WO2016198369A1 - Réduction de sulfure d'hydrogène par l'intermédiaire de l'élimination de trioxyde de soufre - Google Patents
Réduction de sulfure d'hydrogène par l'intermédiaire de l'élimination de trioxyde de soufre Download PDFInfo
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- WO2016198369A1 WO2016198369A1 PCT/EP2016/062830 EP2016062830W WO2016198369A1 WO 2016198369 A1 WO2016198369 A1 WO 2016198369A1 EP 2016062830 W EP2016062830 W EP 2016062830W WO 2016198369 A1 WO2016198369 A1 WO 2016198369A1
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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
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
Definitions
- the present invention relates to the use of gas-solid sepa ⁇ ration unit operations for the removal of sulfur trioxide (SO 3 ) formed by catalytic oxidation of hydrogen sulfide (3 ⁇ 4S) with the purpose of removing 3 ⁇ 4S from a gas. More specifically, this catalytic oxidation of 3 ⁇ 4S first yields sulfur dioxide (S0 2 ) and then SO 3 through the use of known catalysts, and the subsequent recovery of SO 3 takes place in a separation unit, such as a filter or scrubbing unit, using a sorbent, which converts SO 3 to a sulfate to be sep ⁇ arated in said unit.
- SO 3 sulfur trioxide
- 3 ⁇ 4S hydrogen sulfide
- the process of removing 3 ⁇ 4S from a gas can be summarized schematically as follows: A potentially pre-heated 3 ⁇ 4S- containing gas is mixed with air or oxygen, and then the mixture is fed to a first catalyst-containing reactor via a heat exchanger. In this first reactor, 3 ⁇ 4S is oxidized to sulfur dioxide (S0 2 ) ⁇ The effluent from the first reactor is passed to a second catalyst-containing reactor, where the SO 2 is oxidized to SO 3 . Then the S03-containing effluent is fed to a separation unit, into which a sorbent slurry or powder is injected. The purpose of this is to remove SO 3 by converting it to a sulfate that can be separated from the gas.
- the energy efficiency of the plant can be improved signifi ⁇ cantly by means of heat integration, i.e. the cold feed gas is heated to a suitable temperature by the hot effluent gas from the last reactor or the separation unit in a heat exchanger.
- the hot effluent gas can be used to produce steam.
- the first oxidation reactor contains a monolith type cata ⁇ lyst
- the second oxidation reactor contains a supported liquid phase (SLP) catalyst, more specifically a VK cata- lyst.
- SLP supported liquid phase
- the 3 ⁇ 4S can also, on purpose, be oxidized directly to SO 3 in said first reactor by proper choice of oxidation cata ⁇ lyst and reaction conditions.
- the effluent from the first reactor is fed to the particle separation unit for removal of SO 3 in the form of a sulfate.
- oxida ⁇ tion catalyst for this direct oxidation to SO 3 a noble metal catalyst, such as a Pt/Pd catalyst, is used.
- the present invention utilizes catalytic oxidation of 3 ⁇ 4S to SO 2 at temperatures between 150 and 500°C, preferably between 180 and 450°C and most preferably between 200 and 400°C.
- catalytic oxidation therefore of ⁇ fers the possibility of reducing the use of supplemental fuel in order to increase the temperature, thereby lowering the operating costs.
- the catalytic oxidation of 3 ⁇ 4S can be performed at an oxygen concentration of below 2 vol%, measured at the outlet of the 3 ⁇ 4S oxidation reac ⁇ tor, whereas combustion of 3 ⁇ 4S typically requires an oxygen concentration of more than 3 vol% at the outlet of the fur- nace . This means that the process gas flow is reduced com ⁇ pared to combustion, thereby reducing both investment and operating costs.
- the sulfate separated from the gas in the method according to the invention can easily be handled and sold, e.g. for the construction industry, or it can be landfilled. For certain applications, these are cost efficient options for the removal of 3 ⁇ 4S compared to the production of elemental sulfur or sulfuric acid.
- a monolithic type catalyst is preferably used in the reactor converting 3 ⁇ 4S to SO 2 .
- This catalyst is a corrugated fibrous monolith substrate coated with a supporting oxide. It is preferably coated with T1O 2 and subsequently impregnated with V 2 O 5 and/or WO 3 .
- the channel diameter of the corrugated monolith is between 1 and 8 mm, and the wall thickness of the corru ⁇ gated monolith is between 0.1 and 0.8 mm.
