CN114432842A - Method and device for coupling desulfurization and preparing sulfur - Google Patents
Method and device for coupling desulfurization and preparing sulfur Download PDFInfo
- Publication number
- CN114432842A CN114432842A CN202011128055.2A CN202011128055A CN114432842A CN 114432842 A CN114432842 A CN 114432842A CN 202011128055 A CN202011128055 A CN 202011128055A CN 114432842 A CN114432842 A CN 114432842A
- Authority
- CN
- China
- Prior art keywords
- absorbent
- hydrogen sulfide
- absorption
- gas
- sulfur dioxide
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- 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
- B01D53/14—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 by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention relates to a method and a device for coupling desulfurization and preparing sulfur, and SO is used2The gas contacts with sulfur dioxide absorbent to obtain SO2An absorption liquid; adding SO2Absorption liquid and H-containing liquid2S gas is simultaneously fed into a desulfurization reaction system, and H in the desulfurization reaction system2S gas and SO2The absorption liquid reacts to generate S; separating the reaction product to obtain crude sulfur and H2S and SO2Mother liquor of absorbent.
Description
Technical Field
The invention relates to a desulfurization technology, in particular to a method and a device for coupling desulfurization and preparing sulfur.
Background
SO2And H2S is one of the major atmospheric pollutants, the emissions of which are seriously harmful to human health and environmental quality. At present, SO in coal-fired flue gas2Mainly converted into desulfurized gypsum and H in refinery dry gas by calcium method desulfurization technology2S is the production of sulphur by the gas phase Claus process.
The calcium method desulfurizing technique is a non-regenerable desulfurizing technique, and uses limestone slurry as absorbent and SO2Acid-base reaction to generate insoluble calcium saltAnd oxidizing and dehydrating the calcium salt to obtain the desulfurized gypsum. The calcium desulphurization technology is mature, but has obvious defects: the initial investment is large, and the occupied area is wide; the solubility of calcium salt in water is low, so that the scaling and blockage of an operation system are easily caused; the absorption slurry is difficult to regenerate, an absorbent needs to be continuously supplemented, and the sulfur resource cannot be recovered; the absorption product gypsum has low value and is difficult to sell; dehydration of gypsum produces large amounts of industrial waste water, and treatment of the waste water increases desulfurization costs.
The gas phase Claus process makes centralized use of a series of measures such as alcohol amine method desulfurization, Claus method sulfur recovery, matched tail gas treatment and the like. The process comprises recovering H by absorption-desorption unit operation2S, recovered H2S is sent into a combustion furnace and is partially combusted to generate SO2The combustion equation is H2S+1.5O2→SO2+H2O, the oxygen feeding amount is strictly controlled in the combustion process, so that H of 1/3 is ensured2S is converted into SO at about 1200 DEG C2SO formed2With the remainder H2S is subjected to a Claus reaction at a relatively low temperature in a conversion section (600 ℃) by means of a catalyst to generate sulfur, and the reaction equation is 2H2S+SO2→3S+2H2And O. This process is complicated, mainly because of the reactant SO2Is a warp of H2S is prepared by burning at high temperature, so that a large amount of sulfur-containing byproducts are generated, and the tail gas treatment cost is increased.
To avoid H2High temperature combustion of S, researchers are dealing with SO2And H2The claus reaction of S in the liquid phase has been extensively studied, and compared to the gas phase claus reaction, the liquid phase claus reaction is mild in conditions and less in by-products. Patent CN105521696B uses one of N, N-dialkyl imidazole, N-alkyl pyridine, N-dialkyl pyrrolidine or asymmetric tetraalkyl quaternary ammonium salt as cation, and one of chloride ion, tetrafluoroborate ion, trifluoroacetate, trifluorosulfonate or cyanoacetate as anion to synthesize ionic liquid, uses the ionic liquid as absorbent, and divides the ionic liquid into two parts to enter H2S absorption tower and SO2Absorption tower with H at the bottom2Rich solution of S and SO2The two rich liquids are mixedEntering a reactor to generate liquid-phase Claus reaction. Patent CN109529567A will contain H2S gas and SO-containing gas2The gas is introduced into the bottom of the packing tower through a gas distributor, the top of the packing tower is sprayed with an absorbent from a tail gas absorption device, and SO in the gas is obtained under normal temperature and pressure2And H2S is subjected to liquid-phase Claus reaction in a reactor, reaction products are solid sulfur and water, reaction tail gas enters a tail gas absorption device, the reaction products are sent to a separator for solid-liquid separation to obtain sulfur and an absorbent, and the absorbent is sent to the tail gas absorption device.
