CN108499339A - A variety of waste gas treatment process - Google Patents

A variety of waste gas treatment process Download PDF

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Publication number
CN108499339A
CN108499339A CN201710109795.3A CN201710109795A CN108499339A CN 108499339 A CN108499339 A CN 108499339A CN 201710109795 A CN201710109795 A CN 201710109795A CN 108499339 A CN108499339 A CN 108499339A
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China
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liquid
variety
oxide
hydroxide
industrial waste
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CN201710109795.3A
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Chinese (zh)
Inventor
李湘忠
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Shanghai Jingtian Ep-Tech Co Ltd
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Shanghai Jingtian Ep-Tech Co Ltd
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Priority to CN201710109795.3A priority Critical patent/CN108499339A/en
Publication of CN108499339A publication Critical patent/CN108499339A/en
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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
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or 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
    • B01D53/75—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/50—Nitrous acid; Salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/108—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • 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
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • 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
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2047—Hydrofluoric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/122—Gaseous reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/124—Liquid reactants

Abstract

Presently disclosed a variety of waste gas treatment process, including use amino agents as carbon capture agent and metal oxide is used to be reacted into line replacement terminating object, that isolates is recycled containing ammonia liquid, and the compound solid of removing is recycled as industrial raw materials；After recycling strong oxidizer to aoxidize exhaust gas, absorbed into nitrite with alkaline matter, to disposably achieve the purpose that exhaust gas decarburization, desulphurization and denitration, dechlorination, defluorinate, demercuration, Tuo bioxin, de- stench.

