CN101767832B - Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same - Google Patents
Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same Download PDFInfo
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- CN101767832B CN101767832B CN200810247537.2A CN200810247537A CN101767832B CN 101767832 B CN101767832 B CN 101767832B CN 200810247537 A CN200810247537 A CN 200810247537A CN 101767832 B CN101767832 B CN 101767832B
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Abstract
The invention relates to a method for preparing a material containing amorphous iron oxide hydroxide and two methods for regenerating the same after being used as desulfurizer. The content of the amorphous iron oxide hydroxide in the material prepared by the invention is as high as 65% to 100%, so the sulfur capacity of the material is high; and the desulfurizer in the prior art is non-regenerative or costly for regeneration, so that the desulfurizer in a large amount cannot but be dumped as waste liquid in landfills, while the amorphous iron oxide hydroxide in the material of the invention can be repeatedly regenerated and reused after the material is used as the desulfurizer, thereby solving the problems of the waste of effective resources in the original desulfurizer and the severe environmental pollution.
Description
Technical field
The present invention relates to the renovation process after a kind of preparation method of the material that contains amorphous hydrous iron oxide and the prepared material that contains amorphous hydrous iron oxide use as sweetening agent, belong to the sweetening agent technical field.
Background technology
Hydrous iron oxide (FeOOH) is widely used as sweetening agent because having good desulfurization performance at chemical field.As the β that discloses a kind of hydrogen sulfide for removing trade effluent in Japanese documentation JP5329362A-FeOOH sweetening agent and preparation method thereof.in being the article of " different methods prepares the desulphurizing activated research of hydrous iron oxide " (" coal conversion " the 29th the 3rd phase of volume), exercise question studied hydrous iron oxide such as the alpha-feooh of different crystalline state, β-FeOOH, the normal temperature coal gas desulfurization of γ-FeOOH and amorphous hydrous iron oxide is active, wherein amorphous hydrous iron oxide has higher desulphurizing activated, yet this article has mainly been inquired into desulphurizing activated with the resulting different crystalline state hydrous iron oxides of different preparation methods, research can stably not obtain the method for the amorphous hydrous iron oxide material of higher degree, on the other hand, the method of the amorphous hydrous iron oxide of disclosed preparation is laboratory method, need nitrogen protection, the technique more complicated, and exist the product structure that generates fine and close with hydrogen peroxide as oxygenant, the duct is undeveloped, the shortcoming that Sulfur capacity is not high, therefore do not meet the requirement of industrialized mass.In addition, do not have open can regenerate and the content of renovation process about hydrous iron oxide in this article yet.
In prior art, especially aspect industrial application, amorphous FeOOH desulfurizer is less, even sell on market so-called amorphous FeOOH desulfurizer arranged, cause is the content very low (lower than 40%) of amorphous hydrous iron oxide wherein, and the content of the hydrous iron oxide of the oxide compound of other unrenewable iron such as Z 250, ferric oxide or other crystalline state is high, not only desulfurization performance is poor to cause these amorphous oxidation iron sweetening agent products, and the regeneration difficulty, even regeneration does not have practical value yet.
The applicant is devoted to the research of amorphous hydrous iron oxide desulfurization performance always, the laboratory that just discloses amorphous hydrous iron oxide in the article of the exercise question of delivering in 2006 for " a kind of sign of high Sulfur capacity ferric oxide desulfurizer active ingredient " (see national gas sweetening information station 2006 technical conferences collection of thesis the 107th to 111 page) prepares thinking, and the Sulfur capacity of resulting amorphous hydrous iron oxide is measured, and by experiment data verification the reaction mechanism of described amorphous hydrous iron oxide desulfurization and regeneration.