The current liquid-phase Claus reaction process mainly comprises two processes, one process is SO-containing2And a gas containing H2Introducing S gas into a packed tower to perform liquid-phase Claus reaction in an absorbent, wherein the S gas contains SO2And an absorption rich liquid containing H2The absorption rich liquid of S is subjected to liquid phase Claus reaction in the reactor. However, the core of the liquid phase claus process lies in the absorbent, which not only affects the performance of the liquid phase claus reaction, but also determines the rationality of the liquid phase claus process. For example, patent CN105521696B proposes a process in which the same absorbent is introduced into H in two streams2S absorption tower and SO2Absorption towers to respectively realize H2S and SO2Removal of (2) containing H2Rich solution of S and SO2The rich liquid is mixed and enters a reactor to generate liquid phase Claus reaction, and after the reaction, the regenerated absorbent is returned to an absorption tower through operations of drying, centrifugation, flash evaporation and the like, but the method provided by the patent has poor stability and is generally difficult to operate, and residual SO in the reaction is generated2The absorbent is difficult to be desorbed in the subsequent absorbent recovery process, thereby causing the deactivation of the absorbent. When the reaction is finished, the residual H in the materials is difficult to separate out by the reaction system through solid-liquid separation2S brings more pollution to the environment. The water generated by the reaction dilutes the absorbent to cause the accumulation of system moisture, and the oxygen in the flue gas can oxidize the sulfite part in the absorption rich solution into sulfate radical. It is reported that the absorption effect of sulfur dioxide can be reduced by 50% at a sulfate radical mass concentration of 2% at the maximum. In addition, solids are formed in the liquid phase Claus reaction and should therefore be usedThe reaction is avoided in the packed tower, otherwise the tower is easy to be blocked, the process is difficult to operate, and the desulfurization cost is high.
For the problems of difficult operation and high desulfurization cost of the existing liquid-phase Claus process, no document proposes an improved process at present.
Disclosure of Invention
The invention aims to solve the problems that the existing liquid-phase Claus process is difficult to operate and the desulfurization cost is high, and provides a novel method for coupling desulfurization and preparing sulfur so as to further improve the operation stability and the economical efficiency of the liquid-phase Claus process. Effectively remove SO in coal-fired flue gas2Removal of and H from refinery dry gas2The removal of S is coupled, the standard emission of coal-fired flue gas and refinery dry gas is realized, sulfur resources are recycled, and the yield of sulfur is increased. The operation stability is improved and the economic benefit is improved.
In view of the above-mentioned problems, the inventors have found that the reason why the liquid phase Claus reaction is relatively difficult to operate stably is that the selection of the absorbent is dilemma if the selected absorbent is combined with H2S has little chemical interaction, then H2The S removal efficiency is poor, and a large amount of absorbent is needed to realize the standard emission of the gas. However when the absorbent is selected with H2When S has chemical action, H can be removed efficiently2Absorbent of S, but due to H2S is much less acidic than SO2Is acidic and can efficiently remove H2The S absorbent can certainly and efficiently remove SO2This allows the absorbent to react with SO when the Claus reaction is carried out in the absorbent2The strong acting force can reduce H2The conversion of S makes the process still difficult to operate.
Therefore, the invention provides a method for coupling desulfurization and preparing sulfur, which comprises the following steps:
(1) containing SO2The gas contacts with sulfur dioxide absorbent to obtain SO2An absorption liquid;
(2) adding SO2Absorption liquid and H-containing liquid2S gas is simultaneously fed into a desulfurization reaction system, and H in the desulfurization reaction system2S gas and SO2The absorption liquid reacts to generate S;
(3) separating the reaction product in the step (2) to separate out crude products of sulfur and H2S and SO2Mother liquor of absorbent.
Further, the sulfur dioxide absorbent in the step (1) is an alkaline solution which has a chemical action with sulfur dioxide and has no chemical action with hydrogen sulfide. Preferably, the absorbent contains a compound having a functional group of-COO-(carboxyl anion), -NHx- (x ═ 0,1,2,3) or O-More preferably contains a functional group of-COO-(carboxyl anion) or O-At least one of (1). It is further preferred that the absorbent contains a compound selected from at least one of sodium lactate, potassium lactate, tetramethylguanidine lactate, ethanolamine lactate, imidazole, hydroxyethylpiperazine, or sodium phenolate.
Further, the SO is contained in the step (1)2The gas is coal-fired flue gas.
Further, the H content in the step (2)2The S gas is refinery dry gas. Containing H2The S gas is preferably pretreated before being sent to the desulfurization reaction system to remove impurities and concentrate the content. Preferably after concentration, contains H2H in S gas2The concentration of S is 0.05-100%. The pretreatment is preferably carried out using a hydrogen sulfide absorption column and a hydrogen sulfide desorption column. The hydrogen sulfide absorption tower is preferably a packed tower, the operation temperature is 9-60 ℃, and the pressure is 0.05-1 MPaA. The hydrogen sulfide desorption tower is preferably a packed tower, the operation temperature is 100-140 ℃, and the pressure is 0.05-0.3 MPaA. And a condensing device is arranged at the top of the sulfuration desorption tower, and the condensate liquid is subjected to total reflux.
