CN103203242A - 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
- Publication number
- CN103203242A CN103203242A CN2013100718845A CN201310071884A CN103203242A CN 103203242 A CN103203242 A CN 103203242A CN 2013100718845 A CN2013100718845 A CN 2013100718845A CN 201310071884 A CN201310071884 A CN 201310071884A CN 103203242 A CN103203242 A CN 103203242A
- Authority
- CN
- China
- Prior art keywords
- catalyzing
- catalyst system
- industrial
- exhaust gas
- sulphur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Gas Separation By Absorption (AREA)
- Catalysts (AREA)
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 the exhaust-gas treatment field, particularly relate to catalyst system and catalyzing and technology thereof that a kind of industrial sulphur-containing exhaust gas desulfurization is handled.
Background technology
Hydrogen sulfide is one of important sulphur resource, mainly results from the processes such as selexol process, petroleum refining process, coking and coal gasification production to produce.Hydrogen sulfide gas has severe toxicity, characteristic such as inflammable, explosive, can not directly discharge.Therefore, must reclaim hydrogen sulfide gas, be the needs of the utilization of resources, also is requirement on environmental protection.
Sulfide in the crude oil mainly is converted into hydrogen sulfide in refining process, present domestic smeltery generally adopts Claus method that hydrogen sulfide gas is handled Recovered sulphur, present Claus method need carry out more than the sulphur boiling point, because general Claus method adopts fixed bed catalytic reactor, if exist with solid form, must block beds.But claus reaction is strong exothermal reaction, and the sulphur product thermodynamics rule of generation shows that 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 satisfy environmental requirement, and tail gas treatment process more complicated, kind are also many, mainly contains two big classes, and a class is direct oxidation technology or low temperature conversion technology, and a class is solvent wash or solvent oxidation.Direct oxidation or the representative technology of low temperature conversion method have: and super or super excellent claus process, low temperature conversion series (the inferior dew point of MCRC, sulfreen), CLINSULF-DO technology.Super or super excellent claus process, low temperature conversion series (the inferior dew point of MCRC, sulfreen) total sulfur recovery 99%～99.5%, tail gas can not guarantee to reach discharge standard, and the domestic application of CLINSULF-DO technology is less, and actual total sulfur recovery also has only 99.6%.The solvent wash method is divided into two kinds of physics method and chemical methods, the use of can only connecting with the Sulfur Recovery Unit operation of this sulfur recovery technology.Representational technology has: SCOT technology, ammonia process washing process, milk of lime washing process.SCOT technology is most widely used in the refinery at home, and total sulfur recovery can reach 99.8%, can satisfy the environment protection emission requirement, but its hydrogenating reduction workshop section needs external heat source, consume more hydrogen, whole process flow is longer, and operating cost and equipment cost are all higher.
In addition, SO
2Being the arch-criminal who causes acid rain, is one of gas to the tool harmfulness of natural environment.If directly discharging makes a very bad impression to production operation, surrounding enviroment and the workman of plant area, belong to one of environmental contaminants of necessary elimination or control.The discharging of coal-fired plant's sulfur dioxide has caused huge environmental pollution and acid rain.Sulfur dioxide in the requirement enriched flue gas has been arranged at present, be recycled.Introduced the patent S-Zorb of Phillips oil company catalytic gasoline desulfur technology from China Petrochemical Industry, built up the gasoline sweetener that domestic first cover is used this technology in May, 2007 in Yanshan Petrochemical, and achieve success, the S-Zorb desulfur technology has obtained popularization rapidly.But, can produce a large amount of form waste gas of sulfur dioxide in the S-Zorb desulfur technology adsorbent reactivation process, the processing method of present domestic maturation is to absorb with alkali lye, but the spent lye difficult treatment that produces, cost is higher, and has caused the waste of sulphur resource.
Summary of the invention
Based on this, the purpose of this invention is to provide the catalyst system and catalyzing that a kind of industrial sulphur-containing exhaust gas desulfurization is handled.
Concrete technical scheme is as follows:
The catalyst system and catalyzing that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, polyalcohol, the acidic catalyst of 1-40%, surplus that this catalyst system and catalyzing comprises the component of following quality percentage composition: 2-50% are water; Described acidic catalyst is one or more in inorganic acid, inorganic acid salt, organic carboxyl acid or its soluble-salt.
