CN101955193A - Method for preparing hydrogen and fertilizer ammonium sulfate by desulfurizing coal-fired waste gas - Google Patents
Method for preparing hydrogen and fertilizer ammonium sulfate by desulfurizing coal-fired waste gas Download PDFInfo
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- CN101955193A CN101955193A CN 201010283122 CN201010283122A CN101955193A CN 101955193 A CN101955193 A CN 101955193A CN 201010283122 CN201010283122 CN 201010283122 CN 201010283122 A CN201010283122 A CN 201010283122A CN 101955193 A CN101955193 A CN 101955193A
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a method for preparing fuel hydrogen and an agricultural fertilizer ammonium sulfate from a coal-fired waste gas. The method comprises four steps of chemical adsorption of the coal-fired waste gas, forming of ammonium sulfate aqueous solution from an aerosol-state sub-ammonium salt, photo-catalytic reaction and product purification. Namely, on the basis of an ammonia desulfurization method, a photo-catalytic technique and an ammonia desulfurization technique are organically combined together to finish the conversion from the chemical adsorption of the coal-fired waste gas (sulfur dioxide) to the ammonium sulfate (the agricultural fertilizer ammonium sulfate) and the hydrogen (a new energy resource) with higher application value. Thus, the method reduces the operating expenses required by oxidation of the sub-ammonium salt during ammonia desulfurization, increases the product utility value, and has a higher application value.
Description
Technical field
The present invention relates to the method for a kind of coal combustion exhaust desulfurization hydrogen manufacturing and chemical fertilizer sulphur ammonium, belong to coal combustion exhaust and handle and the developmental technology of new energy resources field.
Background technology
Environmental pollution and energy shortage are the significant challenge that current mankind faces, and also are that China implements the necessary top-priority key subjects of the strategy of sustainable development.The gaseous pollutant of industrial discharge is one of important source of topsoil, and wherein toxic harmful exhaust gas causes serious threat to human health and ecological safety.Along with the fast development of industry such as China's electric power, the coal consumption amount increases substantially, and makes sulfur dioxide pollution constantly aggravate.China's sulphur dioxide emission occupy first place in the world at present, and surpass 2,000 ten thousand tons for years, and wherein power plant emission sulfurous gas accounts for 60% of total amount near 50%, two control district sulphur dioxide emission of total amount.China's acid rain and sulfur dioxide pollution are serious, and the acid rain area has accounted for 30% of area, and acid rain and sulfur dioxide pollution cause financial loss every year more than 1,000 hundred million yuan.Therefore, research and development is fit to China's national situation, and has the poisonous and harmful industrial waste gas purifying technology and equipment of independent intellectual property right, and exhaust gas utilization prepares new forms of energy and has important practical significance.
In recent years " ammonia process of desulfurization " because technology simple, front-end investment is few, the routine maintenance amount is little, desulfurization product is that chemical fertilizer advantages such as (ammonium fertilizer-ammonium sulfate) causes people's extensive concern.Its principle is to adopt ammoniacal liquor to contact mixing as desulfurization absorbent with the flue gas that enters reaction tower, the SO in the flue gas
2Generate ammonium sulphite with the ammoniacal liquor reaction, again through at high temperature carrying out generating ammoniumsulphate soln after the oxidizing reaction with oxygen, by making chemical fertilizer ammonium sulfate after crystallization, dehydration, the press filtration, its sales revenue can be supported towards sweetening agent and working cost at last.Ammonia also is a kind of poisonous dusty gas, can produce a large amount of ammonia-contaminated gas in synthetic ammonia or urea production process, itself just has the difficult problems that need to be resolved hurrily such as quantity discharged is big, pollution is heavy, difficult.The theory environmental pollution improvement work of the ammonia process of desulfurization this " with useless pollution treatment " " turning waste into wealth " has great importance.