The desulfurization reaction system in the step (2) is provided with at least one liquid-phase Claus reactor, and the liquid-phase Claus reactor is a stirred tank reactor. The reaction temperature is 9-80 ℃, the pressure is 0.05-1.5 MPaA, and the molar ratio of the hydrogen sulfide to the sulfur dioxide entering the reactor is 0.5-2.5.
And (3) performing separation in at least one centrifugal separation step to realize solid-liquid separation, washing the solid at least once, and centrifuging the washing product at least once to obtain a crude product of sulfur. And (3) returning all the gas generated in the separation process to the desulfurization reaction system in the step (2). The centrifuge and the washing tank are provided with exhaust ducts so that all the gas generated in the centrifuging and washing operations is returned to the desulfurization reaction system.
And (4) drying the crude product sulfur separated in the step (3) at least once to obtain a product sulfur, wherein the drying device is provided with an exhaust pipeline, and light components such as water, hydrogen sulfide and the like absorbed in the crude product sulfur are all returned to the desulfurization reaction system.
Further, SO separated in step (3)2The preferable part of the mother liquid of the absorbent enters a sulfuric acid removal system, and the mass of the mother liquid entering the sulfuric acid removal system is 0.5 to 99.5 percent of the total mass of the mother liquid. The desulfation system is preferably a stirred tank reactor. Adding a desulfurating agent into the desulfurating system, wherein the desulfurating agent is one or more of calcium carbonate, calcium oxide, calcium hydroxide, barium carbonate, barium oxide and barium hydroxide. The ratio of the addition amount of the desulfating agent to the amount of the sulfuric acid is 1:1 in terms of molar ratio. The reaction system is centrifuged at least once to realize solid-liquid separation, the solid is washed at least once, the washing product is centrifuged at least once to obtain sulfate, the centrifuge and the washing tank are provided with exhaust pipelines, and all gas generated in the centrifuging and washing operations returns to the reactor.
Step (3) containing SO2The part of the mother liquid of the absorbent which does not enter the sulfuric acid removal system is mixed with the part of the mother liquid of the absorbent which is subjected to sulfuric acid removal by the sulfuric acid removal system, and the part of the mother liquid of the absorbent which is not introduced into the sulfuric acid removal system is preferably introduced into an absorbent recovery system. The absorbent recovery system includes a stripper that removes unreacted hydrogen sulfide. The stripping tower is a packed tower, the operating temperature is 100-140 ℃, the pressure is 0.05-0.3 MPaA, and the mother liquor at the bottom of the tower is used for removing water, washing water, liquid-phase Claus reaction and generated water of the desulfation reaction in the flue gas carried by the sulfur dioxide absorbent through at least one evaporator. The mother liquor concentrated by the evaporator is sent to a sulfur dioxide absorption system after being cooled in multiple stages to be used as a sulfur dioxide absorbent, gas containing sulfur dioxide is purified to obtain absorption pregnant solution containing sulfur dioxide, and the absorption pregnant solution returns to the reaction system. The sulfur dioxide absorption system is preferably a sulfur dioxide absorption towerPreferably a packed tower, the operating temperature is 9-60 ℃, and the pressure is 0.05-1 MPaA.
In another aspect, the present invention provides a coupled desulfurization and sulfur production apparatus, comprising: the system comprises a sulfur dioxide absorption system, a reaction system and a separation system, wherein the reaction system is connected with the sulfur dioxide absorption system through a pipeline, and the separation system is connected with the reaction system through a pipeline.
Further, a hydrogen sulfide pretreatment system is preferably provided in connection with the reaction system. The hydrogen sulfide pretreatment system is preferably a hydrogen sulfide absorption and desorption system, and the hydrogen sulfide absorption and desorption system comprises unit equipment such as a hydrogen sulfide absorption tower, a hydrogen sulfide desorption tower, a kettle liquid pump and a heat exchanger.
The reaction system comprises unit equipment such as a liquid phase Claus reactor, a pump and the like.
The separation system comprises a centrifuge, a washing tank and other unit equipment. A drying system and a desulphation system are preferably arranged after the separation system and are respectively connected with the separation system. The drying system comprises a preheater, a dryer and other unit equipment. The desulfurating system comprises a desulfurating reactor, a centrifuge, a preheater, a dryer and other unit equipment.
The separation system is preferably connected with an absorbent recovery system, which comprises a stripping tower, a heat exchanger, an evaporator and other unit equipment. The sulfur dioxide absorption system comprises unit equipment such as a sulfur dioxide absorption tower and a kettle liquid pump.
The invention overcomes the dilemma of selecting the existing liquid-phase Claus reaction absorbent, and adopts the absorbent which can react with SO2Has a chemical action with H2Absorbent without chemical action of S for efficiently absorbing SO2And catalysing the liquid phase Claus reaction with H in the gas phase2S and containing SO2The rich solution is reacted in the stirring reaction kettle, the volume of the reactor is reduced, the blockage problem of a packed tower is avoided, the operation is easy to carry out, and the dosage of the absorbent is less. In addition, the reactant SO2Derived from coal-fired flue gas, compared with the prior gas-phase Claus reaction process SO2The preparation method has low combustion temperature, greatly reduces the generation of sulfur-containing VOCs, and has unreacted H2S is all returned to the reaction system to the maximum extentReduces the environmental pollution, and the desulfurating and absorbent pretreatment system can ensure SO2The absorbent maintains stable absorption performance and water content.
