CN105664706A - High-sulfur-capacity low-cost desulfurizing agent and preparation method thereof - Google Patents
High-sulfur-capacity low-cost desulfurizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-sulfur-capacity low-cost desulfurizing agent and a preparation method thereof.The desulfurizing agent comprises the following materials according to parts by weight: 50-95 parts of iron oxide hydroxide, 1-48 parts of an inorganic binding agent and 1-50 parts of an aid, wherein the inorganic binding agent is calcium sulfate and its hydrate and/or alkaline-earth metal hydroxide, and the aid is pulverized coal ash and/or volcanic ash.The preparation method of the desulfurizing agent comprises the following steps: 1), mixing well the iron oxide hydroxide, the inorganic binding agent and the aid to obtain a mixture; 2), adding water to the mixture, and mixing well to obtain strip material to be extruded; 3), extruding the strip material to be extruded to obtain strip material; 4), naturally drying or baking the strip material to obtain the desulfurizing agent.The desulfurizing agent is low in cost and high in sulfur capacity, is high in strength and good in water resistance, is free of argillation and caking during usage and has good environmental and economic benefits.
Description
Technical field
The invention belongs to technical field of desulfurizer preparation, be specifically related to a kind of high sulfur capacity low cost desulfurizing agent and preparation method thereof.
Background technology
Trace sulfide in the industry such as natural gas extraction, petrochemical industry, ammonia synthesizing industry, methanol, coal preparing natural gas, coal liquifaction can make in explained hereafter multiple catalysts used, adsorbent or solvent poisoning, corrode shop equipment and have a strong impact on safety and the economical production of factory, reduce product quality, cause great economic loss. And the sulfide in waste water and gas is directly discharged to the external world, the injury to environment and people and animals can be caused, it is therefore desirable to removed in time by the sulfide in the raw material of industry and waste water and gas, just can carry out subsequent use again.
The elimination of a large amount of hydrogen sulfide at present uses wet desulphurization, main wet desulfurizing process to have tannin process, ADA method, PDS method, HPF method, hydramine method-Crouse, complex iron etc. more. Using solid desulfurating agent elimination the elimination of a small amount of hydrogen sulfide, commonly used solid desulfurating agent has activated carbon desulphurization agent, Zinc oxide desulfurizer and FeOOH desulfurizer more. Activated carbon desulphurization agent is disposable products, the problem having that Sulfur capacity is on the low side and needing oxygenating during desulfurization; Although Zinc oxide desulfurizer desulfurization precision is higher, but Sulfur capacity is on the low side and expensive; The rate of sulphur expulsion of FeOOH is fast, Sulfur capacity is high, and the FeOOH after use can lead to snperoxiaized mode and regenerate, and recycles thus obtaining.
Hydroxyl oxidize iron product many uses organic binder bond of domestic use as binding agent molding, use product prepared by organic binder bond to exist intensity is low, poor water resistance, use time the problems such as easy argillization hardens, production cost is high.
Chinese patent CN101584962A discloses the FeOOH desulfurizer of a kind of high intensity, described desulfurizing agent is made up of the amorphous FeOOH of 50-95wt%, the carrier of 0-45wt% and the organic binder bond of 5-50wt%, wherein, described carrier is one or more in aluminium sesquioxide, kieselguhr, natural zeolite, catalytic cracking spent catalyst, described organic binder bond is one or more in sanlose, sesbania powder, cellulose powder, can obtain desulfurizing agent during preparation after only need to mixed material being dried. In above-mentioned technology, prepared FeOOH desulfurizer is applicable to normal temperature environment desulfurization, and the preparation of desulfurizing agent needs not move through high-temperature roasting, only needs drying process to use, not only increases production efficiency, and saved the energy. In addition, this technology with the addition of inorganic material as carrier, the intensity of desulfurizing agent can be obviously enhanced, but carrier and FeOOH are all inorganic particle, in the process of mixing, although organic binder bond can play certain combination, but owing to not carrying out roasting in the process prepare desulfurizing agent, inorganic material is difficult to be securely joined with FeOOH, therefore desulfurizing agent is easily pulverized because suppressing, and prepared desulfurizing agent poor water resistance, it is easy to the efflorescence because of water suction in a humidity environment.
