromine recycling, NaBr, NH are obtained by the processes such as concentrating, crystallizing4Br or using chlorine or Bromide ion is oxidized to bromine simple substance by hydrogen peroxide oxidation, and then blowing method by extraction or sky again separates bromine simple substance in water.
Wherein, the volatile organic matter being harmful in PTA oxidized tail gas can be passed through catalysis by heat accumulating type catalyst oxidation reactor 3 Oxidation reaction is converted into CO2、H2O, the inorganic molecules compound such as HBr, the process efficient, low energy consumption, processing procedure are given birth to without NOx Into.
Heat accumulating type catalyst oxidation reactor 3 is provided with the first regenerative chamber, the second regenerative chamber, thermal oxidizer and automatically controls dress It puts, wherein automaton can control the automatic switchover of valve, converts the flow direction of PTA oxidized tail gas, makes PTA oxidized tail gas Flow direction is mutually converted between the first regenerative chamber and the second regenerative chamber, by using map function is flowed to, realizes untreated flue gas Heating and handle flue gas heat recovery.
Optionally, the heat accumulating type catalyst oxidation reactor 3 is double bed type heat heat accumulating type catalyst oxidation reactor.
Optionally, the catalyst in the heat accumulating type catalyst oxidation reactor 3 uses ruthenium base honeycomb catalyst.
Existing PTA oxidation waste catalyst include using precious metals pt, Pd as active component catalyst.But Pt, Pd Noble metal catalyst is at high price, is vulnerable to catalyst poisoning caused by bromo element, and activity reduces, while easily generates toxicity more Strong high bromo by-product.The ruthenium base honeycomb catalyst selected in the embodiment of the present application, not only compared with precious metals pt, the valency of Pd Lattice are relatively low, and with good anti-halogen, higher stability and activity.
Optionally, the automaton of the heat accumulating type catalyst oxidation reactor 3 uses PLC automatons.It is logical PLC automatons are crossed, automatically control the flow direction conversion for being passed through PTA oxidized tail gas.
Optionally, the quantity of the heat accumulating type catalyst oxidation reactor 3 is two, and two heat accumulating type catalysis oxidations are anti- Device 3 is answered to be arranged in parallel.
Two heat accumulating type catalyst oxidation reactors 3 are arranged in parallel, when one of heat accumulating type catalyst oxidation reactor 3 During failure, the automaton of heat accumulating type catalyst oxidation reactor 3 automatically switches valve, enters PTA oxidized tail gas another A heat accumulating type catalyst oxidation reactor 3 carries out catalytic oxidation treatment, it is ensured that device normal operation, the disastershutdown of avoiding device.
Shown in the embodiment of the present application a kind of PTA oxidized tail gas purification and bromine retracting device include wind turbine, automatic admission valve, Heat accumulating type catalyst oxidation reactor, expanding machine, tail gas washing tower, bromine recovery tower and PTA tail intake valves；Wherein PTA oxidized tail gas Preheated by the first regenerative chamber in heat accumulating type catalyst oxidation reactor, subsequently into thermal oxidizer catalyst effect Lower carry out catalytic oxidation, by harmful volatile organic matter, that CO is converted into carbon dioxide, water, hydrogen bromide, bromine etc. is inorganic small Molecular compound subsequently enters the second regenerative chamber and recovers energy, wherein the second regenerative chamber temperature after heat is absorbed raises, and Air inlet flow direction takes a turn for the worse, and the pending PTA oxidized tail gas of low temperature is preheated into the second regenerative chamber, the second accumulation of heat room temperature drop It is low, it prepares for heat absorption next time.Tail gas after catalysis oxidation does work subsequently into expanding machine, subsequently enters exhaust gas washing tower, leads to Alkali cleaning removing hydrogen bromide therein, bromine are crossed, the cleaning solution of adsorption saturation finally enters bromine recovery tower, will using chlorine or hydrogen peroxide Bromide ion is oxidized to bromine simple substance, and then blowing method by extraction or sky again separates bromine progress bromine recycling in water.The application is implemented The heat accumulating type catalyst oxidation reactor that example uses carries out heat recovery, and organic efficiency is high, while can realize bromine in PTA oxidized tail gas The recycling of element, obtains NaBr, NH4Br or Br2Bromines product is waited, realizes the recycling of pollutant, there is good economic effect Benefit, social benefit and environmental benefit.