Drawings
FIG. 1 is a schematic diagram of a coupled desulfurization and sulfur production method and apparatus according to the present invention.
In FIG. 1, 1 is refinery dry gas, 2 is purified refinery dry gas, and 3 is H-containing gas from hydrogen sulfide absorption and desorption system2S gas, 4 is H-containing gas from the separation system2S gas, 5 is H-containing gas exiting the drying system2Gas of S, 6 being SO2Absorbing rich liquid, 7 being a reaction product out of the reaction system, 8 being crude sulfur, 9 being product sulfur, and 10 being SO-containing2Mother liquor of absorbent, 11 is H-containing solution of sulfuric acid removal system2S gas 12 is SO-containing gas after sulfuric acid removal2Mother liquor of absorbent 13 is SO-containing liquid entering a condenser at the top of the tower2Mother liquor of absorbent, 14 is top gas of stripping tower, 15 is SO-containing gas entering stripping tower2Mother liquor of absorbent, 16 is waste water, 17 is SO2The absorbent 18 is coal-fired flue gas, 19 is purified coal-fired flue gas, and A is a tower top condenser. B is a mother liquor preheater, C is an absorbent cooler, D is a condenser, E is an evaporator, and F is a stripping tower. S1 is a hydrogen sulfide absorption desorption system, S2 is a separation system, S3 is a drying system, S4 is a desulfation system, S5 is a reaction system, and S6 is a sulfur dioxide absorption system.
Detailed Description
The invention is further illustrated by the following specific examples to illustrate the content of the invention. It should be understood that the scope of the invention is not limited by the specific embodiments.
As shown in figure 1, the refinery dry gas 1 containing hydrogen sulfide realizes gas purification and hydrogen sulfide recovery through a hydrogen sulfide absorption desorption system S1, the purified refinery dry gas 2 is discharged from the hydrogen sulfide absorption desorption system S1, and the refinery dry gas containing H and discharged from a hydrogen sulfide absorption desorption system S12S gas 3 and H-containing gas from separation system S22S gas 4, H-containing gas from drying system S32Gas of SBody 5, H-containing gas from the sulfuric acid removal system of the sulfuric acid removal system S42The gas 11 of S and the stripper overhead gas 14 exiting the absorbent pretreatment system (here, stripper F) are mixed into a reaction system S5.
Containing SO2The coal-fired flue gas 18 enters a sulfur dioxide absorption system S6, and is preheated by a mother liquor preheater B in S62The absorbent 17 is contacted, absorbed and purified, the purified coal-fired flue gas 19 is discharged out of a sulfur dioxide absorption system, and the obtained SO after absorbing sulfur dioxide2The absorbing rich liquid 6 enters the reaction system S5.
In the reaction system S5H2The S gas and sulfur dioxide in the absorption pregnant solution generate liquid-phase Claus reaction to generate solid sulfur and water, the reaction product 7 of the reaction system enters a separation system S2 for solid-liquid separation, and a crude product of sulfur 8 and a mother solution containing sulfur dioxide absorbent are obtained after centrifugation and washing. A part of mother liquor 10 containing sulfur dioxide absorbent enters a sulfuric acid removal system S4, and SO is contained after sulfuric acid is removed in the sulfuric acid removal system2Mother liquor 12 of the absorbent is mixed with the rest mother liquor to form SO-containing liquid entering a tower top condenser2Mother liquor 13 of the absorbent, and SO-containing gas serving as a gas inlet stripping tower after heat exchange between the mixed mother liquor 13 and the overhead gas of the stripping tower2The mother liquor 15 of the absorbent enters the top of the stripping tower, and enters an evaporation system (an evaporator E in the embodiment) for concentration after unreacted hydrogen sulfide is removed. The waste water discharged from the evaporation system is condensed by the condenser D and discharged as waste water 16. The concentrated mother liquor is sent to a sulfur dioxide absorption system S6 to be used as a sulfur dioxide absorbent after being cooled in multiple stages (a mother liquor preheater B and an absorbent cooler C), gas containing sulfur dioxide is purified to obtain sulfur dioxide absorption pregnant solution 6, and the absorption pregnant solution 6 returns to the reaction system. The stripper overhead gas 14 is returned to the reaction system S5 after passing through the overhead condenser a. And (5) conveying the crude product sulfur 8 into a drying system S3 for drying to obtain a product sulfur 9.