Prior art also has and directly FeOOH is carried on carrier and prepares desulfurizing agent, as: Chinese patent literature CN103418230A discloses a kind of amorphous FeOOH desulfurizer of support type and preparation method thereof, this desulfurizing agent at least includes amorphous FeOOH and calcium sulphate dihydrate, and described amorphous FeOOH is carried on described calcium sulphate dihydrate; Preparation method is by 1) green vitriol powder and calcium hydroxide powder kneading are reacted, after reaction, it is shaped; 2) to step 1) in the article shaped that obtains utilize oxygen-containing gas that it is aoxidized, then be dried. But there are the following problems: first amorphous FeOOH is carried on described calcium sulphate dihydrate, there are two parts, a part is carried on calcium sulphate dihydrate surface, another part is carried on inside calcium sulphate dihydrate, but the fine and close intensity of calcium sulphate dihydrate itself is big, it is carried on the amorphous FeOOH within calcium sulphate dihydrate and is difficult to and H2S contact, causes that preparation-obtained desulfurizing agent Sulfur capacity reduces, and desulfuration efficiency is not high.
Summary of the invention
It is an object of the invention to solve that intensity of desulfurizer in prior art is low, poor water resistance and the low technical problem of Sulfur capacity, and then provide a kind of high sulfur capacity low cost desulfurizing agent.
For this, the technical solution used in the present invention is,
A kind of high sulfur capacity low cost desulfurizing agent, including the raw material of following parts by weight:
FeOOH 50～95 parts
Inorganic binder 1～48 part
Auxiliary agent 1～50 part
Wherein, described inorganic binder is calcium sulfate and hydrate thereof and/or alkaline earth metal hydroxide;
Described auxiliary agent is flyash and/or volcanic ash.
Further, including the raw material of following parts by weight:
FeOOH 50～95 parts
Inorganic binder 10～30 parts
Auxiliary agent 5～20 parts
Wherein, described inorganic binder is calcium sulfate and hydrate thereof and/or alkaline earth metal hydroxide;
Described auxiliary agent is flyash and/or volcanic ash.
In above-mentioned high sulfur capacity low cost desulfurizing agent, it is preferable that described raw material also includes the water of 20～40 parts by weight.
Preferably, described alkaline earth metal hydroxide is calcium hydroxide.
Preferably, described FeOOH at least one in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH and unformed FeOOH.
Preferably, the hydrate of described calcium sulfate is half-H 2 O calcium sulphate or calcium sulphate dihydrate.
The preparation method that present invention also offers above-mentioned high sulfur capacity low cost desulfurizing agent, comprises the steps:
1) by FeOOH, inorganic bond and auxiliary agent mix homogeneously, compound is obtained;
2) in compound, add water mix homogeneously, obtain treating extrusion material;
3) treat that extrusion material carries out extruded moulding by described, obtain strip material;
4) by described strip material natural drying or drying, desulfurizing agent is obtained.
In above-mentioned preparation method, step 1) in, described mixing is to carry out in kolleroang or kneader;
Described mixing time >=3min, it is preferable that the time of described mixing is 3～45min.
Preferably, described FeOOH at least one in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH and unformed FeOOH, it is most preferred that for unformed FeOOH.
Preferably, described inorganic bond is calcium sulfate and hydrate thereof and/or calcium hydroxide;
Preferably, described auxiliary agent is flyash and/or volcanic ash.
Preferably, the hydrate of described calcium sulfate is half-H 2 O calcium sulphate or calcium sulphate dihydrate.
In above-mentioned preparation method, step 2) in, described mixing is to carry out in kolleroang or kneader;
Described mixing time >=2min, it is preferable that the time of described mixing is 2～30min.
In above-mentioned preparation method, step 3) in, described extruded moulding is to carry out in screw rod banded extruder or hydraulic strip extruding machine.
In above-mentioned preparation method, step 4) in, the temperature of described natural drying or drying is 0～120 DEG C, and the time is 0.5～24h.