Among some embodiment, polyalcohol, the acidic catalyst of 2-8%, surplus that described catalyst system and catalyzing comprises the component of following quality percentage composition: 10-40% are water therein.
Among some embodiment, described polyalcohol is selected from therein: one or more in ethylene glycol, glycerine, diethylene glycol, the polyethylene glycol.The polyalcohol effect is to increase the solubility of sulfur dioxide and hydrogen sulfide.
Among some embodiment, described inorganic acid is selected from therein: 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 to control the acid-base value of catalyst system and catalyzing and carries out claus reaction as catalytic reactive component sulfur dioxide and hydrogen sulfide in liquid phase.
Among some embodiment, 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 therein.The effect of organic carboxyl acid or its soluble-salt is to control the acid-base value of catalyst system and catalyzing and carries out claus reaction as catalytic reactive component sulfur dioxide and hydrogen sulfide in liquid phase.
Another object of the present invention provides a kind of technology of utilizing above-mentioned catalyst system and catalyzing to carry out industrial sulphur-containing exhaust gas desulfurization processing.
Concrete technical scheme is as follows:
A kind of technology of utilizing above-mentioned catalyst system and catalyzing to carry out industrial sulphur-containing exhaust gas desulfurization processing, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the pretreated hydrogen sulfide containing industrial waste gas of step (1) is mixed back the feeding in the catalyst system and catalyzing carry out absorption reaction with the industrial waste gas that contains sulfur dioxide, adopt paddle to stir in the reactor, guarantee that mist fully contacts with catalyst system and catalyzing, the flow of the gaseous mixture of every liter of described catalyst system and catalyzing processing 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 adopt vacuum filtration or supercharging to filter and reclaim, and the liquid after the filtration is recycling.
Among some embodiment, the absorption reaction of described step (2) absorbs for one or more levels series connection therein.
Among some embodiment, the mixing ratio of described hydrogen sulfide and sulfur dioxide is 2:1 therein.
Among some embodiment, the temperature of described step (2) absorption reaction is controlled at 0-130 ℃ therein, and pressure is controlled at 0.1-3MPa.
Among some embodiment, the temperature of described step (2) absorption reaction is room temperature therein, and pressure is controlled at 0.1-0.2MPa.
Principle of the present invention:
At present, what total sulfur removal rate was the highest in existing Crouse's sulphur recovery technology and the vent gas treatment technology thereof is SCOT technology, reach 99.8%, but its hydrogenating reduction process can not be converted into hydrogen sulfide in actual applications fully, in addition, the 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 are dissolved to absorb in the liquid phase, under acid condition catalytic reaction takes place, 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 technology that the present invention also can adopt secondary even plural serial stage to absorb further improves total sulfur removal rate.
Beneficial effect of the present invention:
The present invention can be applicable to claus tail-gas clean-up in the refinery, smeltery's sulfur-bearing tail gas, FCC regeneration tail gas, power plant's tail gas and oil product deep desulfuration treatment of waste gas, the regeneration processing of oil plant and sewage treatment plant's sour water processing and desulfurizing agent etc.
The main feature of sulfur removal technology of the present invention is and can handles the waste gas of the other sulfide hydrogen of two stocks and sulfur dioxide simultaneously that two strands of gases do not need separation and concentration, does not therefore need to use the 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 has overcome existing high temperature Crouse sulphur recovery technical deficiency (total sulfur removal rate is 99.8%), utilize hydrogen sulfide containing gas and the catalyst system and catalyzing that contains the waste gas reaction Recovered sulphur of sulfur dioxide, course of reaction adopts the water at low temperature phase reaction, low temperature can guarantee that the degree of depth of hydrogen sulfide and sulfur dioxide transforms (total sulfur removal rate is increased to 99.95%), and catalyst system and catalyzing preparation of the present invention is simple, and cost is lower.
Sulfur removal technology operating condition gentleness of the present invention, technical process is comparatively simple, can handle hydrogen sulfide and form waste gas of sulfur dioxide simultaneously, and reclaim elemental sulfur, has effectively reduced the pollution of environment and has saved the sulphur resource.
Description of drawings
Fig. 1 desulfurization process figure of the present invention.
Description of reference numerals:
201, catalyst system and catalyzing storage tank; 202, filter; 203, measuring pump; 204, one-level absorption reaction still; 205, secondary absorption reaction still; 206, pressure-reducing valve; 207, check valve; 208, flowmeter.
The specific embodiment
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, one-level absorption reaction still 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 gas distributor from one-level absorption reaction still bottom after gas flowmeter mixes in pipeline by a certain percentage enters in the still, the waste gas of the overwhelming majority generates elemental sulfur with the catalyst system and catalyzing haptoreaction in one-level absorption reaction still, the catalyst system and catalyzing that contains elemental sulfur can be discharged from the reactor bottom, recyclable sulphur after filtration, remaining waste gas enters secondary absorption reaction still through gas distributor again, sulfurous gas almost completely is absorbed reaction, the direct emptying of tail gas; Required catalyst system and catalyzing adds by measuring pump.
By the following examples the present invention is further elaborated.
Embodiment 1
The quality percentage composition of present embodiment catalyst system and catalyzing consists of: ethylene glycol 40%, sodium dihydrogen phosphate 5%, surplus are water.Ethylene glycol and sodium dihydrogen phosphate are dissolved in the water, and preparation obtains the 1.5L catalyst system and catalyzing.Utilize measuring pump that this solution is got in the reactor.
With reference to figure 1, the technology that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the industrial waste gas of the pretreated sulfide hydrogen of step (1) (volume content is 10%) is mixed the back feed in the catalyst system and catalyzing in the one-level absorption reaction still 204 and carry out absorption reaction with the industrial waste gas that contains sulfur dioxide (volume content is 5%), 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 is more than 100 hours; As shown in Figure 1, the present embodiment absorption reaction is the two-stage tandem reaction, mist in one-level absorption reaction still behind the absorption reaction tail gas enter secondary absorption reaction still and continue absorption reaction, the technology that plural serial stage absorbs can reach the purpose 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, the filtrate cycle utilization.
With gas chromatographic detection tail gas sulfurous gas concentration, the result shows that total sulfur removal rate reaches more than 99.97%.
Embodiment 2
Consisting of of the quality percentage composition of 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 the water, obtains the 1.5L catalyst system and catalyzing, utilize measuring pump that this solution is got in the reactor.
The technology that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the industrial waste gas of the pretreated sulfide hydrogen of step (1) (volume content is 10%) is mixed the back feed in the catalyst system and catalyzing in the reactor and carry out absorption reaction with the industrial waste gas that contains sulfur dioxide (volume content is 5%), wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 1.8:1; Under 50 ℃ and 0.1MPa pressure, keep total gas flow rate 2.4L/min, this catalyst system and catalyzing continuously-running is more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, the filtrate cycle utilization.
With gas chromatographic detection tail gas sulfurous gas concentration, the result shows that total sulfur removal rate reaches more than 99.95%.
Embodiment 3
Consisting of of the quality percentage composition of 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 the water, obtains the 1.5L catalyst system and catalyzing, utilize measuring pump that this solution is got in the reactor.
The technology that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the industrial waste gas of the pretreated sulfide hydrogen of step (1) (volume content is 10%) is mixed the back feed in the catalyst system and catalyzing in the reactor and carry out absorption reaction with the industrial waste gas that contains sulfur dioxide (volume content is 5%), wherein the mixing ratio of hydrogen sulfide and sulfur dioxide is 2.2:1; Under 80 ℃ and 0.1MPa pressure, keep total gas flow rate 1.6L/min, this catalyst system and catalyzing continuously-running is more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, the filtrate cycle utilization.
With gas chromatographic detection tail gas sulfurous gas concentration, the result shows that total sulfur removal rate reaches more than 99.95%.
Embodiment 4
Consisting of of the quality percentage composition of 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 the water, obtains the 1.5L catalyst system and catalyzing, utilize measuring pump that this solution is got in the reactor.
The technology that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the industrial waste gas of the pretreated sulfide hydrogen of step (1) (volume content is 10%) is mixed the back feed in the catalyst system and catalyzing in the reactor and carry out absorption reaction with the industrial waste gas that contains sulfur dioxide (volume content is 5%), 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 is more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, the filtrate cycle utilization.