[ example 1 ]
A certain refinery adopts the liquid phase Claus reaction process shown in FIG. 1, and the inlet flow of refinery dry gas 1 is 30000m3/h，H2The S concentration is 2%, and the hydrogen sulfide absorption and desorption system comprises a hydrogen sulfide absorption tower and a sulfideA hydrogen desorption tower. The operation temperature of the hydrogen sulfide absorption tower is 40 ℃, the pressure is 0.5MPaA, the operation temperature of the hydrogen sulfide desorption tower is 109 ℃, and the operation pressure is 0.14 MPaA. Coal-fired flue gas 18 flow 330000m3/h，SO2Concentration of 1000ppm, SO2The absorbent is 50% ethanolamine lactate aqueous solution. The desulfurating agent is calcium hydroxide, the molar ratio of the calcium hydroxide to sulfuric acid in the mother liquor is 1:1, and H enters a reaction system2S accounts for 80 mass percent and H2S and SO in rich solution2At a reactor temperature of 25 ℃ and a pressure of 0.3MPaA, in a molar ratio of 1.8: 1.
The device runs stably and the dry gas H is discharged2The concentration of S is less than or equal to 1ppm, and the outlet flue gas SO2The concentration is less than or equal to 10ppm, the conversion rate of hydrogen sulfide is more than or equal to 90 percent, the yield of sulfur is 1275kg/h, and the purity is more than or equal to 99.99 percent;
5000 ten thousand of equipment investment and 0.7 yuan/kg SO of desulfurization cost2。
[ example 2 ]
A certain refinery adopts the liquid phase Claus reaction process shown in FIG. 1, and the inlet flow of refinery dry gas 1 is 30000m3/h，H2The S concentration was 2%. The hydrogen sulfide absorption desorption system comprises a hydrogen sulfide absorption tower and a hydrogen sulfide desorption tower. The operation temperature of the hydrogen sulfide absorption tower is 40 ℃, the pressure is 0.5MPaA, the operation temperature of the hydrogen sulfide desorption tower is 109 ℃, and the operation pressure is 0.14 MPaA. Coal-fired flue gas 18 flow 330000m3/h，SO2Concentration of 1000ppm, SO2The absorbent is 50% sodium lactate aqueous solution, the desulfurating agent is calcium hydroxide, the molar ratio of the calcium hydroxide to the sulfuric acid in the mother liquor is 1:1, and H enters a reaction system2S content of 80% by mass, H2S and SO in rich solution2At a reactor temperature of 25 ℃ and a pressure of 0.3MPaA, in a molar ratio of 2.2: 1.
The device runs stably and dry gas H is discharged2The concentration of S is less than or equal to 1ppm, and the outlet flue gas SO2The concentration is less than or equal to 10ppm, the conversion rate of hydrogen sulfide is more than or equal to 95 percent, the yield of sulfur is 1275kg/h, and the purity is more than or equal to 99.99 percent.
5000 ten thousand of equipment investment and 0.6 yuan/kg SO of desulfurization cost2。
[ example 3 ]
From a refineryUsing the liquid phase Claus reaction process shown in FIG. 1, the inlet flow rate of refinery dry gas 1 is 30000m3/h，H2The S concentration was 2%. The hydrogen sulfide absorption desorption system comprises a hydrogen sulfide absorption tower and a hydrogen sulfide desorption tower. The operation temperature of the hydrogen sulfide absorption tower is 30 ℃, the pressure is 0.8MPaA, the operation temperature of the hydrogen sulfide desorption tower is 109 ℃, and the operation pressure is 0.14 MPaA. Coal-fired flue gas 18 flow 330000m3/h，SO2Concentration of 1000ppm, SO2The absorbent is 50% 1-methylimidazole water solution. The desulfurating agent is calcium hydroxide, the molar ratio of the calcium hydroxide to sulfuric acid in the mother liquor is 1:1, and H enters a reaction system2S content of 80% by mass, H2S and SO in rich solution2At a reactor temperature of 60 ℃ and a pressure of 1.2MPaA, in a molar ratio of 1.0: 1.
The device runs stably and dry gas H is discharged2The concentration of S is less than or equal to 1ppm, and the outlet flue gas SO2The concentration is less than or equal to 5ppm, the conversion rate of hydrogen sulfide is more than or equal to 90 percent, the yield of sulfur is 1275kg/h, and the purity is more than or equal to 99.99 percent.
5000 ten thousand of equipment investment and 0.8 yuan/kg SO of desulfurization cost2。
[ example 4 ] A method for producing a polycarbonate
A certain refinery adopts the liquid phase Claus reaction process shown in FIG. 1, and the inlet flow of refinery dry gas 1 is 30000m3/h，H2S concentration 2%, outlet dry gas H2The concentration of S was 2 ppm. The hydrogen sulfide absorption desorption system comprises a hydrogen sulfide absorption tower and a hydrogen sulfide desorption tower. The operating temperature of the hydrogen sulfide absorption tower is 20 ℃, the pressure is 0.3MPaA, the operating temperature of the hydrogen sulfide desorption tower is 120 ℃, and the operating pressure is 0.2 MPaA. Coal-fired flue gas 18 flow 330000m3/h，SO2Concentration of 1000ppm, SO2The absorbent is 50% sodium phenolate water solution, and the outlet flue gas SO2The concentration was 3 ppm. The desulfurating agent is calcium hydroxide, the molar ratio of the calcium hydroxide to sulfuric acid in the mother liquor is 1:1, and H enters a reaction system2S mass percent concentration of 60%, H2S and SO in rich solution2The molar ratio of (1: 0.8) to (4) is 0.1: 1, the temperature of the reactor is 45 ℃, the pressure is 0.1MPaA, the conversion rate of hydrogen sulfide is 80%, the yield of sulfur is 1275kg/h, and the purity is 99.99%.