Compared with prior art, there is advantages that
1) high sulfur capacity low cost desulfurizing agent provided by the present invention, by select flyash and/or volcanic ash as auxiliary agent, calcium sulfate and hydrate thereof and/or calcium hydroxide as inorganic binder, FeOOH as main desulphurizing activated composition, reacted by flyash and/or volcanic ash and alkaline earth metal hydroxide and form the compound of hydraulic gelling property, enhance intensity of desulfurizer and its resistance to water, use procedure does not have argillization and hardens; Further, the effect that desulfurizing agent is solidified is played in the addition of calcium sulfate, further increases intensity of desulfurizer and its resistance to water;
Simultaneously, select flyash and/or volcanic ash as auxiliary agent, because it has many holes gauge structure, and particle diameter is little, specific surface area is big, and it is distributed in inside desulfurizing agent and is equivalent to build countless passages inside desulfurizing agent, is beneficial to sulfurous gas and enters inside desulfurizing agent by this passage, carry out composition haptoreaction with the main active component FeOOH within desulfurizing agent, improve the Sulfur capacity of desulfurizing agent; Further, flyash and volcanic ash itself also contain some sweetening substances (such as CaO, Al2O3), the sulfur in sulfurous gas can be removed further, the sulfur improving desulfurizing agent holds;
Select calcium sulfate and hydrate thereof and/or calcium hydroxide itself as the desulphurizing activated point of auxiliary, the Sulfur capacity strengthening desulfurizing agent can be assisted.
2) high sulfur capacity low cost desulfurizing agent provided by the present invention, by selecting cheap calcium sulfate and hydrate thereof and/or calcium hydroxide, and solid waste coal ash and volcanic ash are as the auxiliary agent of desulfurizing agent, reduce the preparation cost of desulfurizing agent, achieve the utilization of garbage, it is to avoid flyash and volcanic ash intersperse among in air, cause haze, pollutant atmosphere, has good environmental benefit and economic benefit.
3) high sulfur capacity low cost desulfurizing agent provided by the present invention, by limit FeOOH as 50～95 parts, inorganic binder as 1～48 part, auxiliary agent is as 1～50 part, make between each component, to play good coordinated effect, it is ensured that the intensity of desulfurizing agent, resistance to water and Sulfur capacity reach the best.
4) high sulfur capacity low cost desulfurizing agent provided by the present invention, it is not necessary to organic binder bond, thus avoiding organic binder bond can there is moldy metamorphism in the process of long storage time; In use, if containing more steam in unstripped gas, using the decrease in strength that will also result in desulfurizing agent for a long time.
5) preparation method of high sulfur capacity low cost desulfurizing agent provided by the present invention, by by FeOOH, inorganic bond and auxiliary agent mix homogeneously, obtaining compound, makes each component be scattered in sufficiently uniformly in desulfurizing agent; Again through the mix homogeneously that adds water, obtain treating extrusion material, and by its extruded moulding, obtain strip material, natural drying or drying, namely obtain high sulfur capacity low cost desulfurizing agent, natural drying or drying control at 120 DEG C, simultaneously without roasting, it is to avoid calcium sulfate loses water of crystallization, and FeOOH at high temperature degeneration generates other metal-oxides (such as magnetic iron oxide red) and causes that desulfuration efficiency declines.
6) preparation method of high sulfur capacity low cost desulfurizing agent provided by the present invention, by mixing in kolleroang or kneader, and in step 1) in limit mixing time >=3min, in step 2) in limit mixing time >=2min, and carry out extruded in screw rod banded extruder or hydraulic strip extruding machine, each component is made to be scattered in sufficiently uniformly in desulfurizing agent, play the coordinated effect between each component, make desulfurizing agent overall performance stable homogeneous, avoid desulfurizing agent overall performance heterogeneity in follow-up sweetening process stable, effective coordinated effect can not be played, the sulfur reducing desulfurizing agent holds, enhance the mechanical strength of desulfurizing agent simultaneously, make to be securely joined with between each component, damaged in sweetening process will not lose, cause desulfurizing agent cost to increase.