With gas chromatographic detection tail gas sulfurous gas concentration, the result shows that total sulfur removal rate reaches more than 99.95%.
Embodiment 5
Consisting of of the quality percentage composition of 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 the water, obtains the 1.5L catalyst system and catalyzing, utilize measuring pump that this solution is got in the reactor.
The technology that a kind of industrial sulphur-containing exhaust gas desulfurization is handled, described industrial sulphur-containing exhaust gas comprises following steps for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the industrial waste gas of the pretreated sulfide hydrogen of step (1) (volume content is 10%) is mixed the back feed in the catalyst system and catalyzing in the reactor and carry out absorption reaction with the industrial waste gas that contains sulfur dioxide (volume content is 5%), 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 is more than 100 hours;
(3) the product elemental sulfur of filtered and recycled step (2) absorption reaction, the filtrate cycle utilization.
With gas chromatographic detection tail gas sulfurous gas concentration, the result shows that total sulfur removal rate reaches more than 99.95%.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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 (10)
1. the catalyst system and catalyzing that industrial sulphur-containing exhaust gas desulfurization is handled is characterized in that polyalcohol, the acidic catalyst of 1-40%, surplus that this catalyst system and catalyzing comprises the component of following quality percentage composition: 2-50% are water; Described acidic catalyst is one or more in inorganic acid, inorganic acid salt, organic carboxyl acid or its soluble-salt.
2. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization processing according to claim 1 is characterized in that polyalcohol, the acidic catalyst of 2-8%, surplus that described catalyst system and catalyzing comprises the component of following quality percentage composition: 10-40% are water.
3. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization processing according to claim 1 and 2 is characterized in that described polyalcohol is selected from: one or more in ethylene glycol, glycerine, diethylene glycol, the polyethylene glycol.
4. the catalyst system and catalyzing of industrial sulphur-containing exhaust gas desulfurization processing according to claim 1 and 2 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.
5. the catalyst system and catalyzing handled of industrial sulphur-containing exhaust gas desulfurization according to claim 1 and 2, 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.
6. one kind is utilized each described catalyst system and catalyzing of claim 1-5 to carry out the technology that industrial sulphur-containing exhaust gas desulfurization is handled, and described industrial sulphur-containing exhaust gas is characterized in that for containing the industrial waste gas of hydrogen sulfide and sulfur dioxide respectively, comprises following steps:
(1) waste gas preliminary treatment: two strands of industrial waste gases that contain hydrogen sulfide and sulfur dioxide are respectively carried out preliminary treatment, guarantee that non-sulphur gas can not react with reaction medium and reactant in 2 strands of industrial waste gases under reaction condition;
(2) absorption reaction: the pretreated hydrogen sulfide containing industrial waste gas of step (1) is mixed back the feeding in the catalyst system and catalyzing carry out absorption reaction with the industrial waste gas that contains sulfur dioxide, the flow of the gaseous mixture of every liter of described catalyst system and catalyzing processing 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.
7. the technology of industrial sulphur-containing exhaust gas desulfurization processing according to claim 6 is characterized in that, the absorption reaction of described step (2) is that one or more levels series connection absorbs.
8. according to the technology of claim 6 or 7 described industrial sulphur-containing exhaust gas desulfurization processing, it is characterized in that the mixing ratio of described hydrogen sulfide and sulfur dioxide is 2:1.
9. according to the technology of claim 6 or 7 described industrial sulphur-containing exhaust gas desulfurization processing, it is characterized in that the temperature control of described step (2) absorption reaction is at 0-130 ℃, pressure is controlled at 0.1-3MPa.
10. the technology of industrial sulphur-containing exhaust gas desulfurization processing according to claim 9 is characterized in that the temperature of described step (2) absorption reaction is room temperature, and pressure is controlled at 0.1-0.2MPa.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310071884.5A CN103203242B (en) | 2013-03-06 | 2013-03-06 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103203242A true CN103203242A (en) | 2013-07-17 |
| CN103203242B CN103203242B (en) | 2015-02-25 |
Family
ID=48750769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310071884.5A Expired - Fee Related CN103203242B (en) | 2013-03-06 | 2013-03-06 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103203242B (en) |
| WO (1) | WO2014134917A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014134917A1 (en) * | 2013-03-06 | 2014-09-12 | 广州博能能源科技有限公司 | Catalyst system for desulfurization treatment of industrial sulphur-containing waste gas and process thereof |
| 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 |
| CN106467292A (en) * | 2015-08-19 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of sulfur recovery method |
| CN108636078A (en) * | 2018-05-17 | 2018-10-12 | 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 |
| CN109534297A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| 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 |
| 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 |
| CN115340887A (en) * | 2022-10-18 | 2022-11-15 | 山东鹏达生态科技股份有限公司 | Blast furnace gas fine desulfurization and sulfur recycling process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106004A (en) * | 2018-12-29 | 2019-08-09 | 河南农业大学 | Methane desulfurizer, sulfur method and purifying technique |
Citations (4)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-03-06 CN CN201310071884.5A patent/CN103203242B/en not_active Expired - Fee Related
- 2013-09-30 WO PCT/CN2013/084793 patent/WO2014134917A1/en active Application Filing
Patent Citations (4)
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014134917A1 (en) * | 2013-03-06 | 2014-09-12 | 广州博能能源科技有限公司 | Catalyst system for desulfurization treatment of industrial sulphur-containing waste gas and process thereof |
| 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 |
| CN106467292A (en) * | 2015-08-19 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of sulfur recovery method |
| 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 |
| CN109534297A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| 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 |
| CN108636078A (en) * | 2018-05-17 | 2018-10-12 | 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 |
| 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 |
| CN115340887A (en) * | 2022-10-18 | 2022-11-15 | 山东鹏达生态科技股份有限公司 | Blast furnace gas fine desulfurization and sulfur recycling process |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014134917A1 (en) | 2014-09-12 |
| CN103203242B (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103203242B (en) | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas | |
| CN102151476B (en) | Method for removing hydrogen sulfide in gas phase through oxidization under high gravity field | |
| AU2014253837B2 (en) | Absorbent, process for producing an absorbent, and process and device for separating off hydrogen sulphide from an acidic gas | |
| CN103111177B (en) | Method and device for removing hydrogen sulfide in gas phase through oxidation | |
| CN103768916A (en) | Oxidative desulphurization and brimstone recycling method | |
| CN101318099B (en) | Process for removing organic sulfur in low-temperature condition | |
| CN103432902B (en) | The method of hydrodesulfurization tail gas clean-up recovering liquid hydrocarbon and NaHS | |
| CN103318846B (en) | Method for obtaining sulfur from sulfur compounds in coal chemical plant and electric power plant | |
| CN102125802B (en) | Method for recovering and purifying waste gas during crude benzene hydrogenation refining production | |
| CN102078813A (en) | Catalyst for hydrolyzing carbonyl sulfide at low temperature and preparation method of catalyst | |
| CN101319150B (en) | Hot-soda washing desulfurization method | |
| CN103432879B (en) | The method of the ferrous flue gas desulfurization and denitrification of hypergravity complexing | |
| CN104119946B (en) | A kind of catalytic cracking flue gas desulfurization and Acidic Gas Treating technique | |
| CN103846003A (en) | Method for removing hydrogen sulfide gas | |
| CN103638802A (en) | Device and method for processing acid gas of refinery plant | |
| CN102218260B (en) | Absorbent used for removing sulfides in malodorous gases | |
| CN103801175B (en) | Polyoxometallate, preparation and application thereof | |
| CN103432889B (en) | The method of the ferrous denitrating flue gas of hypergravity complexing | |
| CN104119947A (en) | Catalytic cracking flue gas desulfurization and after-treatment process | |
| CN103894058B (en) | Method for removing hydrogen sulfide gas by using polyoxometallate | |
| CN103432878A (en) | Integrated method for wet-process desulfurization, denitrification demercuration and dearsenification of complexing ferroporphyrin smoke based on supergravity | |
| CN103768915A (en) | Liquid phase oxidative desulphurization and brimstone recycling method | |
| CN102559313B (en) | Offshore oil platform natural gas seawater Claus hydrogen sulfide removing process method | |
| CN214715580U (en) | Water injection pipeline hydrogen sulfide desulphurization unit | |
| CN205700144U (en) | A kind of low concentration hydrogen sulphide acid tail gas processing means |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150225 Termination date: 20160306 |