The device runs stably and dry gas H is discharged2The concentration of S is lower thanLess than or equal to 2ppm, and outlet flue gas SO2The concentration is less than or equal to 3ppm, the conversion rate of hydrogen sulfide is more than or equal to 80 percent, the yield of sulfur is 1275kg/h, and the purity is more than or equal to 99.99 percent.
5000 ten thousand of equipment investment and 0.6 yuan/kg SO of desulfurization cost2。
[ COMPARATIVE EXAMPLE 1 ]
The SO in coal-fired flue gas is removed by calcium desulphurization technology in a certain refinery2And gas phase Claus reaction process for removing H in refinery dry gas2S, the inlet flow of refinery dry gas is 30000m3/h，H2S concentration 2%, outlet dry gas H2The concentration of S is 1ppm, the operation temperature of a hydrogen sulfide absorption tower is 40 ℃, the pressure is 0.5MPaA, the operation temperature of a hydrogen sulfide desorption tower is 109 ℃, the operation pressure is 0.14MPaA, and the flow rate of coal-fired flue gas is 330000m3/h，SO2Concentration is 1000ppm, outlet flue gas SO2The concentration is 30ppm, the limestone consumption is 1200kg/h, the solid waste generation is 1200kg/h, and the waste water is 10000 kg/h.
1.6 million yuan equipment investment and 1.6 yuan per kg SO desulfurization cost2。
[ COMPARATIVE EXAMPLE 2 ]
A certain refinery adopts the process reported by CN105521696B at present, takes N, N-dialkyl imidazole trifluoroacetate as an absorbent, the process conditions are as in example 1, the device runs stably in the initial running stage, and dry gas H is discharged2The concentration of S is less than or equal to 5ppm, and the outlet flue gas SO2The concentration is less than or equal to 25ppm, the conversion rate of hydrogen sulfide is more than or equal to 90 percent, the yield of sulfur is 1275kg/h, the purity is more than or equal to 99.99 percent, the content of sulfate radical in the absorption pregnant solution reaches 3 percent by weight after the device runs for 2 months, and the sulfur content is 3 percent by weight for SO2Absorption capacity is reduced by 30%, and SO is discharged2The concentration is increased to 200ppm, the absorbent is deactivated, and the device is shut down and overhauled.
Claims (14)
1. The method for coupled desulfurization and sulfur preparation is characterized by comprising the following steps:
(1) containing SO2The gas contacts with sulfur dioxide absorbent to obtain SO2An absorption liquid;
(2) adding SO2Absorption liquid and H-containing liquid2S gas is simultaneously sent into a desulfurization reaction systemH in desulfurization reaction system2S gas and SO2The absorption liquid reacts to generate S;
(3) separating the reaction product in the step (2) to separate out crude products of sulfur and H2S and SO2Mother liquor of absorbent.
2. The method according to claim 1, wherein the sulfur dioxide absorbent in step (1) is an alkaline solution which has a chemical interaction with sulfur dioxide and no chemical interaction with hydrogen sulfide; preferably, the absorbent contains a compound having a functional group of-COO-(carboxyl anion), -NHx- (x ═ 0,1,2,3) or O-More preferably contains a functional group of-COO-(carboxyl anion) or O-At least one of (1).
3. The method according to claim 1 or 2, characterized in that the sulphur dioxide absorbent in step (1) contains a compound selected from at least one of sodium lactate, potassium lactate, tetramethylguanidine lactate, ethanolamine lactate, imidazole, hydroxyethylpiperazine or sodium phenolate.
4. The method according to claim 1, wherein the H is contained in the step (2)2The S gas is pretreated before being sent into a desulfurization reaction system to concentrate the content; after concentration, contains H2H in S gas2The concentration of S is 0.05% -100%.
5. The method according to claim 4, wherein the pretreatment is performed using a hydrogen sulfide absorption column and a hydrogen sulfide desorption column; the hydrogen sulfide absorption tower is a packed tower, the operation temperature is 9-60 ℃, and the pressure is 0.05-1 MPaA; the hydrogen sulfide desorption tower is a packed tower, the operation temperature is 100-140 ℃, and the pressure is 0.05-0.3 MPaA.
6. The method of claim 1, wherein the desulfurization reaction system in step (2) has at least one liquid phase Claus reactor, and the liquid phase Claus reactor is a stirred tank reactor; the reaction temperature is 9-80 ℃, the pressure is 0.05-1.5 MPaA, and the molar ratio of the hydrogen sulfide to the sulfur dioxide entering the reactor is 0.5-2.5.