7) high sulfur capacity low cost desulfurizing agent provided by the present invention, can effectively be suitable for the desulfurizing and purifying of unstripped gas such as natural gas, associated gas, shale gas, biogas, the synthesis gas of High water cut vapour, and desulfuration efficiency is high.
Detailed description of the invention
Described in each embodiment following and comparative example, the method for testing of the Sulfur capacity of desulfurizing agent is as follows: being loaded in desulfurizer by 1g desulfurizing agent ,-5-45 DEG C is measured at ambient pressure, inputs containing 40000ppmH to desulfurizer air inlet2The gas of S, and the H of desulfurizer gas outlet is measured by domestic WDL-94 trace sulfur analyzer2S content, as H in the gas of gas outlet2When the content of S reaches 1ppm, stop air inlet, due to the H contained in air inlet2Metrical instrument can be caused corrosion by S, therefore records the gas volume V of gas outlet, and is calculated according to equation below:
Described in each embodiment following and comparative example, the method for testing of the radial direction anti-crushing power of desulfurizing agent is as follows: adopt domestic ZOJ-II Intelligent testing machine for particle to test, and carries out testing according to HG/T2782 standard and calculating obtains radially anti-crushing power.
Embodiment 1,
1) by 1000g FeOOH, 100g volcanic ash, 100g flyash, 100g calcium hydroxide is put into and is stopped mixed grind in kolleroang after mixed grind 30min, obtains compound;
2) in above-mentioned compound, 400g water, mixed grind 10min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 60 DEG C, drying time 8h, namely obtaining high sulfur capacity low cost desulfurizing agent A, the Sulfur capacity measuring desulfurizing agent A is 45%, and radially anti-crushing power is 89N/cm.
Embodiment 2,
1) by 1500g FeOOH, 50g volcanic ash, 200g flyash, 200g calcium sulfate is put into and is stopped mixed grind in kolleroang after mixed grind 10min, obtains compound;
2) in above-mentioned compound, 550g water, mixed grind 15min are added; What mixed grind was good treats that extrusion material enters hydraulic strip extruding machine extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 110 DEG C, drying time 2h, namely obtaining high sulfur capacity low cost desulfurizing agent B, the Sulfur capacity measuring desulfurizing agent B is 42%, and radially anti-crushing power is 135N/cm.
Embodiment 3,
1) by 1000g FeOOH, 300g flyash, 100g half-H 2 O calcium sulphate, put into and kolleroang stops after mixed grind 35min mixed grind, obtain compound;
2) in above-mentioned material, 350g water, mixed grind 20min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 10 DEG C, drying time 24h, obtaining high sulfur capacity low cost desulfurizing agent C, the Sulfur capacity measuring desulfurizing agent C is 36%, and radially anti-crushing power is 125N/cm.
Embodiment 4,
1) by 800g FeOOH, 200g volcanic ash, 100g calcium sulphate dihydrate, put into and kolleroang stops after mixed grind 3min mixed grind, obtain compound;
2) in above-mentioned compound, 350g water, mixed grind 30min are added; What mixed grind was good treats that extrusion material enters hydraulic strip extruding machine extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 80 DEG C, drying time 6h, namely obtaining high sulfur capacity low cost desulfurizing agent D, the Sulfur capacity measuring desulfurizing agent D is 35%, and radially anti-crushing power is 88N/cm.
Embodiment 5,
1) by 1000g FeOOH, 950g volcanic ash, 50g flyash, 200g half-H 2 O calcium sulphate is put into and is stopped mixed grind in kolleroang after mixed grind 25min, obtains compound;
2) in above-mentioned compound, 600g water, mixed grind 18min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8-4.2mm, is dried by strip material at 120 DEG C, drying time 0.5h, namely obtaining high sulfur capacity low cost desulfurizing agent E, the Sulfur capacity measuring desulfurizing agent E is 32%, and radially anti-crushing power is 185N/cm.
Embodiment 6,
1) by 1000g FeOOH, 50g volcanic ash, 900g flyash, 300g calcium sulfate, 50g half-H 2 O calcium sulphate, put into and kolleroang stops after mixed grind 8min mixed grind, obtain compound;
2) in above-mentioned compound, 650g water, mixed grind 25min are added; What mixed grind was good treats that extrusion material enters hydraulic strip extruding machine extrusion, obtains the strip material that diameter is 3.8-4.2mm, is dried by strip material at 30 DEG C, drying time 12h, namely obtaining high sulfur capacity low cost desulfurizing agent F, the Sulfur capacity measuring desulfurizing agent F is 30%, and radially anti-crushing power is 178N/cm.
Embodiment 7,
1) by 1000g FeOOH, 500g volcanic ash, 500g flyash, 50g calcium sulfate, 400g calcium hydroxide is put into and is stopped mixed grind in kolleroang after mixed grind 45min, obtains compound;
2) in above-mentioned compound, 700g water, mixed grind 8min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8-4.2mm, is dried by strip material at 50 DEG C, drying time 9h, namely obtaining high sulfur capacity low cost desulfurizing agent G, the Sulfur capacity measuring desulfurizing agent G is 28%, and radially anti-crushing power is 165N/cm.
Embodiment 8,
1) by 1000g FeOOH, 100g volcanic ash, 100g calcium hydroxide is put into and is stopped mixed grind in kolleroang after mixed grind 30min, obtains compound;
2) in above-mentioned compound, 400g water, mixed grind 10min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 60 DEG C, drying time 8h, namely obtaining high sulfur capacity low cost desulfurizing agent A, the Sulfur capacity measuring desulfurizing agent A is 38%, and radially anti-crushing power is 78N/cm.
Embodiment 9,
1) by 800g FeOOH, 200g volcanic ash, 200g calcium sulphate dihydrate, 400g calcium hydroxide, put into and kolleroang stops after mixed grind 10min mixed grind, obtain compound;
2) in above-mentioned compound, 500g water, mixed grind 30min are added; What mixed grind was good treats that extrusion material enters hydraulic strip extruding machine extrusion, obtains the strip material that diameter is 3.8mm-4.2mm, is dried by strip material at 80 DEG C, drying time 5h, namely obtaining high sulfur capacity low cost desulfurizing agent D, the Sulfur capacity measuring desulfurizing agent D is 34%, and radially anti-crushing power is 96N/cm.
Comparative example 1,
1) by 1000g FeOOH, 100g calcium hydroxide is put into and is stopped mixed grind in kolleroang after mixed grind 30min, obtains compound;
2) in above-mentioned compound, 400g water, mixed grind 10min are added; What mixed grind was good treats that extrusion material enters hydraulic strip extruding machine extrusion, obtains the strip material that diameter is 3.8-4.2mm, is dried by strip material at 60 DEG C, drying time 8h, namely obtaining high sulfur capacity low cost desulfurizing agent A, the Sulfur capacity measuring desulfurizing agent A is 34%, and radially anti-crushing power is 35N/cm.
Comparative example 2,
1) by 1000g FeOOH, 100g volcanic ash, 100g flyash, put into and kolleroang stops after mixed grind 30min mixed grind, obtain compound;
2) in above-mentioned compound, 400g water, mixed grind 10min are added; What mixed grind was good treats that extrusion material enters screw rod banded extruder extrusion, obtains the strip material that diameter is 3.8-4.2mm, is dried by strip material at 60 DEG C, drying time 8h, namely obtaining high sulfur capacity low cost desulfurizing agent A, the Sulfur capacity measuring desulfurizing agent A is 31%, and radially anti-crushing power is 28N/cm.
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the restriction to embodiment. For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description. Here without also cannot all of embodiment be given exhaustive. And the apparent change thus extended out or variation are still among the protection domain of the invention.
Claims (10)
1. a desulfurizing agent, including the raw material of following parts by weight:
FeOOH 50～95 parts
Inorganic binder 1～48 part
Auxiliary agent 1～50 part
Wherein, described inorganic binder is calcium sulfate and hydrate thereof and/or alkaline earth metal hydroxide;
Described auxiliary agent is flyash and/or volcanic ash.
2. desulfurizing agent according to claim 1, it is characterised in that: described raw material also includes the water of 20～40 parts by weight.
3. desulfurizing agent according to claim 1 and 2, it is characterised in that: described FeOOH at least one in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH and unformed FeOOH;
Described alkaline earth metal hydroxide is calcium hydroxide.
4. the desulfurizing agent according to any one of claim 1-3, it is characterised in that: the hydrate of described calcium sulfate is half-H 2 O calcium sulphate or calcium sulphate dihydrate.
5. the preparation method of the desulfurizing agent according to any one of claim 1-4, comprises the steps:
1) by FeOOH, inorganic bond and auxiliary agent mix homogeneously, compound is obtained;
2) in compound, add water mix homogeneously, obtain treating extrusion material;
3) treat that extrusion material carries out extruded moulding by described, obtain strip material;
4) by described strip material natural drying or drying, desulfurizing agent is obtained.
6. preparation method according to claim 5, it is characterised in that: step 1) in, described mixing is to carry out in kolleroang or kneader;
Described mixing time >=3min, be specially 3～45min.
7. the preparation method according to claim 5 or 6, it is characterised in that: step 2) in, described mixing is to carry out in kolleroang or kneader;
Described mixing time >=2min.
8. preparation method according to claim 7, it is characterised in that: the time of described mixing is 2～30min.
9. the preparation method according to any one of claim 5-8, it is characterised in that: step 3) in, described extruded moulding is to carry out in screw rod banded extruder or hydraulic strip extruding machine.
10. the preparation method according to any one of claim 5-9, it is characterised in that: step 4) in, the temperature of described natural drying or drying is 0～120 DEG C, and the time is 0.5～24h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107596904A (en) * | 2017-11-09 | 2018-01-19 | 湖南环达环保有限公司 | A kind of high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof |
| CN108273369A (en) * | 2018-02-08 | 2018-07-13 | 曹子涵 | A method of preparing dry desulfurization block using flyash and chloride waste residue, waste liquid |
| CN109182653A (en) * | 2018-10-16 | 2019-01-11 | 含山县林头宝兴铸造厂 | A kind of high-efficiency desulfurization method of iron casting |
| CN112791581A (en) * | 2020-12-23 | 2021-05-14 | 南京工业大学 | High-efficiency desulfurizer using industrial waste residue as active raw material, and preparation method and application thereof |
| CN112940795A (en) * | 2021-02-23 | 2021-06-11 | 湖北华特尔净化科技股份有限公司 | Iron-based desulfurizer for blast furnace gas and preparation method thereof |
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| CN114643056A (en) * | 2022-03-31 | 2022-06-21 | 西安元创化工科技股份有限公司 | High-sulfur-capacity FeOOH desulfurization catalyst and preparation method thereof |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3518411C2 (en) * | 1985-05-22 | 1988-02-25 | Gebr. Knauf Westdeutsche Gipswerke Kg, 8715 Iphofen, De | |
| DE3821657A1 (en) * | 1988-06-27 | 1989-12-28 | Rheine Kalkwerke Gmbh | METHOD FOR PRODUCING A BINDER AND ITS USE |
| CN1583984A (en) * | 2004-06-02 | 2005-02-23 | 刘汉东 | Catalytic coal desulfurizer and preparing method thereof |
| CN101235324A (en) * | 2007-11-13 | 2008-08-06 | 沈阳航空工业学院 | High-temperature coal gas desulfurizer using coal ash as carrier and desulfurization device thereof |
| CN101279261A (en) * | 2008-05-23 | 2008-10-08 | 清华大学 | Preparation of iron-based selective catalytic reduction denitration catalyst |