- the monolith type catalyst is preferably manufactured from a support material comprising one or more oxides of metals selected from aluminium, silicon and titanium, and the active catalytic components preferably comprise one or more oxides of a metal selected from vanadium, chromium, tungsten, molybdenum, cerium, niobium, manganese and copper. Said materials are effective in the catalytic oxidation of hydrogen sulfide at low temperatures.
- VK catalysts are specifically designed by the applicant to be used for converting SO 2 to SO 3 in any sulfuric acid plant. They are generally vanadium-based and may contain cesium as an additional catalyst promoter to enhance the action of the vanadium and activate the catalyst at a much lower temperature than conventional non-cesium catalysts. A major leap in activity has been obtained with VK catalysts containing a high fraction of vanadium in the active oxida- tion state V 5+ .
- Monoliths are increasingly being used, developed, and eval ⁇ uated as catalyst supports in many new reactor applications such as chemical and refining processes, catalytic oxida- tion, ozone abatement etc.
- the active catalyst When the active catalyst has a monolithic structure, it displays a low pressure drop.
- a number of gas-solid separation units and unit operations can be used for the removal of SO 3 formed by catalytic oxidation of 3 ⁇ 4S.
- the separation units include metal filters, electrofilters , bag filters, ceramic filters, mist filters, cyclones and scrubbers, and unit operations for the gas-solid separation include use of low velocity filter, wet ESP (electrostatic precipitator) and other kinds of polishing technologies. Wet and dry scrubbing processes are widely used to remove
- the SO2 levels from power plants are in the range from 100 to 2000 ppm, with corresponding
- the amount of SO 3 in the tail gas is within the range from 0.5% to 5% of the total SO x ( S0 2 + S0 3 ) amount, giving an SO2 to SO 3 ratio in the range of 20 to 200.
- the present invention utilizes catalytic oxidation of SO2 to SO 3 . Typically, more than 80%, preferably more than 90% and most preferably more than 95% of the SO2 is converted to SO 3 , resulting in an SO2 to SO 3 ratio below 0.25, prefer ⁇ ably below 0.11 and most preferably below 0.05.
- the high content of SO 3 makes the dry scrubbing process more effi ⁇ cient, resulting in lower scrubbing costs.
- a dry scrubber system is described in US 2013/0294992, which concerns an air quality control system useful for processing a gas stream, such as a flue gas stream emitted from a fossil fuel fired boiler, for at least partial re- moval of acidic and other polluting species, such as SO 2 ,
- US 4.314.983 describes a process for converting H 2 S to SO 2 with a solid catalyst comprising at least 5 wt% of bismuth. Essentially no SO 3 is formed in the catalytic process. In this patent it is stated that the bismuth content is neces ⁇ sary to stabilize the catalyst.
- US 2014/020399 describes a method for generating current from an exhaust gas containing 3 ⁇ 4S. The exhaust gas is com ⁇ busted, possibly under addition of supplementary fuel, and the heat released is used for current generation. The SO 2 and the SO 3 in the gas after combustion of the 3 ⁇ 4S are de- livered for desulfurization .
- US 2004/0109807 describes a method for removing SO 3 from flue gases, where a calcium hydroxide slurry is injected into the off-gases in the exhaust duct of an industrial plant, wherein sulfur-containing fuels are combusted.
- the calcium hydroxide slurry reacts with SO 3 produced as a re ⁇ sult of the combustion process and forms a primary solid calcium sulfate reaction product.
- the industrial plant in ⁇ cludes a wet scrubbing system which utilizes wet slaking of calcium oxide for the removal of sulfur oxides from off- gases .
- US 6,143,263 describes a method and a system for removing SO 3 and SO 2 from a flue gas produced by combusting of a fossil fuel.
- a calcium-based, sodium-based or magnesium- based dry sorbent is injected into the flue gas to react with and remove substantially all of the SO 3 from the flue gas, thereby producing a substantially S03-free flue gas containing both reacted dry sorbent and unreacted dry sorbent.
- the flue gas with reacted and unreacted dry sorbent is then fed to a wet scrubber to remove both the reacted and the unreacted dry sorbent, thereby making the unreacted dry sorbent available as a wet reagent for SO 2 removal .
- a method for treating a flue gas stream to remove strong acid compounds selected from HF, HC1, H 2 SO 4 and SO 3 .
- the compounds are removed by injecting a sodium sorbent, selected from sodium sesquicarbonate, sodium carbonate-bicarbonate and various forms of x trona' (trisodium hydrogen dicarbonate-dihydrate, a non- marine evaporite mineral also called sodium sesquicarbonate dihydrate; Na 3 (C0 3 ) (HC0 3 ) ⁇ 2H 2 0) into the flue gas stream.
- a sodium sorbent selected from sodium sesquicarbonate, sodium carbonate-bicarbonate and various forms of x trona' (trisodium hydrogen dicarbonate-dihydrate, a non- marine evaporite mineral also called sodium sesquicarbonate dihydrate; Na 3 (C0 3 ) (HC0 3 ) ⁇ 2H 2 0) into the flue gas stream.
- Substantially all of the sodium sorbent is calcined in the presence of the flue gas stream to form a soda ash, and the concentration of the strong acid compounds in the flue gas is reduced by reaction with the soda ash to form a sodium- based by-product.
- US 2010/0096594 describes a process for decontaminating syngas by contacting the syngas with one or more sorbents upstream of a catalytic candle filter containing a mixed cracking catalyst, wherein ammonia and tars are removed, leaving a purified syngas.
- US 2009/0277325 discloses an emission treatment system, in which particles entrained in an emission stream can be removed using various separation devices, such as electro- static precipitators, cyclone collectors and filter devic ⁇ es, e.g. candle filters.
- WO 2004/037369 describes a system and a method for removing 3 ⁇ 4S and SOx from a gas.
- the system comprises a sorbent slurry feeder and at least one reaction zone con ⁇ figured for introduction of a sorbent and the gas, and it also comprises fabric filter bags, wet scrubbing and elec ⁇ trostatic precipitator technologies.
- it does not comprise a mist filter in combination with the separation unit for removal of acid mist and also not a quench scrub ⁇ ber for the removal of residual SO 3 , which is not present as a mist.
- the treatment method for the removal of sulfur trioxide un- derlying the present invention differs from the prior art techniques in that a pre-heated gas containing 3 ⁇ 4S is mixed with air, and the mixture is fed to a first catalyst- containing reactor via a heat exchanger. In this first reactor, 3 ⁇ 4S is oxidized to sulfur dioxide (S0 2 ) according to the reaction
- the catalyst in the first reactor is a monolith type cata ⁇ lyst as described earlier.
- the catalyst can be manufactured from various ceramic mate ⁇ rials used as a carrier, such as titanium oxide, and active catalytic components are usually either oxides of base met ⁇ als (such as vanadium, molybdenum and tungsten) , zeolites, or various precious metals.
- Catalysts of monolithic struc- ture are known to provide favourable performance with re ⁇ spect to selectivity when the desired reaction is fast and the undesired reaction is slow.
- the catalyst used in this reaction is selected among the applicant's VK catalysts, which are so-called supported liquid phase (SLP) catalysts.
- SLP catalysts With SLP catalysts, the oxi- dation of SO 2 takes place as a homogeneous reaction in a liquid film consisting of V 2 O 5 dissolved in alkali-metal pyrosulfates on an inactive porous silica support made from diatomaceous earth.
- This second catalytic step results in an SO 2 to SO 3 ratio which is much lower than what is seen in desulfurization processes utilizing sorbents for direct removal of SO 2 .
- this catalytic step is deemed to be particularly inventive because it makes the desulfurisation of the gas stream, here in the form of adsorbing SO 3 , sulfate formation and separation, very cost effective compared to known wet scrubbing solutions for S0 2 .
- a sorbent preferably an alkaline sorbent
- S03 is absorbed as sulfate.
- the gas and solid is fed to a gas-solid sepa ⁇ ration unit, where the spent sorbent with sulfur is sepa- rated from the gas.
- the solid discharge of sulfate and par ⁇ tially spent sorbent can be mixed with water and re ⁇ injected in the system.
- a preferred alkaline sorbent to be injected is calcium hy- droxide (Ca(OH)2), but instead of calcium hydroxide, calci ⁇ um carbonate may be used.
- Other alkaline sorbents may be used as well.
- a magnesi ⁇ um-based sorbent such as magnesium oxide or magnesium hydroxide
- a sodium-based sorbent such as sodium car- bonate .
- sodium-based alka ⁇ line sorbents such as sodium bicarbonate ( aHCOs) and Tro- na (trisodium hydrogendicarbonate dihydrate, also known as sodium sesquicarbonate dihydrate; Na 3 (C0 3 ) (HC0 3 ) ⁇ 2 ⁇ 2 0) , are more reactive with SO 2 than calcium-based sorbents in the temperature range from 135 to 500°C.
- the present invention concerns a method for removing sulfur trioxide from a gas obtained by oxidizing hydrogen sulfide to sulfur trioxide in at least one catalyst- containing reactor, said method comprising feeding the effluent from the last reactor to a separation unit for sul ⁇ fur trioxide removal, wherein the effluent from the last reactor is mixed with a slurry or powder of a sorbent or a combination of sorbents, injected into the mixture through one or more injection points in the separation unit or upstream of it, to form a mixture of a sulfate, unused sorbent and a hot clean gas, from which the sulfate and unused sorbent is subsequently separated by any means selected among gas-solid separation unit operations, and wherein a mist filter in combination with the separation unit is used for removal of acid mist, while residual SO 3 , which is not present as a mist, is removed in a quench scrubber .
- the sorbents are preferably alkaline sorbents.
- the separation unit which constitutes the crux of the pre ⁇ sent invention, can be selected from a range of devices based on gas-solid separation unit operations and suitable for the removal of absorbed SO 3 formed by catalytic oxida ⁇ tion of 3 ⁇ 4S. As already mentioned, a number of gas-solid separation units and unit operations can be used for said removal of SO 3 .
- These separation units include (without be ⁇ ing limited thereto) various metal filters, electrofilters , bag filters, ceramic filters, mist filters, cyclones and dry scrubbers. The preferred choices are bag filters, metal filters and ceramic filters because of build-up of filter cake, which enhances the scrubbing efficiency.
- the filter unit may be a catalytic filter unit.
- the unit operations for the gas-solid separation include use of polishing technologies such as low velocity filter, wet ESP (electrostatic precipitator) and other kinds of technologies.
- polishing technologies such as low velocity filter, wet ESP (electrostatic precipitator) and other kinds of technologies.
- Use of these technologies in combination with a dry scrubber makes it possible to go from 10-30 ppm SO 3 at the outlet of the separation unit down to practically 0 ppm emissions.
- the sorbent can be injected into the ducting or an absorption unit, such as a fluidized bed or entrained flow reactor, placed between the last reactor, in which the catalytic oxidation of SO 2 to SO 3 takes place, and a separation unit, e.g. a bag filter or a ceramic filter, to lower the acid dew point by removing SO 3 from the gas, and enable cooling of the gas to a temperature that is suitable for bag filter operation. This temperature will typically be in the range from 150 to 500°C.
- an absorption unit such as a fluidized bed or entrained flow reactor
- one or more sorbent injection points can be either in the separation unit, upstream of it or a combination of both.
- one injection point may be placed in the ducting between the last reactor and the separation unit and a second injection point may be placed in the housing of the separation unit.
- Different modes of sorbent injection can be used. These in ⁇ clude (without being limited thereto) dry injection, spray drying injection and in-duct injection.
- a mist filter in combination with the separation unit is used for removal of any acid mist.
- Residual SO 3 which is not present as a mist, is removed in a quench scrubber, e.g. a venturi scrubber.
- a venturi scrubber is designed to effectively use the energy from an inlet gas stream to atomize the liquid being used to scrub the gas stream.
- the present invention is con- sidered to be a cost effective method for desulfurization in a range between lean and strong 3 ⁇ 4S gases, specifically in the range from 25 ppm to 50000 ppm 3 ⁇ 4S, preferably from 100 ppm to 20000 ppm 3 ⁇ 4S and most preferably from 200 ppm to 15000 ppm 3 ⁇ 4S.
- An especially preferred interval is from 300 ppm to 10000 ppm 3 ⁇ 4S. Especially the investment costs are considered to be lower than those of competitive tech ⁇ nologies in these intervals.
- the catalyst for oxidizing the 3 ⁇ 4S to SO 2 is preferably im- pregnated with V 2 O 5 and one or more oxides of a metal se ⁇ lected from chromium, tungsten, molybdenum, cerium, niobium, manganese and copper. Preferably a part of the effluent from the first or the second reactor is recycled to the 3 ⁇ 4S containing feed gas.
- the overall method according to the invention can be carried out in a plant for oxidizing hydrogen sulfide to sul ⁇ fur trioxide.
- Such plant which is depicted on the appended figure, mainly consists of two oxidation reactors Rl and R2 for the above oxidation reactions (1) and (2), respective- ly, and a separation unit for the removal of absorbed sul ⁇ fur trioxide from the process gas.