7. The method of claim 1, wherein the SO separated in step (3) is2The absorbent mother liquor enters a sulfuric acid removal system, and the mass of the mother liquor entering the sulfuric acid removal system is 0.5-99.5% of the total mass of the mother liquor.
8. The method of claim 7, wherein a desulfating agent is added to the desulfating system, and the desulfating agent is one or more of calcium carbonate, calcium oxide, calcium hydroxide, barium carbonate, barium oxide, and barium hydroxide.
9. The method of claim 7, wherein step (3) comprises SO2The part of the mother liquor of the absorbent which does not enter the sulfuric acid removal system is mixed with the part of the mother liquor of the absorbent which is subjected to the sulfuric acid removal by the sulfuric acid removal system and enters the absorbent recovery system; the absorbent recovery system includes a stripper that removes unreacted hydrogen sulfide.
10. The method of claim 9, wherein the stripping column is a packed column operating at a temperature of 100 ℃ to 140 ℃ and a pressure of 0.05mpa to 0.3mpa, and the mother liquor at the bottom of the stripping column is used to remove water, washing water, and water produced by the liquid phase claus reaction and the desulfation reaction from the flue gas entrained by the sulfur dioxide absorbent through at least one evaporator.
11. The method as claimed in claim 10, wherein the mother liquor concentrated by the evaporator is sent to a sulfur dioxide absorption system as a sulfur dioxide absorbent after being cooled in multiple stages, the sulfur dioxide absorption system is a sulfur dioxide absorption tower, the sulfur dioxide absorption tower is a packed tower, the operation temperature is 9-60 ℃, and the pressure is 0.05-1 MPaA.
12. An apparatus for coupled desulfurization and sulfur production, the apparatus comprising: the system comprises a sulfur dioxide absorption system, a reaction system and a separation system, wherein the reaction system is connected with the sulfur dioxide absorption system through a pipeline, and the separation system is connected with the reaction system through a pipeline.
13. The device according to claim 12, wherein a hydrogen sulfide pretreatment system is connected to the reaction system, the hydrogen sulfide pretreatment system is a hydrogen sulfide absorption and desorption system, and the hydrogen sulfide absorption and desorption system comprises a hydrogen sulfide absorption tower, a hydrogen sulfide desorption tower, a kettle liquid pump and a heat exchanger.
14. The apparatus of claim 12, wherein a desulphation system is provided in connection with the separation system after the separation system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011128055.2A CN114432842A (en) | 2020-10-20 | 2020-10-20 | Method and device for coupling desulfurization and preparing sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011128055.2A CN114432842A (en) | 2020-10-20 | 2020-10-20 | Method and device for coupling desulfurization and preparing sulfur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114432842A true CN114432842A (en) | 2022-05-06 |
Family
ID=81357109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011128055.2A Pending CN114432842A (en) | 2020-10-20 | 2020-10-20 | Method and device for coupling desulfurization and preparing sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114432842A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB980751A (en) * | 1961-01-16 | 1965-01-20 | Shell Int Research | Removal of acidic gases from gaseous mixtures |
| US4855124A (en) * | 1985-03-08 | 1989-08-08 | Jgc Corporation | Process for the desulfurization of gas containing hydrogen sulfide |
| JPH0248018A (en) * | 1988-06-21 | 1990-02-16 | Inst Fr Petrole | Burning and desulfurization method and device in circulating bed for gas outflow including incomplete combustion gas, so2, so3 and/or h2s |
| CN101015766A (en) * | 2006-12-30 | 2007-08-15 | 苏建华 | Electricity factory desulfurization unit using sodium citrate-sulfur method |
| CN203200228U (en) * | 2013-02-01 | 2013-09-18 | 济钢集团有限公司 | Self-circulating desulfurizer |
| CN103406007A (en) * | 2013-05-16 | 2013-11-27 | 福建省双旗山矿业有限责任公司 | Recovery process for sulphur in gold concentrate roasting smoke |
| CN103551018A (en) * | 2013-11-07 | 2014-02-05 | 中天环保产业(集团)有限公司 | Sulfur-containing tail gas purifying and recycling method |
| CN105521696A (en) * | 2015-11-26 | 2016-04-27 | 南京大学 | Room-temperature liquid-phase Claus process taking ionic liquid as media |
| CN107297123A (en) * | 2017-08-21 | 2017-10-27 | 太原师范学院 | A kind of use carboxylic acid salt solution absorbing sulfur dioxide in flue and the process of equality of temperature regeneration |
| CN108704474A (en) * | 2018-05-31 | 2018-10-26 | 武汉钢铁有限公司 | Coke oven flue gas and Claus tail gases combined treatment process |