Ammonia desulfurizing process is according to ammonia (NH
3) and sulfurous gas (SO
2), the water basic mechanism that is reacted into desulfurization product carries out, and mainly contains wet-type ammonia, electron beam ammonia process, impulse electric corona ammonia process, simple and easy ammonia process etc.Wherein wet-type ammonia is more sophisticated at present, industrialized ammonia desulfurizing process.The wet-type ammonia technological process generally is divided into three big steps: desulfurization absorption, intermediates are handled, the byproduct manufacturing.Different according to process and by product, wet-type ammonia can be divided into ammonia-fertile method, ammonia-acid system, ammonia-ammonium sulfite etc. again.Wherein ammonia-fertile method is divided into fertile method of ammonia-ammonia sulfate and the fertile method of ammonia-ammonium phosphate again according to the product difference.The fertile method of ammonia-ammonia sulfate is a most popular method in the wet ammonia process desulfurizing technology.
The oxide treatment of the intermediates of the ammonia process of desulfurization-imonium salt is the key of decision ammonia desulfuration equipment economical operation, and methods such as pressure oxidation, catalyzed oxidation are arranged usually, all need build a cover oxidation unit in addition, makes the working cost of total system be difficult to descend.Therefore development new technologies, ammonium sulphite bring great economic benefit will for enterprise and society to the required expense of the transformation of ammonium sulfate in the reduction ammonia process of desulfurization.
Photochemical catalysis can be converted into highdensity chemical energy, electric energy with low-density solar energy; can directly utilize simultaneously in sunlight degraded and the mineralized water and airborne all contaminations; by light-catalysed method; making full use of the sunlight of cheapness and " green ", is an important channel that solves present global energy crisis and environmental pollution.Photocatalysis technology is comparatively extensive in the research of directions such as organic pollutant improvement and water decomposition hydrogen manufacturing, yet utilizes photochemical catalysis to carry out the research of coal combustion exhaust desulfurization, does not see relevant report both at home and abroad so far, and also relevant patent relates to this partial content.
Present patent application is on the basis of ammoniacal liquor doctor treatment photocatalysis technology and ammoniacal liquor desulfurization technology organically to be combined, finish conversion from the chemisorption of coal combustion exhaust (sulfurous gas) to ammonium sulfate with higher using value (agricultural fertilizer sulphur ammonium) and hydrogen (new forms of energy), reduce in the ammonia process of desulfurization because of the required working cost of imonium salt oxidation, increase product utilization and be worth, have higher application prospect.
Summary of the invention
The object of the present invention is to provide a kind of coal combustion exhaust (SO that utilizes
2) carry out utilization of waste material and prepare hydrogen and the agricultural method with chemical fertilizer sulphur ammonium.
Know-why of the present invention
The present invention is a kind of technology of utilizing coal combustion exhaust to carry out photochemical catalysis desulfurization hydrogen manufacturing and chemical fertilizer sulphur ammonium of developing on the basis of simple and easy ammoniacal liquor doctor treatment.
Simple and easy ammonia process technology is simple, working cost is cheap, but the desulfurization product major part of simple and easy ammonia process is the unsettled imonium salt of aerosol state, reclaims very difficultly, and its desulfurization product (unsettled imonium salt) decomposites sulfurous gas (SO with having part after the flue gas emptying again
2), form secondary pollution.
Photochemical catalysis ammoniacal liquor method is on the basis of simple and easy ammonia process photocatalysis technology and ammonia process technology organically to be combined, utilize sun power to finish from waste gas (sulfurous gas) to ammonium sulfate the conversion of (agricultural with chemical fertilizer sulphur ammonium) and hydrogen (new forms of energy) with higher using value, because of the required working cost of imonium salt oxidation, increase product utilization and be worth in the reduction ammonia process of desulfurization.
The main process of photochemical catalysis ammoniacal liquor method is carried out in two steps:
At first utilize the H under the gas phase condition
2O, NH
3With SO
2Between rapid reaction design easy reaction device carry out the ammonia process of desulfurization, its desulfurization product mainly is the unsettled imonium salt of aerosol state;
Make the product (imonium salt) of ammonia process of desulfurization step change into stable ammonium salt by light-catalysed step again and prepare hydrogen (new forms of energy) simultaneously with higher using value.
Technical scheme of the present invention
The method of a kind of coal combustion exhaust desulfurization hydrogen manufacturing and chemical fertilizer sulphur ammonium, this method comprises the steps:
1. the chemisorption of coal combustion exhaust:
Sulfurous gas (SO in the coal combustion exhaust
2) and ammonia (NH
3) and water (H
2O) rapid reaction generates aerosol state imonium salt ((NH
4)
2SO
3);
2. the aerosol state imonium salt formation ammonium sulphite aqueous solution
At ammonia (NH
3) under the protective atmosphere, prepared aerosol state imonium the salt ((NH of step 1
4)
2SO
3) feed in the normal-temperature water, forming concentration is the ammonium sulphite aqueous solution of 0.1～6mol/L;
3. photochemical catalysis step
The ammonium sulphite aqueous solution of step 2 preparation, be transferred to the light-catalyzed reaction chamber, utilize high-activity photocatalyst (photocatalyst), as Cadmium Sulfide photocatalysts such as (CdS), the ammonium sulphite aqueous solution is carried out solar irradiation, make the ammonium sulphite aqueous solution be finally converted into ammonium sulfate solution (product) and hydrogen (product) through the photochemical catalytic oxidation reduction reaction;
The reaction equation that is taken place is:
Photocatalyst (photocatalyst) is 0.09～0.2% of an ammonium sulphite aqueous solution weight as the consumption of Cadmium Sulfide photocatalysts such as (CdS).
4. product purification
The resulting product in step 3 reaction back comprises liquid ammonium sulfate solution and gasiform hydrogen;
Wherein gaseous product can be removed remaining ammonia to extract hydrogen after water filtration;
The ammonium sulfate solution that generates is through heating evaporation moisture, and chemical fertilizer sulphur ammonium is prepared in crystallization.
The photocatalyst of above-mentioned coal combustion exhaust desulfurization hydrogen manufacturing and chemical fertilizer sulphur ammonium is solid particulate or film, and is reusable after filtering.
Beneficial effect of the present invention
The present invention is because the technical scheme that has adopted photochemical catalysis and ammoniacal liquor method to combine, thereby has the effect of effectively removing coal combustion exhaust toxic pollutant and industrial ammonia pollutent, simultaneously can also Hydrogen Energy be can be by conversion solar, hydrogen (new forms of energy) and chemical fertilizer sulphur ammonium prepared at last with higher using value.Utilize this technology can improve the product income that coal combustion exhaust is administered, reduce the cost that coal combustion exhaust is administered, have comparatively wide application prospect.
Description of drawings
Fig. 1, photochemical catalysis ammoniacal liquor method are handled the process flow diagram of coal combustion exhaust hydrogen manufacturing and chemical fertilizer sulphur ammonium.