| CN101559317A (en) * | 2008-04-16 | 2009-10-21 | 宇星科技发展(深圳)有限公司 | Fly ash calcium based flue gas desulfurizer and method for manufacturing same |
| CN102008873A (en) * | 2009-09-09 | 2011-04-13 | 蒋历辉 | Desulfurizing agent and preparation method thereof |
| CN102284244A (en) * | 2011-06-13 | 2011-12-21 | 福建工程学院 | Preparation method of pulverized fuel ash desulfurizing agent |
| CN103212369A (en) * | 2012-01-19 | 2013-07-24 | 北京三聚环保新材料股份有限公司 | High-strength ferric hydroxide desulfurizer for normal temperature desulfurization, and preparation method thereof |
| CN104511242A (en) * | 2013-10-08 | 2015-04-15 | 杜淑卿 | Flue gas desulfurizing agent preparing method |
-
2016
- 2016-01-19 CN CN201610034718.1A patent/CN105664706A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3518411C2 (en) * | 1985-05-22 | 1988-02-25 | Gebr. Knauf Westdeutsche Gipswerke Kg, 8715 Iphofen, De | |
| DE3821657A1 (en) * | 1988-06-27 | 1989-12-28 | Rheine Kalkwerke Gmbh | METHOD FOR PRODUCING A BINDER AND ITS USE |
| CN1583984A (en) * | 2004-06-02 | 2005-02-23 | 刘汉东 | Catalytic coal desulfurizer and preparing method thereof |
| CN101235324A (en) * | 2007-11-13 | 2008-08-06 | 沈阳航空工业学院 | High-temperature coal gas desulfurizer using coal ash as carrier and desulfurization device thereof |
| CN101559317A (en) * | 2008-04-16 | 2009-10-21 | 宇星科技发展(深圳)有限公司 | Fly ash calcium based flue gas desulfurizer and method for manufacturing same |
| CN101279261A (en) * | 2008-05-23 | 2008-10-08 | 清华大学 | Preparation of iron-based selective catalytic reduction denitration catalyst |
| CN102008873A (en) * | 2009-09-09 | 2011-04-13 | 蒋历辉 | Desulfurizing agent and preparation method thereof |
| CN102284244A (en) * | 2011-06-13 | 2011-12-21 | 福建工程学院 | Preparation method of pulverized fuel ash desulfurizing agent |
| CN103212369A (en) * | 2012-01-19 | 2013-07-24 | 北京三聚环保新材料股份有限公司 | High-strength ferric hydroxide desulfurizer for normal temperature desulfurization, and preparation method thereof |
| CN104511242A (en) * | 2013-10-08 | 2015-04-15 | 杜淑卿 | Flue gas desulfurizing agent preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 郭启超: "活性石灰/粉煤灰制备烧结烟气脱硫剂的试验研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107596904A (en) * | 2017-11-09 | 2018-01-19 | 湖南环达环保有限公司 | A kind of high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof |
| CN107596904B (en) * | 2017-11-09 | 2018-08-21 | 湖南环达环保有限公司 | A kind of high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof |
| CN108273369A (en) * | 2018-02-08 | 2018-07-13 | 曹子涵 | A method of preparing dry desulfurization block using flyash and chloride waste residue, waste liquid |
| CN109182653A (en) * | 2018-10-16 | 2019-01-11 | 含山县林头宝兴铸造厂 | A kind of high-efficiency desulfurization method of iron casting |
| CN112791581A (en) * | 2020-12-23 | 2021-05-14 | 南京工业大学 | High-efficiency desulfurizer using industrial waste residue as active raw material, and preparation method and application thereof |
| CN112940795A (en) * | 2021-02-23 | 2021-06-11 | 湖北华特尔净化科技股份有限公司 | Iron-based desulfurizer for blast furnace gas and preparation method thereof |
| CN114345115A (en) * | 2022-01-05 | 2022-04-15 | 武汉紫实科技有限公司 | High-selectivity desulfurizer under acid gas working condition and preparation method thereof |
| CN114643056A (en) * | 2022-03-31 | 2022-06-21 | 西安元创化工科技股份有限公司 | High-sulfur-capacity FeOOH desulfurization catalyst and preparation method thereof |
| CN116328739A (en) * | 2023-02-22 | 2023-06-27 | 东洋和光净化材料(江苏)有限公司 | Hydrophobic VOC adsorbent and production method thereof |
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