- the plant further com ⁇ prises a unit for pre-heating the H 2 S-containing gas, and a heat exchanger (Hex) .
- the gas is heated to a temperature of 150-500°C before entering the first reactor Rl .
- the effluent gas is either fed to the reactor R2 at a temperature of 300-500°C or fed directly to the separation unit (as shown by the dotted line in the figure) .
- the reaction (2) in R2 the resulting S0 3 -containing gas is led to the separation unit, where a sorbent, preferably an alkaline sorbent, or a combination of two or more such sorbents is injected to remove SO 3 .
- the SO 3 ends up as sulfate in the filter cake, possibly to- gether with an excess of oxide.
- the cleaned gas with a tem ⁇ perature around 150-500°C is passed through the heat ex ⁇ changer for heating up the feed gas, and it leaves the heat exchanger as a cleaned gas with a temperature around 100 °C.
- all oxidation catalysts can fit into the reactors, and the separation unit is replacing similar technologies where wet caustic scrubber systems are used.
- a major advantage in this respect is that the caustic chemicals cost will be markedly reduced, and a hot clean gas is produced, which can be used in the heat exchanger of the plant as mentioned above.
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Abstract
L'invention concerne le trioxyde de soufre qui est éliminé d'un gaz obtenu par oxydation de sulfure d'hydrogène en trioxyde de soufre dans au moins un réacteur contenant un catalyseur. Le procédé consiste à acheminer l'effluent provenant du dernier réacteur vers une unité de séparation pour l'élimination de trioxyde de soufre, et il est caractérisé en ce que l'effluent est mélangé avec une boue ou poudre d'un sorbant ou d'une combinaison de sorbants, injectée dans le mélange à travers un ou plusieurs points d'injection dans l'unité de séparation ou en amont de cette dernière, pour former un mélange d'un sulfate et d'un gaz pur chaud, à partir duquel le sulfate est ensuite séparé par un moyen quelconque choisi parmi des opérations d'unité de séparation gaz-solide, et un filtre de brouillard en combinaison avec l'unité de séparation étant utilisé pour l'élimination de brouillard d'acide tandis que S03 résiduel, qui n'est pas présent sous forme de brouillard, est éliminé dans un épurateur de trempe.
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Cited By (5)
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CN108187481A (zh) * | 2018-03-09 | 2018-06-22 | 福建龙净环保股份有限公司 | 一种干法烟气脱硫装置 |
CN108686478A (zh) * | 2017-04-06 | 2018-10-23 | 中国石油化工股份有限公司 | 一种烟气脱硫及脱硫废水的处理方法与装置 |
CN110479058A (zh) * | 2019-09-03 | 2019-11-22 | 攀枝花攀钢集团设计研究院有限公司 | 硫酸法钛白粉酸解尾气净化装置及方法 |
CN112430480A (zh) * | 2020-11-13 | 2021-03-02 | 上海逐源机械科技有限公司 | 一种煤气精脱硫方法 |
US11618677B2 (en) | 2019-05-03 | 2023-04-04 | Haldor Topsøe A/S | Revamping of a claus plant with a sulfuric acid plan |
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CN108187481A (zh) * | 2018-03-09 | 2018-06-22 | 福建龙净环保股份有限公司 | 一种干法烟气脱硫装置 |
CN108187481B (zh) * | 2018-03-09 | 2023-12-19 | 福建龙净环保股份有限公司 | 一种干法烟气脱硫装置 |
US11618677B2 (en) | 2019-05-03 | 2023-04-04 | Haldor Topsøe A/S | Revamping of a claus plant with a sulfuric acid plan |
US11691877B2 (en) | 2019-05-03 | 2023-07-04 | Haldor Topsøe A/S | Method for production of sulfur and sulfuric acid |
US11807527B2 (en) | 2019-05-03 | 2023-11-07 | Haldor Topsøe A/S | Method for production of elemental sulfur by part or fully catalytic oxidation of Claus tail gas |
CN110479058A (zh) * | 2019-09-03 | 2019-11-22 | 攀枝花攀钢集团设计研究院有限公司 | 硫酸法钛白粉酸解尾气净化装置及方法 |
CN112430480A (zh) * | 2020-11-13 | 2021-03-02 | 上海逐源机械科技有限公司 | 一种煤气精脱硫方法 |
CN112430480B (zh) * | 2020-11-13 | 2021-10-01 | 上海逐源机械科技有限公司 | 一种煤气精脱硫方法 |
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