Description

A variety of waste gas treatment process
Technical field
The present invention relates to the green technology technology fields that Industrial Boiler, kiln, chemical industry etc. discharge waste gas pollution control and treatment.
Background technology
Sulfur dioxide (chemical formula：SO2) it is one of Air Pollutant Discharge.It is closed since coal and oil usually all contain vulcanization Object, therefore can generate sulfur dioxide when burning.When sulfur dioxide is soluble in water, sulfurous acid (main component of acid rain) can be formed. High risks are caused to health, farming and animal husbandry is made to cause the underproduction, keep industrial building corrosion and ageing serious etc..
Greenhouse effects have caused the extensive concern of international community, combustion of fossil fuel to be the largest the source of atmospheric pollution, and CO2The main source of release of greenhouse gases.Estimate that, if do not taken action resolutely, the year two thousand fifty has with the energy according to International Energy Agency (IEA) Carbon dioxide (the CO of pass2) discharge capacity will than 2005 increase by 130%.CO2 emission can be such that earth mean temperature increases, EI Nino phenomenon getting worse.So that the earth is occurred, sea level rise floods city, super typhoon unusual weather conditions, sandstorm and stream Frequent, the agriculture underproduction wave of refugees of row disease outburst emerges in large numbers, and extreme influence is generated to the existence of the mankind.
Currently, exhuast gas desulfurization Technical comparing maturation includes the ammonia process of desulfurization, it is that sulfur dioxide is changed into chemical fertilizer using ammonium hydroxide The method utilized again.Exhaust gas denitration Technical comparing it is ripe include SCR methods and SNCR methods, be using ammonia in the case where there is catalyst or Nitrogen oxides is transformed into nitrogen discharge under high temperature.Exhaust gas decarburization technique only takes CCS technologies at present, is by carbon dioxide (CO2) capture and the technology sealed up for safekeeping.At this stage, the engineering reliability, economic feasibility of CCS and environmental safety be at home and abroad Endure dispute to the fullest extent.Including：
1) energy consumption cost is significantly increased.
2) core technology is still immature.
3) the following financing gap is larger.
4) there are certain risks in market.
5) potential environmental impact is great.
Invention content
A variety of waste gas treatment process of the present invention are related to using amino agents as absorption in an absorbing reaction device Agent, and reacted into line replacement with the termination object of above-mentioned absorbing reaction using metal oxide, it isolates
Ammonia liquid is recycled, is recycled as industrial raw materials after the compound drying of separation.It not only removes in this way Carbon dioxide in exhaust gas, reaches exhaust gas decarburization purpose, and be to recycle.The present invention has small investment, operating cost It is low, removal efficiency is high, non-secondary pollution while the advantages of remove a variety of exhaust gas.
Presently disclosed a variety of waste gas treatment process, the exhaust gas can be fossil fuel (coal, oil, petroleum coke) and/ Or formed in waste boiler, kiln combustion process, can also be chemical industry equipment discharge carbon dioxide, sulfur dioxide, one Nitrogen oxide, hydrogen sulfide, hydrogen chloride, hydrogen fluoride, bioxin, stench and mercury.Pernicious gas removal rate in exhaust gas is up to 50% ~99%.
Description of the drawings
Fig. 1 is the canonical schema of the present invention, illustrates a variety of waste gas treatment process process citings, but not limited to this.
Specific implementation mode
A variety of exhaust gas 1 are introduced into the absorbing reaction device 3 in emission-control equipment 2, the amino agents 4 being passed through, and will reaction Liquid afterwards is collected in rich solution pond 5.
It is passed through metal oxide 6 in rich solution pond 5 and is mixed using blender 7.Mixed slurry is transported to solid-liquid In separator 8.
That isolates is sent into amino agents 4 in the first absorbing reaction device 3 containing ammonia liquid by pump 9 and pipeline 10 together； 11 solid of carbon compound isolated is dried, is packed, is sold.
The exhaust gas 12 of purification enters in oxidation reactor 13, is passed through strong oxidizer 14.Exhaust gas enters back into the second absorbing reaction Device 15 is passed through akaline liquid 16, and neutralization reactant is flowed into equipment for separating liquid from solid 17.Nitrogenous compound solid 18 is dried Dry, packaging, sale, clean gas 19 are discharged into air.
Subtractive process describes：
Amino agents first choice ammonium hydroxide described in typical case of the present invention, metal oxide base reagent first choice oxidation Magnesium, the strong oxidizer first choice chlorine dioxide, the akaline liquid first choice calcium hydroxide.Carbon dioxide in exhaust gas, two Sulfur oxide, hydrogen chloride, hydrogen fluoride are reacted with ammonium hydroxide generates the ammonium salts liquid such as ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium fluoride.
Ammonium salt liquid is mixed with magnesium hydroxide solution, displacement reaction occurs.The ammonium hydroxide reflected is replaced to follow again Ring uses, to reduce operating cost；The magnesium such as the magnesium carbonate and relatively small number of magnesium sulfate, magnesium chloride, magnesium fluoride that cement out It can be reapplied in industrial production after the processing of salt drying.
Although magnesia is insoluble in pure water and organic solvent, acid, ammonium salt solution can be dissolved in and in water because of dioxy Change carbon presence and the increased characteristic of solubility.
The chemical equation that ammonium carbonate, ammonium sulfate, ammonium chloride, ammonium fluoride are reacted with magnesium hydroxide into line replacement：
(NH4)2CO3+Mg(OH)2→MgCO3↓+2NH3·H2O
(NH4)2SO4+Mg(OH)2→MgSO4↓+2NH3·H2O
2NH4Cl+Mg(OH)2→MgCl2↓+2NH3·H2O
2NH4F+Mg(OH)2→MgF2↓+2NH3·H2O
MgCO3、MgSO4、MgCl2、MgF2Than Mg (OH)2Molecule more preferably stablize, chemical reaction will be to more stable side To variation.
Magnesium carbonate can be used as the thermal insulation material of refractory material, boiler and pipeline and the additive of rubber, ink etc., solution acid Agent, drier, color stabilizer, carrier, anti-caking agent.
There are many source of magnesia, and China, which mainly uses, to be obtained using magnesite, dolomite as raw material.In order to aoxidized The pollution again of carbon dioxide does not occur when magnesium, it is proposed that refining method using seawater obtains magnesia.Its technique is：
1) it obtains magnesium chloride enriched bittern cake in multipurpose use of sea water or carries the brine after bromine to be raw material.
2) plus sodium hydroxide generates magnesium hydrate precipitate.
Exhaust gas after absorbing reaction device is directly entered in oxidation reactor 13, after being passed through strong oxidizer 14, in exhaust gas NO be oxidized to NO2.Exhaust gas carries out neutralization reaction in the second absorbing reaction device 15 with the calcium hydroxide liquid 16 being passed through, raw At high added value calcium nitrite solid 18 and reapply in industrial production.
The big effect of the three of calcium nitrite
3500 yuan or so of the calcium nitrite market price has very high commercial value.
1, concrete corrosion resistant agent：Calcium nitrite can prevent or slow down anode as Anodic Type antirust for reinforced concrete Tarnishing processes play the role of protection anode, cathode are isolated, and form " passivating film " in steel surface, can make building, structures Service life extend 20-50.The sodium salt of nitrous acid is efficiently solved, " alkali " may be caused and to concrete performance The shortcomings that adversely affecting or generate local corrosion and accelerating corrosion.
2, concrete antifreezer：Calcium nitrite fundamentally overcomes and occurs in concrete as concrete antifreezer " alkali-aggregate reaction " and the defect of electrochemical corrosion improves the physical and mechanical property and durability of concrete, obtains high-quality coagulation Soil.Be a new generation without antifreezing agent of the chlorine without " alkali-aggregate reaction ", fresh concrete freezing point, construction temperature reachable -25 can be reduced DEG C, under the conditions of subzero temperature, the hydration reaction of cement Mineralss can be promoted.
3, cement hardener：Calcium nitrite is as hardening of cement inorganic agent, i.e. early strength agent.The time that thes cement solidifies can be shortened, So that early strength of concrete is improved, at the same can make concrete material occur again the presetting period it is long when, carry out hardening of cement Processing, makes the setting time of concrete building structures and compression strength meet national standard.

Claims (10)

  1. More than 1. kinds of industrial waste gas treatment process, it is characterised in that：It is comprised the steps of：
    (a) a variety of industrial waste gases react in the first absorbing reaction device with amino agents, and the rich solution of generation is collected；
    (b) metal oxide reagent hybrid concurrency life displacement is carried out with the rich solution to react；
    (c) liquid is separated by solid-liquid separation after reacting displacement；
    (d) a variety of industrial waste gases enter back into oxidation reactor is reacted with strong oxidizer；
    (e) a variety of industrial waste gases are entered back into the second absorbing reaction device and are reacted with akaline liquid, and neutralization reactant is consolidated Liquid detaches.
  2. 2. the method as described in claim 1, it is characterised in that：It includes to be followed what the separation of solid and liquid obtained containing ammonia liquid Ring spray enters in the first absorbing reaction device.
  3. 3. the method as described in claim 1, it is characterised in that：It includes to contain carbon compound by what is obtained after the separation of solid and liquid Object solid drying and processing.
  4. 4. the method as described in claim 1, it is characterised in that：A variety of industrial waste gases refer to but are not limited to titanium dioxide Carbon, sulfur dioxide, nitric oxide, hydrogen sulfide, hydrogen chloride, hydrogen fluoride, bioxin, stench and heavy metal.
  5. 5. the method as described in claim 1, it is characterised in that：The amino agents refer to but are not limited to ammonium hydroxide, urea, ammonia Base ammonium formate, amine and other ammonium-containing compounds.
  6. 6. the method as described in claim 1, it is characterised in that：The metal oxide reagent refers to but is not limited to aoxidize One or more metallic compounds of magnesium, calcium oxide, manganese oxide, zinc oxide, aluminium oxide.
  7. 7. the method as described in claim 1, it is characterised in that：The strong oxidizer includes ozone, hydrogen peroxide, titanium dioxide Chlorine, sodium hypochlorite, sodium chlorite, calcium chlorite, calcium hypochlorite, bleaching powder one or several kinds of mixtures.
  8. 8. the method as described in claim 1, it is characterised in that：The akaline liquid refers to but is not limited to calcium hydroxide, hydrogen Sodium oxide molybdena, magnesium hydroxide, one kind of manganous hydroxide or most kind of hydroxide.
  9. 9. the method as described in claim 1, it is characterised in that：It further includes the control supply amino agents quantity, gold The step of belonging to oxide reagent quantity, quantity containing ammonia liquid, strong oxidizer quantity, akaline liquid quantity.
  10. 10. the method as described in claim 1, it is characterised in that：It includes by whole chemical reaction processes at one It is carried out in container or in multiple containers.
CN201710109795.3A 2017-02-27 2017-02-27 A variety of waste gas treatment process Pending CN108499339A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109289491A (en) * 2018-11-13 2019-02-01 上海氯碱化工股份有限公司 A kind of processing method of carbonated tail gas
CN109647152A (en) * 2019-01-29 2019-04-19 中南大学 A kind of purification method and its purification device containing chlorine or/and sulphur-containing exhaust gas
CN110559827A (en) * 2019-08-26 2019-12-13 山鹰国际控股股份公司 Treatment process of papermaking waste gas
TWI760662B (en) * 2019-11-27 2022-04-11 超重力股份有限公司 Manufacturing method of solid nitrogen fertilizer
CN114471124A (en) * 2022-03-15 2022-05-13 南京沃野化工科技有限公司 Carbon and sulfur emission reduction and carbon and sulfur fixation method
CN115445577A (en) * 2022-08-19 2022-12-09 广西夏阳环保科技有限公司 Ammonia water-calcium hydroxide composite atmospheric treatment agent and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1345621A (en) * 2000-09-22 2002-04-24 张至德 Removing sulfur dioxide from industrial waste gas by ammonia regeneration circulation process
CN104147909A (en) * 2014-08-06 2014-11-19 华北电力大学 Denitration, demercuration and deep desulfurization system and method based photocatalytic oxidation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1345621A (en) * 2000-09-22 2002-04-24 张至德 Removing sulfur dioxide from industrial waste gas by ammonia regeneration circulation process
CN104147909A (en) * 2014-08-06 2014-11-19 华北电力大学 Denitration, demercuration and deep desulfurization system and method based photocatalytic oxidation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109289491A (en) * 2018-11-13 2019-02-01 上海氯碱化工股份有限公司 A kind of processing method of carbonated tail gas
CN109647152A (en) * 2019-01-29 2019-04-19 中南大学 A kind of purification method and its purification device containing chlorine or/and sulphur-containing exhaust gas
CN109647152B (en) * 2019-01-29 2022-03-29 中南大学 Method and device for purifying waste gas containing chlorine or/and sulfur
CN110559827A (en) * 2019-08-26 2019-12-13 山鹰国际控股股份公司 Treatment process of papermaking waste gas
TWI760662B (en) * 2019-11-27 2022-04-11 超重力股份有限公司 Manufacturing method of solid nitrogen fertilizer
CN114471124A (en) * 2022-03-15 2022-05-13 南京沃野化工科技有限公司 Carbon and sulfur emission reduction and carbon and sulfur fixation method
CN115445577A (en) * 2022-08-19 2022-12-09 广西夏阳环保科技有限公司 Ammonia water-calcium hydroxide composite atmospheric treatment agent and preparation method thereof

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Application publication date: 20180907