The embodiment of the present application second aspect shows that a kind of PTA oxidized tail gas purification and bromine recovery process, the technique include Following steps：
Step 1：Using fresh air auxiliary fuel effect under pre-heating heat accumulation type catalyst oxidation reactor (3)；
Step 2：After PTA oxidized tail gas is preheated into the first regenerative chamber, into thermal oxidizer catalyst effect Lower carry out catalytic oxidation.Preheating can improve heat utilization ratio, the thermal loss of PTA oxidized tail gas be reduced, compared with biography On the other hand catalytic oxidizing equipment and the heat exchanger combination of system, heat recovery efficiency higher can reduce gas and reach initiation temperature Time.
Step 3：The substance obtained in the step 2 is transmitted to the second regenerative chamber and carries out heat recovery, heat accumulating type is urged Oxidation device (3) exports tail gas and does work by expanding machine (4)；
Step 4：The substance obtained in the step 3 is transmitted in exhaust gas washing tower (5) and utilizes lye absorption tail gas In HBr and Br2, the lye of adsorption saturation enters bromine recovery tower (6), obtains NaBr, NH4Br or Br2Bromine recycles product.
Mainly contain N in purified gas after alkali cleaning2、CO2And H2O, pollution components are thoroughly removed.
The chemical reaction mainly occurred in heat accumulating type catalytic reactor 3 is as follows：
2CO+O2=2CO2；
2CH3COOCH3+7O2=6CO2+6H2O；
2C8H10+21O2=16CO2+10H2O；
CH3COOH+2O2=2CO2+2H2O；
2CH3OH+3O2=2CO2+4H2O；
2CH3Br+3O2=2CO2+2H2O+2HBr；
4CH3Br+7O2=2CO2+2H2O+2Br2。
Optionally, double bed type heat heat accumulating type catalyst oxidation reactor can be used in heat accumulating type catalyst oxidation reactor 3.
Optionally, the quantity of the heat accumulating type catalyst oxidation reactor 3 is two, and two heat accumulating type catalysis oxidations are anti- Device 3 is answered to be arranged in parallel.Two heat accumulating type catalyst oxidation reactors 3 are arranged in parallel, when one of heat accumulating type catalysis oxidation During 3 failure of reactor, the automaton of heat accumulating type catalyst oxidation reactor 3 automatically switches valve, make PTA oxidized tail gas into Enter another heat accumulating type catalyst oxidation reactor 3 and carry out catalytic oxidation treatment, it is ensured that device normal operation, avoiding device accident are stopped Vehicle.
Optionally, 3 inlet temperature of heat accumulating type catalyst oxidation reactor is 300-350 DEG C, outlet temperature 50-80 DEG C, operating pressure 0.8-1.2MPa.
Optionally, the inlet pressure of the expanding machine 4 is 0.8-1.2MPa, outlet pressure 0.1MPa.
Optionally, the lye of the exhaust gas washing tower 5 uses the sodium hydrate aqueous solution or ammonium hydroxide of 10-15%, and exhaust gas is washed It is 45-60 DEG C to wash temperature in tower.Lye of the mass fraction for 10-15% is used, it, should while with good alkali cleaning effect The corrosivity of the lye of concentration is poor, it is possible to reduce the corrosion to exhaust gas washing tower 5.5 inside of exhaust gas washing tower is equipped with filler, it Mass transfer surfaces are provided for vapor-liquid two phases contact in tower, which has larger specific surface area and good wetability, also has Compared with high voidage, gas-flow resistance is small, corrosion-resistant, mechanical strength is big the advantages that.There is demisting silk screen on 5 top of exhaust gas washing tower and fills out Material, to remove most of moisture.
Exemplified by using sodium hydroxide solution as cleaning solution, following chemical reaction mainly has occurred in alkaline cleaning procedure：
HBr+NaOH=NaBr+H2O；
Br2+ 2NaOH=NaBr+NaBrO+H2O。
By taking ammonium hydroxide is cleaning solution as an example, following chemical reaction mainly has occurred in alkaline cleaning procedure：
HBr+NH3H2O=NH4Br+H2O；
3Br2+8NH3H2O=6NH4Br+8H2O+4N2。
Optionally, the bromine recovery tower 6 is using the lye of 5 adsorption saturation of exhaust gas washing tower as raw material, by concentrating, crystallizing work Sequence obtains NaBr, NH4Br or by chlorine or hydrogen peroxide oxidation, is oxidized to bromine simple substance by bromide ion, then passes through extraction again Method or sky blow bromine simple substance in method separation water.
Optionally, it is necessary to which the lye of saturation is added in hydrochloric acid adjusts Ph values to 2 before hydrogen peroxide oxidation of being lived by chlorine.
Wherein, sky blows method using acetic acid or paraxylene adsorption solvent the most.
Bromine simple substance can also be collected by paraxylene extraction, and the paraxylene solution of bromine is recycled to PTA productions Device is used to prepare terephthalic acid (TPA), realizes the recycling of bromine.
The specific embodiment of the present invention is illustrated with reference to example.
Embodiment 1：
Go into operation warm-up phase, and fresh air is passed through under the action of auxiliary fuel to heat accumulating type catalysis oxidation using wind turbine 1 Reactor 3 is preheated, and the first regenerative chamber that subsequent PTA oxidized tail gas enters heat accumulating type catalyst oxidation reactor 3 is preheated It to 350 DEG C, is reacted into thermal oxidizer, catalyst uses ruthenium base honeycomb catalyst, with volatile organic matter catalysis oxidation, releases Thermal discharge raises exhaust temperature, and subsequent tail gas carries out heat recovery into the second regenerative chamber, and the heat accumulating type catalysis oxidation is anti- The outlet temperature of device 3 is answered as 80 DEG C, operating pressure is 1.2MPa in reactor.Treated carries out after tail gas enters expanding machine 4 Acting, inlet pressure 1.2MPa, outlet pressure 0.1MPa.Subsequent tail gas enters exhaust gas washing tower 5, with 10% hydroxide Sodium water solution washing removes HBr and Br2, temperature is 60 DEG C in exhaust gas washing tower.Enter bromine recovery tower after cleaning solution adsorption saturation 6, concentration adds in hydrochloric acid and adjusts Ph values to 2, then adds in hydrogen peroxide, bromide ion in solution is oxidized to bromine simple substance, is blown by sky Method collects bromine simple substance.
Embodiment 2：
Go into operation warm-up phase, and fresh air is passed through under the action of auxiliary fuel to heat accumulating type catalysis oxidation using wind turbine 1 Reactor 3 is preheated, and the first regenerative chamber that subsequent PTA oxidized tail gas enters heat accumulating type catalyst oxidation reactor 3 is preheated It to 300 DEG C, is reacted into thermal oxidizer, catalyst uses ruthenium base honeycomb catalyst, with volatile organic matter catalysis oxidation, releases Thermal discharge raises flue-gas temperature, and subsequent tail gas flue gas carries out heat recovery into the second regenerative chamber, and the heat accumulating type is catalyzed oxygen Change the outlet temperature of reactor 3 as 50 DEG C, operating pressure is 0.8MPa in reactor.Treated after tail gas enters expanding machine 4 It does work, inlet pressure 0.8MPa, outlet pressure 0.1MPa.Subsequent tail gas enters exhaust gas washing tower 5, with 10% it is dilute Ammonia scrubbing removes HBr and Br2, temperature is 45 DEG C in exhaust gas washing tower.It is dense into bromine recovery tower 6 after cleaning solution adsorption saturation Contracting, crystallization, obtain NH4Br。
Embodiment 3：
Go into operation warm-up phase, and fresh air is passed through under the action of auxiliary fuel to heat accumulating type catalysis oxidation using wind turbine 1 Reactor 3 is preheated, and the first regenerative chamber that subsequent PTA oxidized tail gas enters heat accumulating type catalyst oxidation reactor 3 is preheated It to 325 DEG C, is reacted into thermal oxidizer, catalyst uses ruthenium base honeycomb catalyst, with volatile organic matter catalysis oxidation, releases Thermal discharge raises flue-gas temperature, and subsequent tail gas flue gas carries out heat recovery into the second regenerative chamber, and the heat accumulating type is catalyzed oxygen Change the outlet temperature of reactor 3 as 60 DEG C, operating pressure is 0.8MPa in reactor.Treated after tail gas enters expanding machine 4 It does work, inlet pressure 1.0MPa, outlet pressure 0.1MPa.Subsequent tail gas enters exhaust gas washing tower 5, with 15% hydrogen Aqueous solution of sodium oxide washing removes HBr and Br2, temperature is 50 DEG C in exhaust gas washing tower.It is returned after cleaning solution adsorption saturation into bromine Tower 6 is received, concentration adds in hydrochloric acid and adjusts Ph values to 2, then adds in hydrogen peroxide, bromide ion in solution is oxidized to bromine simple substance, is passed through Paraxylene extraction collects bromine simple substance, and the paraxylene solution of bromine is recycled to PTA process units, is used to prepare to benzene two Formic acid realizes the recycling of bromine.
The embodiment of the present application shows a kind of PTA oxidized tail gas purification and bromine retracting device and technique, and the embodiment of the present application will The volatile organic matter being harmful in PTA oxidized tail gas is converted into CO by catalytic oxidation2、H2O, the inorganic molecules such as HBr Object is closed, the process efficient, low energy consumption, processing procedure are generated without NOx.The heat accumulating type catalytic oxidation that the embodiment of the present application uses Device carries out heat recovery, and organic efficiency is high, while can realize the recycling of bromo element in PTA oxidized tail gas, obtains NaBr, NH4Br Or Br2Bromines product is waited, realizes the recycling of pollutant, with good economic efficiency, social benefit and environmental benefit.
Those skilled in the art will readily occur to the present invention its after considering specification and putting into practice invention disclosed herein Its embodiment.This application is intended to cover the present invention any variations, uses, or adaptations, these modifications, purposes or Person's adaptive change follows the general principle of the present invention and including undocumented common knowledge in the art of the invention Or conventional techniques.Description and embodiments are considered only as illustratively, and true scope and spirit of the invention are by following Claim is pointed out.
It should be appreciated that the invention is not limited in the precision architecture for being described above and being shown in the drawings, and And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is only limited by appended claim.

Claims (10)

1. a kind of PTA oxidized tail gas purification and bromine retracting device, which is characterized in that including wind turbine (1), automatic admission valve (2) stores Hot type catalyst oxidation reactor (3), expanding machine (4), tail gas washing tower (5), bromine recovery tower (6) and PTA tail gas intake valve (7)；
The heat accumulating type catalyst oxidation reactor (3) is provided with heat accumulating type catalyst oxidation reactor import (31) and heat accumulating type catalysis Oxidation reactor exports (32)；
The heat accumulating type catalyst oxidation reactor (3) is provided with the first regenerative chamber, the second regenerative chamber, thermal oxidizer and automatically controls Device；
The expanding machine (4) is provided with expander inlet (41) and expander outlet (42)；
The bottom of towe side wall of the tail gas washing tower (5) is provided with tail gas washing tower import (51), the tower of the tail gas washing tower (5) Bottom is provided with tail gas washing tower outlet (52), and the tower top of the tail gas washing tower (5) is equipped with cleaning of off-gas and exports (53), the tail The tower top side wall of gas wash tower (5) is equipped with alkali liquor inlet (54)；
The bromine recovery tower (6) is provided with bromine recovery tower import (61) and bromine recovery tower outlet (62)；
The wind turbine (1) is connected by the automatic admission valve (2) with the heat accumulating type catalyst oxidation reactor import (31)；
The PTA tail gas intake valve (7) is connected with the heat accumulating type catalyst oxidation reactor import (31)；
The heat accumulating type catalyst oxidation reactor outlet (32) is connected with the expander inlet (41)；
The expander outlet (42) is connected with the tail gas washing tower import (51)；
The tail gas washing tower outlet (52) is connected with the bromine recovery tower import (61).
2. the apparatus according to claim 1, which is characterized in that the heat accumulating type catalyst oxidation reactor (3) is double bed type heat Heat accumulating type catalyst oxidation reactor.
3. according to the device described in claim 1-2, which is characterized in that urging in the heat accumulating type catalyst oxidation reactor (3) Agent uses ruthenium base honeycomb catalyst.
4. the apparatus according to claim 1, which is characterized in that the automatic control of the heat accumulating type catalyst oxidation reactor (3) Device processed uses PLC automatons.
5. the apparatus according to claim 1, which is characterized in that the quantity of the heat accumulating type catalyst oxidation reactor (3) is Two, two heat accumulating type catalyst oxidation reactors (3) are arranged in parallel.
6. a kind of PTA oxidized tail gas purification and bromine recovery process, suitable for claim 1-5 any one of them devices, feature It is, the technique comprises the following steps：
Step 1：Using fresh air auxiliary fuel effect under pre-heating heat accumulation type catalyst oxidation reactor (3)；
Step 2：After PTA oxidized tail gas is preheated into the first regenerative chamber, into thermal oxidizer under the effect of the catalyst into Row catalytic oxidation；
Step 3：The substance obtained in the step 2 is transmitted to the second regenerative chamber and carries out heat recovery, heat accumulating type catalysis oxygen Change reactor (3) and export tail gas by expanding machine (4) acting；
Step 4：The substance obtained in the step 3 is transmitted in exhaust gas washing tower (5) using in lye absorption tail gas HBr and Br2, the lye of adsorption saturation enters bromine recovery tower (6), obtains NaBr, NH4Br or Br2Bromine recycles product.
7. technique according to claim 5, which is characterized in that heat accumulating type catalyst oxidation reactor (3) inlet temperature For 300-350 DEG C, outlet temperature is 50-80 DEG C, operating pressure 0.8-1.2MPa.
8. technique according to claim 5, which is characterized in that the inlet pressure of the expanding machine (4) is 0.8-1.2MPa, Outlet pressure is 0.1MPa.
9. technique according to claim 5, which is characterized in that the lye of the exhaust gas washing tower (5) is using 10-15%'s Sodium hydrate aqueous solution or ammonium hydroxide, temperature is 45-60 DEG C in exhaust gas washing tower.
10. technique according to claim 5, which is characterized in that the bromine recovery tower (6) is adsorbed with exhaust gas washing tower (5) The lye of saturation is raw material, and NaBr, NH are obtained by concentration, Crystallization Procedure4Br passes through chlorine or hydrogen peroxide oxidation, general Bromide ion is oxidized to bromine simple substance, and then blowing method by extraction or sky again separates bromine simple substance in water.
CN201711415474.2A 2017-12-22 2017-12-22 A kind of PTA oxidized tail gas purification and bromine retracting device and technique Pending CN108057330A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114906964A (en) * 2021-02-09 2022-08-16 大连波美科技有限公司 PTA wastewater treatment system and application method
WO2023088016A1 (en) * 2021-11-22 2023-05-25 山东海王化工股份有限公司 Production method for sodium bromide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301579A (en) * 2008-06-20 2008-11-12 上海东化环境工程有限公司 High-pressure tail gas treatment process in purified terephthalic acid
CN101940869A (en) * 2010-06-13 2011-01-12 浙江逸盛石化有限公司 Purification method and device of exhaust gas of purified terephthalic acid oxidizing device
CN102923663A (en) * 2012-11-06 2013-02-13 绍兴汉青环保科技有限公司 Method for recovering bromine from pure terephthalic acid (PTA) waste water
CN105126834A (en) * 2015-09-10 2015-12-09 中国科学院过程工程研究所 Integral type ruthenium catalyst used for purifying PTA oxidized tail gas as well as preparation method and application of integral type ruthenium catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101301579A (en) * 2008-06-20 2008-11-12 上海东化环境工程有限公司 High-pressure tail gas treatment process in purified terephthalic acid
CN101940869A (en) * 2010-06-13 2011-01-12 浙江逸盛石化有限公司 Purification method and device of exhaust gas of purified terephthalic acid oxidizing device
CN102923663A (en) * 2012-11-06 2013-02-13 绍兴汉青环保科技有限公司 Method for recovering bromine from pure terephthalic acid (PTA) waste water
CN105126834A (en) * 2015-09-10 2015-12-09 中国科学院过程工程研究所 Integral type ruthenium catalyst used for purifying PTA oxidized tail gas as well as preparation method and application of integral type ruthenium catalyst

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
温泉等: "《水土修复技术》", 31 October 2017, 吉林大学出版社 *
范伟粹: "《国外油气新技术》", 31 March 1993, 中国石油天然气总公司情报研究所 *
郝晓霞等: "PTA尾气治理技术概述", 《当代化工》 *
马广大主编: "《大气污染控制工程 第2版》", 30 June 2004, 中国环境科学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114906964A (en) * 2021-02-09 2022-08-16 大连波美科技有限公司 PTA wastewater treatment system and application method
CN114906964B (en) * 2021-02-09 2023-07-21 大连波美科技有限公司 PTA wastewater treatment system and application method
WO2023088016A1 (en) * 2021-11-22 2023-05-25 山东海王化工股份有限公司 Production method for sodium bromide

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Application publication date: 20180522