Fig. 2, utilize Cadmium Sulfide CdS photocatalysis Decomposition (NH
4)
2SO
3Solution hydrogen manufacturing test.Reaction conditions: photocatalyst 0.5g CdS; Reaction solution 1M (NH
4)
2SO
3Solution 300ml; Light source: standard 1.5AM simulated solar irradiation (1000W xenon lamp), illuminating area 200 cm
2
Fig. 3, CdS photocatalysis Decomposition (NH
4)
2SO
3The endurance life test of solution hydrogen production activity.Reaction conditions: photocatalyst 0.5g CdS; Reaction solution 1M (NH
4)
2SO
3Solution 300ml; Light source: standard 1.5AM simulated solar irradiation (1000W xenon lamp), illuminating area 33 cm
2
Fig. 4, the ammonium sulphite aqueous solution chromatography of ions figure after light-catalyzed reaction.Test conditions: photocatalyst 0.5g CdS; Reaction solution 1M (NH
4)
2SO
3Solution 300ml; Light source: standard 1.5AM simulated solar irradiation (1000W xenon lamp), illuminating area 33 cm
2
Fig. 5, ammonium sulphite concentration of aqueous solution are to the influence of photocatalytic hydrogen production activity.Test conditions: photocatalyst 0.5g CdS; Reaction solution 1M (NH
4)
2SO
3Solution 300ml; Light source: standard 1.5AM simulated solar irradiation (1000W xenon lamp), illuminating area 33 cm
2
The consumption of Fig. 6, photocatalyst Cadmium Sulfide is to the influence of photocatalytic hydrogen production activity.Test conditions: photocatalyst CdS; Reaction solution 1M (NH
4)
2SO
3Solution 300ml; Light source: standard 1.5AM simulated solar irradiation (1000W xenon lamp), illuminating area 33 cm
2
Embodiment
Also in conjunction with the accompanying drawings the present invention is further set forth below by embodiment, but do not limit the present invention.
Utilize visible light catalytic material Cadmium Sulfide (CdS) to carry out the hydrogen manufacturing of coal combustion exhaust photochemical catalysis ammonia spirit desulfurization.Utilize ammoniacal liquor absorption sulfurous gas to generate ammonium sulfite solution, under the irradiation of simulated solar irradiation, utilize CdS to carry out the photochemical catalytic oxidation and the water decomposition hydrogen manufacturing of ammonium sulfite solution.Specifically the process flow diagram of reaction is as shown in Figure 1:
Wherein ammoniacal liquor and coal combustion exhaust are had feasibility by ammoniacal liquor method proof in conjunction with what generate the sulfurous acid aqueous solution, mainly illustrate for example to use photocatalysis technology and make the photochemical catalytic oxidation of the sulfurous acid aqueous solution generate the feasibility of sulphur ammonium and hydrogen herein.
Starting material
Commercial Cadmium Sulfide (CdS); (0.5g purity 99.99%) (Alfa Aesar company)
Ammonium sulfite solution: (feeding ammoniacal liquor by sulfurous gas generates)
PdCl
2(purity 99.99%) (Aldrich company)
Cr (NO
3)
3(purity 98%) (Aldrich company)
NaBH
4, 98%, Acros Organics company
Polyvinlylpyrolidone (PVP, K30, average MW 40,000), Fluka company
Experimental procedure
The ammonium sulfite solution of configuration different concns: 0.1M, 0.3M, 0.35M, 0.5M, 1M, 3M, 6M;
Configuration light promotor Pd/Cr
2O
3:
The PdCl of configuration 1M
2And Cr (NO
3)
3The aqueous solution is pressed Pd:Cr
2O
3Mass ratio be that 4:1 mixes, add 0.03783g NaBH subsequently
4Pd/Cr is prepared in reduction
2O
3Light promoter metal colloidal sol adds 0.02g PVP and prevents that metal nanoparticle from precipitating because of reunion.
Photocatalysis hydrogen production and sulphur ammonium
Get the 300ml ammonium sulfite solution in photo catalysis reactor, add 0.5gCdS, under stirring state, add 2.5mgPd/Cr
2O
3The light promotor utilizes simulated solar irradiation (xenon lamp (1.5AM) Newport company) to carry out photocatalysis hydrogen production and the experiment of sulphur ammonium subsequently.
Catalyzed reaction result's experiment
The feasibility of photochemical catalytic oxidation reduction ammonium sulfite solution hydrogen manufacturing and chemical fertilizer sulphur ammonium
Fig. 2 is Cadmium Sulfide CdS photocatalysis Decomposition (NH
4)
2SO
3Solution hydrogen manufacturing test-results.As shown in Figure 2, the CdS that does not add promotor has possessed the ability of photocatalysis Decomposition ammonium sulfite solution, but hydrogen production activity is lower, and its hydrogen-producing speed has only 0.46 mL/min.
In concentration is the photocatalyst Cadmium Sulfide (CdS) that adds 0.5g in the ammonium sulphite aqueous solution of 1mol/L, adds photochemical catalysis promotor Pd/Cr simultaneously
2O
3Its result contrasts as can be seen, and the photocatalytic activity of CdS is greatly improved, in photochemical catalysis promotor add-on is 0.5% o'clock of photocatalyst quality, and it goes out hydrogen speed and rises to 2.5ml/min fast, and this photo-quantum efficiency that is reflected in 350 to 520nm the light scope has reached 50%.Test-results shows that can reduce the mode of ammonium sulfite solution by photochemical catalytic oxidation makes hydrogen.
Embodiment2
Photochemical catalytic oxidation reduction ammonium sulfite solution hydrogen production activity is stable
The reactive behavior that CdS photocatalysis Decomposition ammonium sulfite solution goes out hydrogen is comparatively stable.Fig. 3 shows the active endurance life test result who utilizes 0.5g photocatalyst Cadmium Sulfide (CdS) decomposition 1M ammonium sulphite aqueous solution hydrogen manufacturing test.As shown in the figure, CdS can keep the high reactivity non-stop run a few days, and the ammonium sulphite complete oxidation in solution is ammonium sulfate and prepares hydrogen near 5 liters.This result shows and utilizes photocatalysis technology redox ammonium sulphite hydrogen manufacturing effectively, and can keep higher hydrogen manufacturing speed and the sun power effciency of energy transfer to Hydrogen Energy.
Embodiment3
The thoroughness of photochemical catalytic oxidation reduction ammonium sulfite solution hydrogen manufacturing
But utilize light-catalysed method complete oxidation reduction ammonium sulfite solution, as shown in Figure 4, after the 1M ammonium sulfite solution is carried out the photocatalysis Decomposition hydrogen production reaction, sulfite ion in the solution can be converted into sulfate ion fully, and this result shows and utilizes photocatalysis technology can realize the ammonium sulphite complete oxidation is generated ammonium sulfate and prepares the purpose of hydrogen.
Embodiment4
Ammonium sulfite solution concentration is to the influence of photocatalytic hydrogen production activity
Research ammonium sulphite concentration of aqueous solution is to the active influence factor of photocatalytic hydrogen production by water decomposition.The ammonium sulphite aqueous solution of choosing concentration and be 0.1 mol to 6 mol saturation concentration is that reaction solution carries out the photocatalysis hydrogen production experiment.Fig. 5 shows that the concentration of the ammonium sulphite aqueous solution is bigger to the influence of photocatalytic hydrogen production activity, and when its concentration was in 0.5 mol to 6 mol, the hydrogen manufacturing of the photochemical catalysis ammonium sulphite aqueous solution was the highest to the utilising efficiency of sun power.
Embodiment5
The photocatalyst consumption is to the influence of photocatalytic hydrogen production activity
The consumption of photocatalyst has certain influence to photocatalytic hydrogen production activity.Fig. 6 has shown the influence of different amounts CdS photocatalyst to photocatalysis Decomposition ammonium sulfite solution hydrogen production activity.Experimental result show the consumption when Cadmium Sulfide (CdS) be ammonium sulphite aqueous solution weight 0.09～0.22% the time, catalyzer can show higher photocatalytic activity.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.。
Claims (10)
1. a coal combustion exhaust desulfurization hydrogen production process is characterized in that this method comprises the steps:
(1), the chemisorption of coal combustion exhaust:
Sulfurous gas (SO in the coal combustion exhaust
2) can with ammonia (NH
3) and water (H
2O) rapid reaction generates aerosol state imonium salt ((NH
4)
2SO
3);
(2), the aerosol state imonium salt formation ammonium sulphite aqueous solution
With ammonia (NH
3) be protective atmosphere, prepared aerosol state imonium the salt ((NH of step (1)
4)
2SO
3) feed in the normal-temperature water, forming concentration is the ammonium sulphite aqueous solution of 0.1～6mol/L;
(3), photochemical catalysis step
The ammonium sulphite aqueous solution of step (2) preparation, be transferred to the light-catalyzed reaction chamber, utilize photocatalyst, the ammonium sulphite aqueous solution is carried out solar irradiation, make the ammonium sulphite aqueous solution be finally converted into ammonium sulfate solution and hydrogen through the photochemical catalytic oxidation reduction reaction;
The reaction equation that is taken place is:
The consumption of photocatalyst is 0.09～0.2% of an ammonium sulphite aqueous solution weight;
(4) product purification
The resulting product gasiform hydrogen in step (3) reaction back is removed remaining ammonia after water filtration.
2. a kind of coal combustion exhaust desulfurization hydrogen production process as claimed in claim 1 is characterized in that step (3) institute
The photocatalyst of stating (photocatalyst) is preferably Cadmium Sulfide (CdS).
3. a kind of coal combustion exhaust desulfurization hydrogen production process as claimed in claim 1 or 2 is characterized in that step (3)
When preferably adding photocatalyst in the described photochemical catalysis step, add the promotor Pd/Cr of photocatalyst
2O
3, its add-on is 0.5% of a photocatalyst weight.
4. a kind of coal combustion exhaust desulfurization hydrogen production process as claimed in claim 1 or 2 is characterized in that step (2)
In the described aerosol state imonium salt formation ammonium sulphite aqueous solution step, the sulfurous acid that is preferably formed
Aqueous ammonium concentration is 0.5～6mol/L.
5. the method for the fertile sulphur ammonium of coal combustion exhaust desulfurization inhibition and generation is characterized in that this method comprises the steps:
(1), the chemisorption of coal combustion exhaust:
Sulfurous gas (SO in the coal combustion exhaust
2) can with ammonia (NH
3) and water (H
2O) rapid reaction generates aerosol state imonium salt ((NH
4)
2SO
3);
(2), the aerosol state imonium salt formation ammonium sulphite aqueous solution
With ammonia (NH
3) be protective atmosphere, prepared aerosol state imonium the salt ((NH of step (1)
4)
2SO
3) feed in the normal-temperature water, forming concentration is the ammonium sulphite aqueous solution of 0.1～6mol/L;
(3), photochemical catalysis step
The ammonium sulphite aqueous solution of step (2) preparation, be transferred to the light-catalyzed reaction chamber, utilize photocatalyst, the ammonium sulphite aqueous solution is carried out solar irradiation, make the ammonium sulphite aqueous solution be finally converted into ammonium sulfate solution and hydrogen through the photochemical catalytic oxidation reduction reaction;
The reaction equation that is taken place is:
(4) product purification
Step (3) is reacted the resulting product ammonium sulfate solution in back through heating evaporation moisture, the crystallizable chemical fertilizer sulphur ammonium of preparing.
6. the method for the fertile sulphur ammonium of a kind of coal combustion exhaust desulfurization inhibition and generation as claimed in claim 5 is characterized in that the described photocatalyst of step (3) (photocatalyst) is preferably Cadmium Sulfide (CdS).
7. the method for the fertile sulphur ammonium of a kind of coal combustion exhaust desulfurization inhibition and generation as claimed in claim 5, the consumption that it is characterized in that the described photocatalyst of step (3) is 0.09～0.2% of an ammonium sulphite aqueous solution weight.
8. as the method for claim 5, the fertile sulphur ammonium of 6 or 7 described a kind of coal combustion exhaust desulfurization inhibition and generation, when it is characterized in that adding photocatalyst in the described photochemical catalysis step of step (3), preferably add the promotor Pd/Cr of photocatalyst
2O
3, its add-on is 0.1～1% of a photocatalyst weight.
9. the method for the fertile sulphur ammonium of a kind of coal combustion exhaust desulfurization inhibition and generation as claimed in claim 8 is characterized in that the promotor Pd/Cr of photocatalyst in the described photochemical catalysis step of step (3)
2O
3Add-on be 0.5% of photocatalyst weight.
10. as the method for claim 5, the fertile sulphur ammoniums of 6 or 7 described a kind of coal combustion exhaust desulfurization inhibition and generation, it is characterized in that the ammonium sulphite concentration of aqueous solution that is preferably formed is 0.5～6mol/L in the described aerosol state imonium of step (2) the salt formation ammonium sulphite aqueous solution step.
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|---|---|---|---|
| CN2010102831228A CN101955193B (en) | 2010-09-16 | 2010-09-16 | Method for preparing hydrogen and fertilizer ammonium sulfate by desulfurizing coal-fired waste gas |
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|---|---|---|---|
| CN2010102831228A CN101955193B (en) | 2010-09-16 | 2010-09-16 | Method for preparing hydrogen and fertilizer ammonium sulfate by desulfurizing coal-fired waste gas |
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| CN101955193B CN101955193B (en) | 2012-06-20 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862063A (en) * | 2016-06-02 | 2016-08-17 | 复旦大学 | Method for simultaneously recovering sulfur dioxide and producing hydrogen |
| CN108970353A (en) * | 2018-07-16 | 2018-12-11 | 西安华大骄阳绿色科技有限公司 | A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia |
| US11708267B2 (en) | 2020-12-18 | 2023-07-25 | Uop Llc | Process for managing hydrogen sulfide in a refinery |
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| US3676059A (en) * | 1970-06-01 | 1972-07-11 | Albert B Welty Jr | Sulfate control in ammonia flue gas desulfurization |
| CN1843575A (en) * | 2006-03-29 | 2006-10-11 | 华北电力大学 | Method and apparatus for optic catalytic oxidizing, desulfurizing and denitrifying flue gas simultaneously |
| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN101543724A (en) * | 2009-03-25 | 2009-09-30 | 南京东大苏威能源环保工程有限公司 | Ammonia desulphurization method suitable for sintering flue gas treatment |
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2010
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|---|---|---|---|---|
| US3676059A (en) * | 1970-06-01 | 1972-07-11 | Albert B Welty Jr | Sulfate control in ammonia flue gas desulfurization |
| CN1843575A (en) * | 2006-03-29 | 2006-10-11 | 华北电力大学 | Method and apparatus for optic catalytic oxidizing, desulfurizing and denitrifying flue gas simultaneously |
| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN101543724A (en) * | 2009-03-25 | 2009-09-30 | 南京东大苏威能源环保工程有限公司 | Ammonia desulphurization method suitable for sintering flue gas treatment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862063A (en) * | 2016-06-02 | 2016-08-17 | 复旦大学 | Method for simultaneously recovering sulfur dioxide and producing hydrogen |
| CN105862063B (en) * | 2016-06-02 | 2018-07-24 | 复旦大学 | A method of the hydrogen manufacturing simultaneously of recovery processing sulfur dioxide |
| CN108970353A (en) * | 2018-07-16 | 2018-12-11 | 西安华大骄阳绿色科技有限公司 | A kind of synthesis desulfurating method of denitration being catalyzed flue gas and the sour gas containing ammonia |
| CN108970353B (en) * | 2018-07-16 | 2021-04-30 | 西安华大骄阳绿色科技有限公司 | Comprehensive desulfurization and denitrification method for catalytic flue gas and ammonia-containing acid gas |
| US11708267B2 (en) | 2020-12-18 | 2023-07-25 | Uop Llc | Process for managing hydrogen sulfide in a refinery |
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| Publication number | Publication date |
|---|---|
| CN101955193B (en) | 2012-06-20 |
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