| CN108910830A (en) * | 2018-08-07 | 2018-11-30 | 中国恩菲工程技术有限公司 | The method for preparing sulphur using the sulfur dioxide in flue gas |
| CN109529567A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of technique of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| CN109876601A (en) * | 2019-03-19 | 2019-06-14 | 北京化工大学 | A kind of functionalized ion liquid absorbing sulfur dioxide in flue and with the process of claus reaction low-temp recovery |
-
2020
- 2020-10-20 CN CN202011128055.2A patent/CN114432842A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB980751A (en) * | 1961-01-16 | 1965-01-20 | Shell Int Research | Removal of acidic gases from gaseous mixtures |
| US4855124A (en) * | 1985-03-08 | 1989-08-08 | Jgc Corporation | Process for the desulfurization of gas containing hydrogen sulfide |
| JPH0248018A (en) * | 1988-06-21 | 1990-02-16 | Inst Fr Petrole | Burning and desulfurization method and device in circulating bed for gas outflow including incomplete combustion gas, so2, so3 and/or h2s |
| CN101015766A (en) * | 2006-12-30 | 2007-08-15 | 苏建华 | Electricity factory desulfurization unit using sodium citrate-sulfur method |
| CN203200228U (en) * | 2013-02-01 | 2013-09-18 | 济钢集团有限公司 | Self-circulating desulfurizer |
| CN103406007A (en) * | 2013-05-16 | 2013-11-27 | 福建省双旗山矿业有限责任公司 | Recovery process for sulphur in gold concentrate roasting smoke |
| CN103551018A (en) * | 2013-11-07 | 2014-02-05 | 中天环保产业(集团)有限公司 | Sulfur-containing tail gas purifying and recycling method |
| CN105521696A (en) * | 2015-11-26 | 2016-04-27 | 南京大学 | Room-temperature liquid-phase Claus process taking ionic liquid as media |
| CN107297123A (en) * | 2017-08-21 | 2017-10-27 | 太原师范学院 | A kind of use carboxylic acid salt solution absorbing sulfur dioxide in flue and the process of equality of temperature regeneration |
| CN109529567A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of technique of hydrogen sulfide and sulfur dioxide reaction desulfuration |
| CN108704474A (en) * | 2018-05-31 | 2018-10-26 | 武汉钢铁有限公司 | Coke oven flue gas and Claus tail gases combined treatment process |
| CN108910830A (en) * | 2018-08-07 | 2018-11-30 | 中国恩菲工程技术有限公司 | The method for preparing sulphur using the sulfur dioxide in flue gas |
| CN109876601A (en) * | 2019-03-19 | 2019-06-14 | 北京化工大学 | A kind of functionalized ion liquid absorbing sulfur dioxide in flue and with the process of claus reaction low-temp recovery |
Non-Patent Citations (1)
| Title |
|---|
| 童志权等: "《工业废气污染控制与利用》", 31 January 1989, 化学工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2011320511B2 (en) | Regenerative recovery of sulfur dioxide from effluent gases | |
| CA1106147A (en) | Recovering sulfur from gas streams containing hydrogen sulfur | |
| US3438722A (en) | Removal of sulfur oxides from flue gas | |
| CN102181308B (en) | Vacuum potassium carbonate coke oven gas desulfurization-sulfuric acid preparation process and processing system thereof | |
| MX2014013257A (en) | Regenerative recovery of contaminants from effluent gases. | |
| RU2126863C1 (en) | Method of separating out of sulfur compounds (versions) | |
| US3944649A (en) | Multistage process for removing sulfur dioxide from stack gases | |
| US4133650A (en) | Removing sulfur dioxide from exhaust air | |
| US3971844A (en) | Method for removing sodium sulfate from aqueous solutions | |
| US3438727A (en) | Absorbent regeneration using carbon regenerant | |
| WO2002072243A1 (en) | Process for producing ammonium thiosulphate | |
| EP0097240B1 (en) | Process for removal of sulfur oxides from hot gases | |
| CN114854457A (en) | Decarbonization and desulfurization method for mixed gas containing combustible gas | |
| US4634582A (en) | Sulfur dioxide removal process | |
| CN110252090B (en) | Method for improving absorption capacity and utilization rate of sodium sulfite desulfurization process by using triethanolamine | |
| CN114432842A (en) | Method and device for coupling desulfurization and preparing sulfur | |
| CN1155434C (en) | Process for preparation of fertilizers and sulfure compounds | |
| CN109803747B (en) | Method for cleaning waste gas from viscose production and catalyst therefor | |
| CN111821844B (en) | Desulfurization process method combining dry oxidation and wet oxidation | |
| CN115477963A (en) | Absorption method for acid gas in coal-to-methanol synthesis gas | |
| US4021202A (en) | Apparatus for removing sulfur dioxide from stack gases | |
| US4206187A (en) | Process for removing sulfur dioxide from gas | |
| PT100100B (en) | PROCESS FOR RECOVERING ENERGY AND CHEMICALS FROM BLACK LIQUOR | |
| JPH02214523A (en) | Process for removing hyurogen sulfide from gas mixture | |
| CA1079492A (en) | Process for removing sulfur dioxide from a gas stream |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |