CN103203242B - Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas - Google Patents
Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas Download PDFInfo
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- CN103203242B CN103203242B CN201310071884.5A CN201310071884A CN103203242B CN 103203242 B CN103203242 B CN 103203242B CN 201310071884 A CN201310071884 A CN 201310071884A CN 103203242 B CN103203242 B CN 103203242B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
- B01D53/8615—Mixtures of hydrogen sulfide and sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/068—Polyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes
Abstract
The invention discloses a catalytic system and a process for the desulfuration of industrial sulfur-bearing waste gas. The catalytic system comprises, by weight percent, 2-50 % of polyhydric alcohol, 1-40 parts of acid catalyst, and the balance of water. The acid catalyst is one or combination of inorganic acid, inorganic acid/slat, and organic carboxylic acid or soluble salt thereof. The process includes: waste gas pretreatment, absorption reaction and sulphur recovery. Low-temperature aqueous phase reaction is applied in the reaction process, and low temperature ensures deep conversion between hydrogen sulfide and sulfur dioxide (total desulfuration rate is increased to 99.95%). The catalytic system is simple to prepare and low in cost.
Description
Technical field
The present invention relates to exhaust-gas treatment field, particularly relate to a kind of catalyst system and catalyzing and technique thereof of industrial sulphur-containing exhaust gas desulfurization process.
Background technology
Hydrogen sulfide is one of important Sulphur ressource, mainly results from the processes such as selexol process, petroleum refining process, coking and coal gasification production and produces.Hydrogen sulfide gas has severe toxicity, the characteristic such as inflammable, explosive, can not directly discharge.Therefore, must reclaim hydrogen sulfide gas, be the needs of the utilization of resources, is also the requirement of environmental protection.
Sulfide in crude oil is converted mainly into hydrogen sulfide in refining process, current domestic smeltery generally adopts Claus method to carry out process Recovered sulphur to hydrogen sulfide gas, current Claus method needs to carry out more than sulphur boiling point, because general Claus method adopts fixed bed catalytic reactor, if existed in solid form, beds must be blocked.But claus reaction is strong exothermal reaction, the sulphur product Thermodynamic Law of generation shows, pyroreaction must cause lower conversion ratio, and the rate of recovery of sulphur can only reach 94 ~ 97%.Therefore, its tail gas must arrange exhaust gas processing device could meet environmental requirement, tail gas treatment process more complicated, and kind is also many, and mainly contain two large classes, a class is direct oxidation process or low temperature conversion technique, and a class is solvent wash or solvent oxidation.Direct oxidation or the representative technique of low temperature conversion method have: super or super excellent claus process, low temperature conversion series (the sub-dew point of MCRC, sulfreen), CLINSULF-DO technique.Super or super excellent claus process, low temperature conversion series (the sub-dew point of MCRC, sulfreen) total sulfur recovery 99% ~ 99.5%, tail gas can not ensure to reach discharge standard, and CLINSULF-DO technique domestic application is less, and actual total sulfur recovery also only has 99.6%.Solvent wash method is divided into Physical and chemical method two kinds, and this sulfur recovery technology can only be connected with Sulfur Recovery Unit operation and be used.Representational technique has: SCOT technique, ammonia process washing process, milk of lime washing process.SCOT technique is most widely used in refinery at home, and total sulfur recovery can reach 99.8%, can meet environment protection emission requirement, but its hydrogenating reduction workshop section needs external heat source, consume more hydrogen, whole technological process is longer, and operating cost and equipment cost are all higher.
In addition, SO
2being the arch-criminal causing acid rain, is to one of gas of natural environment most harmfulness.If directly discharge makes a very bad impression to production operation, surrounding enviroment and plant area workman, belong to one of environmental contaminants that must eliminate or control.The discharge of coal-fired plant's sulfur dioxide has caused huge environmental pollution and acid rain.There is the sulfur dioxide in requirement enriched flue gas at present, be recycled.Phillips oil company patent S-Zorb catalytic gasoline desulfur technology has been introduced from China Petrochemical Industry, built up in Yanshan Petrochemical the gasoline sweetener that domestic first set applies this technology in May, 2007, and obtaining successfully, S-Zorb desulfur technology obtains popularization rapidly.But can produce a large amount of form waste gas of sulfur dioxide in S-Zorb desulfur technology adsorbent reactivation process, the processing method of current domestic maturation is with alkali liquor absorption, but the spent lye difficult treatment produced, cost is higher, and causes the waste of Sulphur ressource.
Summary of the invention
Based on this, the object of this invention is to provide a kind of catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization process.
Concrete technical scheme is as follows:
A catalyst system and catalyzing for industrial sulphur-containing exhaust gas desulfurization process, this catalyst system and catalyzing comprises the component of following mass percentage: the polyalcohol of 2-50%, the acidic catalyst of 1-40%, surplus are water; Described acidic catalyst is one or more in inorganic acid, inorganic acid salt, organic carboxyl acid or its soluble-salt.
Wherein in some embodiments, described catalyst system and catalyzing comprises the component of following mass percentage: the polyalcohol of 10-40%, the acidic catalyst of 2-8%, surplus are water.
Wherein in some embodiments, described polyalcohol is selected from: one or more in ethylene glycol, glycerine, diethylene glycol, polyethylene glycol.Polyalcohol effect is the solubility increasing sulfur dioxide and hydrogen sulfide.
Wherein in some embodiments, described inorganic acid is selected from: phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid; Inorganic acid salt is selected from: niter cake, potassium acid sulfate, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate.The effect of inorganic acid or inorganic acid salt is the acid-base value of control catalyst system and catalyzing and carries out claus reaction in the liquid phase as catalytic reactive component sulfur dioxide and hydrogen sulfide.
Wherein in some embodiments, described organic carboxyl acid or its soluble-salt are selected from: citric acid, natrium citricum, potassium citrate, Sodium Benzoate, Potassium Benzoate, sodium phthalate or sodium salicylate.The effect of organic carboxyl acid or its soluble-salt is the acid-base value of control catalyst system and catalyzing and carries out claus reaction in the liquid phase as catalytic reactive component sulfur dioxide and hydrogen sulfide.
Another object of the present invention is to provide a kind of technique utilizing above-mentioned catalyst system and catalyzing to carry out industrial sulphur-containing exhaust gas desulfurization process.
Concrete technical scheme is as follows:
Utilize above-mentioned catalyst system and catalyzing to carry out a technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass in catalyst system and catalyzing after pretreated for step (1) hydrogen sulfide containing industrial waste gas is mixed with the industrial waste gas containing sulfur dioxide and carry out absorption reaction, paddle is adopted to stir in reactor, guarantee that mist fully contacts with catalyst system and catalyzing, the flow of the gaseous mixture of often liter of described catalyst system and catalyzing process is 100-2000ml/min, and wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 1.8-2.2:1;
(3) the product elemental sulfur of recycling step (2) absorption reaction, elemental sulfur adopts vacuum filtration or pressurizing filter to reclaim, and the liquid-circulating after filtration utilizes.
Wherein in some embodiments, the absorption reaction of described step (2) is one or more levels series connection absorption.
Wherein in some embodiments, the mixing ratio of described hydrogen sulfide and sulfur dioxide is 2:1.
Wherein in some embodiments, the temperature of described step (2) absorption reaction controls at 0-130 DEG C, and Stress control is at 0.1-3MPa.
Wherein in some embodiments, the temperature of described step (2) absorption reaction is room temperature, and Stress control is at 0.1-0.2MPa.
Principle of the present invention:
At present, what in existing Crouse's sulphur recovery technology and tail gas disposal technique thereof, total sulfur removal rate was the highest is SCOT technique, reach 99.8%, but its hydrogenating reduction process can not be converted into hydrogen sulfide in actual applications completely, in addition, solvent absorption process has been difficult to go to improve its absorption efficiency again.
The sweetening process that the present invention relates to and principle: hydrogen sulfide and sulfur dioxide in liquid phase, in acid condition catalytic reaction are occurred by solution absorption, and the key reaction of generation is expressed as:
2H
2s+SO
3 2-+ 2H
+==3S+3H
2o or 4H
2s+S
2o
5 2-+ 2H
+==6S+5H
2o
Be swift in response, both can 100% complete reaction in theory.In addition, the present invention also can adopt the secondary even technique of plural serial stage absorption, improves total sulfur removal rate further.
Beneficial effect of the present invention:
The present invention can be applicable to claus tail-gas clean-up in refinery, smeltery's sulfur-containing tail gas, FCC regeneration tail gas, the process of flue gas of power plants and oil product deep desulfuration waste gas, the regeneration process etc. of oil plant and sewage treatment plant's sour water process and desulfurizing agent.
The main feature of inventive desulfurization technique is to process the waste gas of the other sulfide hydrogen of two stocks and sulfur dioxide simultaneously, and two strands of gases do not need separation and concentration, does not therefore need to use organic amine adsorbent, does not have the problem of froth breaking; Do not need heating, do not need to add iron catalyst yet.
Sulfur removal technology of the present invention overcomes existing high temperature Crouse sulphur recovery technical deficiency (total sulfur removal rate is 99.8%), utilize the catalyst system and catalyzing of hydrogen sulfide containing gas and the waste gas reaction Recovered sulphur containing sulfur dioxide, course of reaction adopts water at low temperature phase reaction, low temperature can ensure that the deep conversion (total sulfur removal rate is increased to 99.95%) of hydrogen sulfide and sulfur dioxide, and catalyst system and catalyzing preparation of the present invention is simple, cost is lower.
Sulfur removal technology operating condition of the present invention is gentle, and technical process is comparatively simple, can process simultaneously, and reclaim elemental sulfur, effectively decrease the pollution of environment and saved Sulphur ressource hydrogen sulfide and form waste gas of sulfur dioxide.
Accompanying drawing explanation
Fig. 1 inventive desulfurization process chart.
Description of reference numerals:
201, catalyst system and catalyzing storage tank; 202, filter; 203, measuring pump; 204, first order absorption reactor; 205, secondary absorption reaction still; 206, pressure-reducing valve; 207, check valve; 208, flowmeter.
Detailed description of the invention
With reference to figure 1, the flow chart of the present invention's industry sulphur-containing exhaust gas sulfur removal technology, comprises catalyst system and catalyzing storage tank 201, filter 202, measuring pump 203, first order absorption reactor 204, secondary absorption reaction still 205, pressure-reducing valve 206, check valve 207 and flowmeter 208.
The waste gas of the other sulfide hydrogen of two stocks and sulfur dioxide enters in still from the gas distributor bottom first order absorption reactor through gas flowmeter by a certain percentage after mixing in pipeline, the waste gas of the overwhelming majority generates elemental sulfur with catalyst system and catalyzing haptoreaction in first order absorption reactor, catalyst system and catalyzing containing elemental sulfur can be discharged bottom reactor, recyclable sulphur after filtration, remaining waste gas enters secondary absorption reaction still through gas distributor again, sulfurous gas is almost completely by absorption reaction, and tail gas is directly emptying; Required catalyst system and catalyzing is added by measuring pump.
By the following examples the present invention is further elaborated.
Embodiment 1
The mass percentage of the present embodiment catalyst system and catalyzing consists of: ethylene glycol 40%, sodium dihydrogen phosphate 5%, surplus are water.Be dissolved in water by ethylene glycol and sodium dihydrogen phosphate, preparation obtains 1.5L catalyst system and catalyzing.Measuring pump is utilized to be got in reactor by this solution.
With reference to figure 1, a kind of technique of industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass into after being mixed with the industrial waste gas containing sulfur dioxide (volume content is 5%) by the industrial waste gas of step (1) pretreated sulfide hydrogen (volume content is 10%) in the catalyst system and catalyzing in first order absorption reactor 204 and carry out absorption reaction, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 2:1; Under room temperature and 0.1MPa pressure, keep total gas flow rate 0.6L/min, this catalyst system and catalyzing continuously-running more than 100 hours; As shown in Figure 1, the present embodiment absorption reaction is two-stage tandem reaction, mist in first order absorption reactor after absorption reaction tail gas enter secondary absorption reaction still continue absorption reaction, the technique that plural serial stage absorbs can reach the object of deep desulfuration, and series-connected stage is several to be required to decide according to desulfurization depth.
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, filtrate cycle utilizes.
By gas chromatographic detection tail gas sulfurous gas concentration, result shows total sulfur removal rate and reaches more than 99.97%.
Embodiment 2
Consisting of of the mass percentage of the present embodiment catalyst system and catalyzing: 20% polyethylene glycol, 0.1% sulfuric acid, 1% citric acid, 1% sodium hydrogen phosphate, all the other are water.Above-mentioned raw materials is dissolved in water, obtains 1.5L catalyst system and catalyzing, utilize measuring pump to be got in reactor by this solution.
A technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass into after being mixed with the industrial waste gas containing sulfur dioxide (volume content is 5%) by the industrial waste gas of step (1) pretreated sulfide hydrogen (volume content is 10%) in the catalyst system and catalyzing in reactor and carry out absorption reaction, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 1.8:1; Under 50 DEG C and 0.1MPa pressure, keep total gas flow rate 2.4L/min, this catalyst system and catalyzing continuously-running more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, filtrate cycle utilizes.
By gas chromatographic detection tail gas sulfurous gas concentration, result shows total sulfur removal rate and reaches more than 99.95%.
Embodiment 3
Consisting of of the mass percentage of the present embodiment catalyst system and catalyzing: 30% glycerine, 5% phosphoric acid, 0.5% Sodium Benzoate, all the other are water.Above-mentioned raw materials is dissolved in water, obtains 1.5L catalyst system and catalyzing, utilize measuring pump to be got in reactor by this solution.
A technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass into after being mixed with the industrial waste gas containing sulfur dioxide (volume content is 5%) by the industrial waste gas of step (1) pretreated sulfide hydrogen (volume content is 10%) in the catalyst system and catalyzing in reactor and carry out absorption reaction, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 2.2:1; Under 80 DEG C and 0.1MPa pressure, keep total gas flow rate 1.6L/min, this catalyst system and catalyzing continuously-running more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, filtrate cycle utilizes.
By gas chromatographic detection tail gas sulfurous gas concentration, result shows total sulfur removal rate and reaches more than 99.95%.
Embodiment 4
Consisting of of the mass percentage of the present embodiment catalyst system and catalyzing: 10% polyethylene glycol, 2% sodium salicylate, 4% sodium hydrogen phosphate, all the other are water.Above-mentioned raw materials is dissolved in water, obtains 1.5L catalyst system and catalyzing, utilize measuring pump to be got in reactor by this solution.
A technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass into after being mixed with the industrial waste gas containing sulfur dioxide (volume content is 5%) by the industrial waste gas of step (1) pretreated sulfide hydrogen (volume content is 10%) in the catalyst system and catalyzing in reactor and carry out absorption reaction, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 2:1; Under room temperature and 0.2MPa pressure, keep total gas flow rate 3.0L/min, this catalyst system and catalyzing continuously-running more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, filtrate cycle utilizes.
By gas chromatographic detection tail gas sulfurous gas concentration, result shows total sulfur removal rate and reaches more than 99.95%.
Embodiment 5
Consisting of of the mass percentage of the present embodiment catalyst system and catalyzing: 15% diethylene glycol, 2% sodium phthalate, 0.5% niter cake, all the other are water.Above-mentioned raw materials is dissolved in water, obtains 1.5L catalyst system and catalyzing, utilize measuring pump to be got in reactor by this solution.
A technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass into after being mixed with the industrial waste gas containing sulfur dioxide (volume content is 5%) by the industrial waste gas of step (1) pretreated sulfide hydrogen (volume content is 10%) in the catalyst system and catalyzing in reactor and carry out absorption reaction, wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 2:1; Under room temperature and 0.2MPa pressure, keep total gas flow rate 2.0L/min, this catalyst system and catalyzing continuously-running more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, filtrate cycle utilizes.
By gas chromatographic detection tail gas sulfurous gas concentration, result shows total sulfur removal rate and reaches more than 99.95%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a catalyst system and catalyzing for industrial sulphur-containing exhaust gas desulfurization process, it is characterized in that, this catalyst system and catalyzing comprises the component of following mass percentage: the polyalcohol of 10-40%, the acidic catalyst of 2-8%, surplus are water; Described acidic catalyst is one or more in inorganic acid, inorganic acid salt, organic carboxyl acid or its soluble-salt; Described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide.
2. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization process according to claim 1, it is characterized in that, described polyalcohol is selected from: one or more in ethylene glycol, glycerine, diethylene glycol, polyethylene glycol.
3. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization process according to claim 1, is characterized in that described inorganic acid is selected from: phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid; Inorganic acid salt is selected from: niter cake, potassium acid sulfate, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate.
4. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization process according to claim 1, it is characterized in that, described organic carboxyl acid or its soluble-salt are selected from: citric acid, natrium citricum, potassium citrate, Sodium Benzoate, Potassium Benzoate, sodium phthalate or sodium salicylate.
5. utilize catalyst system and catalyzing described in any one of claim 1-4 to carry out a technique for industrial sulphur-containing exhaust gas desulfurization process, described industrial sulphur-containing exhaust gas is the industrial waste gas respectively containing hydrogen sulfide and sulfur dioxide, it is characterized in that, comprises following steps:
(1) waste gas pretreatment: pretreatment is carried out to two strands of industrial waste gases respectively containing hydrogen sulfide and sulfur dioxide, guarantees that in 2 strands of industrial waste gases, non-sulphur gas can not react with reaction medium and reactant at reaction conditions;
(2) absorption reaction: pass in catalyst system and catalyzing after pretreated for step (1) hydrogen sulfide containing industrial waste gas is mixed with the industrial waste gas containing sulfur dioxide and carry out absorption reaction, the flow of the gaseous mixture of often liter of described catalyst system and catalyzing process is 100-2000ml/min, and wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 1.8-2.2:1;
(3) the product elemental sulfur of recycling step (2) absorption reaction.
6. the technique of industrial sulphur-containing exhaust gas desulfurization process according to claim 5, is characterized in that, the absorption reaction of described step (2) is one or more levels series connection absorption.
7. the technique of the industrial sulphur-containing exhaust gas desulfurization process according to claim 5 or 6, is characterized in that, the mixing ratio of described hydrogen sulfide and sulfur dioxide is 2:1.
8. the technique of the industrial sulphur-containing exhaust gas desulfurization process according to claim 5 or 6, it is characterized in that, the temperature of described step (2) absorption reaction controls at 0-130 DEG C, and Stress control is at 0.1-3MPa.
9. the technique of industrial sulphur-containing exhaust gas desulfurization process according to claim 8, it is characterized in that, the temperature of described step (2) absorption reaction is room temperature, and Stress control is at 0.1-0.2MPa.
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| CN201310071884.5A CN103203242B (en) | 2013-03-06 | 2013-03-06 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
| PCT/CN2013/084793 WO2014134917A1 (en) | 2013-03-06 | 2013-09-30 | Catalyst system for desulfurization treatment of industrial sulphur-containing waste gas and process thereof |
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| CN103203242B (en) * | 2013-03-06 | 2015-02-25 | 广州博能能源科技有限公司 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
| CN104801153A (en) * | 2015-04-16 | 2015-07-29 | 广东省宜华木业股份有限公司 | Spraying liquid for workshop tail-gas treatment and preparation method of spraying liquid |
| CN106467292B (en) * | 2015-08-19 | 2018-09-25 | 中国石油化工股份有限公司 | A kind of sulfur recovery method |
| CN109534297B (en) * | 2017-09-21 | 2021-07-09 | 中国石油化工股份有限公司 | Method for desulfurizing hydrogen sulfide and sulfur dioxide through reaction |
| CN108636078B (en) * | 2018-05-17 | 2021-01-29 | 中国石油天然气股份有限公司 | Pretreatment agent and pretreatment method for organic waste gas of oil and gas operation station |
| CN109569498A (en) * | 2018-12-26 | 2019-04-05 | 西安元创化工科技股份有限公司 | A kind of preparation method of renewable hydrogen sulfide gas adsorbent |
| CN110106004A (en) * | 2018-12-29 | 2019-08-09 | 河南农业大学 | Methane desulfurizer, sulfur method and purifying technique |
| CN110551543A (en) * | 2019-09-12 | 2019-12-10 | 欧润吉生态环保(浙江)有限公司 | Device for deep desulfurization of biogas |
| CN115340887B (en) * | 2022-10-18 | 2023-01-31 | 山东鹏达生态科技股份有限公司 | Blast furnace gas fine desulfurization and sulfur recycling process |
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| CN103203242B (en) * | 2013-03-06 | 2015-02-25 | 广州博能能源科技有限公司 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
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- 2013-09-30 WO PCT/CN2013/084793 patent/WO2014134917A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040518A (en) * | 1988-09-02 | 1990-03-21 | 罗纳布朗克化学公司 | Gaseous effluent is handled catalyst and processing method |
| CN101322915A (en) * | 2007-06-14 | 2008-12-17 | 兰州理工大学 | Composite adsorption desulfurizing agent and preparation method thereof |
| CN101417230A (en) * | 2007-10-26 | 2009-04-29 | 中国石油化工股份有限公司 | Processing method before applying hydrogenation catalyst |
| CN102527202A (en) * | 2012-01-06 | 2012-07-04 | 肖天存 | Process and equipment for desulfurizing sulfur-containing waste gas and recovering elemental sulfur |
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| CN103203242A (en) | 2013-07-17 |
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