Yet, above-mentioned research also is in the laboratory stage of fumbling, still contain the hydrous iron oxide of relatively large Z 250, ferric oxide and other crystalline state in prepared product, the content of amorphous hydrous iron oxide does not reach desirable degree, and its renovation process is not furtherd investigate yet, only disclosing the prepared product that contains amorphous hydrous iron oxide can oxidation regeneration in air under state of nature, and it is not studied at industrial renovation process.
the final purpose that the applicant carries out above-mentioned research be for realize industrial can produce purity and the high amorphous hydrous iron oxide of Sulfur capacity and described amorphous hydrous iron oxide in enormous quantities and use after in industrial regeneration in enormous quantities, if these 2 can be realized that for the sweetening agent field be a great change, can solve existing following two shortcomings of sweetening agent of the prior art: (1) is because the preparation of hydrous iron oxide is subject to reaction conditions such as pH value, temperature, the strong effect of oxygenant etc., the oxide compound that different preparation methods will obtain the hydrous iron oxide of different crystalline phases or obtain other iron is (as Z 250, ferric oxide), so content of amorphous hydrous iron oxide low (lower than 40%) in prepared material, cause its Sulfur capacity low, can not regenerate etc., as being to disclose the preparation method of a kind of γ-FeOOH in the Chinese patent literature of CN1944273A at publication number, it mixes ferrous sulfate saturated solution and carbonate saturated solution in retort, controlling ph value of reaction is the 8-9 reaction, generate iron protocarbonate and vitriol, pass into air and carry out oxidation, washing, filtration in retort, the drying materials after filtering is namely got described γ-FeOOH, due to the difference of the reaction conditions of controlling and step, so the method preparation is that main component is the material of γ-FeOOH, be not that main component is the material of amorphous hydrous iron oxide, and γ-FeOOH Sulfur capacity is low, reproducibility is poor, (2) now the sweetening agent of other type used can not regenerate or regeneration cost high, cause and can only with useless agent landfill in a large number, not only waste the efficient resource in former sweetening agent, and cause serious pollution to environment.
Summary of the invention
For this reason, technical problem to be solved by this invention is the low problem of amorphous hydroxyl oxidize iron level in material prepared in prior art, thus propose a kind of can be in industrial method of in enormous quantities, stably producing the high material of amorphous hydroxyl oxidize iron level.
Another technical problem to be solved by this invention is to provide the method that repeats to regenerate after the described material that contains amorphous hydrous iron oxide uses as sweetening agent.
For solving the problems of the technologies described above, a kind of preparation method who contains the material of amorphous hydrous iron oxide of the present invention comprises the following steps: (1) is mixed with respectively solution for later use with solid solubility ferrous salt and solid dissolvable acid carbonate or solubility acid carbonate; (2) described soluble ferrite solution is mixed with described soluble carbonate salt or solubility acid carbonate solution both are reacted; (3) with the resulting material filtering of step (2), the soluble salt that elimination generates, and wash resulting filter cake with water; (4) filter cake that obtains in step (3) is made into suspension, passes into oxygenous gas and carry out oxidation, then filter, drying, namely obtain containing the material of amorphous hydrous iron oxide.
In described step (2), described solid dissolvable acid carbonate is Na
2CO
3, (NH
4)
2CO
3Or K
2CO
3, described solid solubility acid carbonate is NaHCO
3, NH
4HCO
3Or KHCO
3In described step (2), when controlling reaction end, the scope of the pH value of solution is 7.5-8.5.In described step (3), filter cake washes with water, makes Na in described filter cake
+, K
+Or NH
4 +Mass percentage concentration less than 0.5%.In described step (4), the solid masses percentage composition in the described suspension of preparing is 5-30%, preferred 10-15%.In described step (4), described drying temperature is no more than 100 ℃, and described drying temperature is 80 ℃ to 100 ℃.In described step (4), described oxygenous gas is air.In described step (4), pass into oxygenous gas and carry out oxidation, until in suspension the mass ratio of ferrous ion and ferro element less than 1%.In prepared material, the quality percentage composition of amorphous hydrous iron oxide is 65-100%, and all the other components are water and byproduct of reaction.
Renovation process after the described material that contains amorphous hydrous iron oxide uses as sweetening agent comprises the following steps: the useless agent after (a) the described material that contains amorphous hydrous iron oxide being used as sweetening agent grinds to form particle, obtains useless agent powder; (b) described useless agent powder is made into suspension, passes into oxygenous gas and carry out oxidation, make the iron sulfide in described suspension be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain described amorphous hydrous iron oxide and elemental sulfur; (c) filter described slurries and obtain solid materials, with the elemental sulfur in the described solid materials of solvent extraction, after extraction, remaining solid is the material of the amorphous hydrous iron oxide that contains regeneration.
The regeneration of described material is actually the regeneration of contained amorphous hydrous iron oxide, and the principle of amorphous hydrous iron oxide desulfurization and regeneration is: 2FeOOH+3H
2S=Fe
2S
3H
2O+3H
2O, Fe
2S
3H
2O+3/2O
2=2FeOOH+3S.
In described step (a) before, also comprise a step that washes described useless agent with water.In described step (c), the solution of telling after extraction is through the concentrated elemental sulfur that obtains crystallization.In described step (b), the solid masses percentage composition in the suspension of preparing is 5-30%, preferred 10-15%.In described step (b), described oxygenous gas is air.In described step (c), solvent for use is non-polar solvent.Described non-polar solvent is tetracol phenixin or dithiocarbonic anhydride.In described step (a), useless agent is ground to 100-400 purpose particle, is preferably 200 orders.
Renovation process after the described material that contains amorphous hydrous iron oxide uses as sweetening agent comprises the following steps: the useless agent after (I) the described material that contains amorphous hydrous iron oxide being used as sweetening agent grinds to form particle, obtains useless agent powder; (II) described useless agent powder is made into suspension, passes into oxygenous gas and carry out oxidation, make the iron sulfide in described suspension be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain described amorphous hydrous iron oxide and elemental sulfur; (III) be placed in container with described slurries or with the solid materials that obtains after described dope filtration, pass into air, make described elemental sulfur floating, the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regeneration.
In described step (I) before, also comprise the step that washes described useless agent with water.In described step (III) afterwards, also comprise the step that the elemental sulfur of described floating is told.In described step (II), the solids content in the suspension of preparing is 5-30%, preferred 10-15%.In described step (II), described oxygenous gas is air.In described step (III), add auxiliary agent to be beneficial to the floating of described elemental sulfur in described container.Described auxiliary agent is water glass and kerosene.In described step (III), container used is flotation cell.In described step (I), useless agent is ground to 100-400 purpose particle.The agent of giving up is ground to 200 purpose particles.
Sauerstoffatom in amorphous hydrous iron oxide of the present invention is the cubic close packing structure, iron ion is arranged in tetrahedron or the octahedral voids that Sauerstoffatom forms, both formed on one-piece construction and be attributed to short range order and the unordered structure of long-range, this structure has extremely strong and the stability sulphur atom combination, therefore Sulfur capacity is high, and sweetening effectiveness is good.
Technique scheme of the present invention compared with prior art has the following advantages: the method that (1) preparation of the present invention contains the material of amorphous hydrous iron oxide is not limited to the laboratory, can be in industrial production in enormous quantities, and the content of amorphous hydrous iron oxide high (65-100%), Sulfur capacity high (can reach 62%) in the material of producing, having solved in the prior art can not be stably, the difficult problem of mass industrialized production purity and the good amorphous hydrous iron oxide of desulfurization performance.(2) through studying for a long period of time, the applicant finds that low temperature and oxidation rate are conducive to generate amorphous hydrous iron oxide soon, and is unfavorable for generating the hydrous iron oxide of Z 250 and other crystalline state, the present invention prepares amorphous hydrous iron oxide by soluble ferrite solution and soluble carbonate salt or acid carbonate solution reaction, be normal-temperature reaction because this reacts not heat release, therefore do not need deliberately to control the generation that temperature namely is conducive to amorphous hydrous iron oxide, in addition, the present invention is after soluble ferrite and carbonate or acid carbonate reaction, remove by filter soluble salt such as sodium sulfate that reaction generates, sodium-chlor, Repone K etc., this step is that when passing into the described suspension of atmospheric oxidation for fear of next step, the solubleness of oxygen in suspension is little, oxidation rate is slow, thereby generate the hydrous iron oxide of other crystalline state, the present invention has guaranteed finally to generate amorphous hydrous iron oxide after material reaction by above-mentioned preparation method, and mainly do not generate the oxide compound of other iron of the hydrous iron oxide of other crystalline phase or the iron such as Z 250, ferric oxide, thereby improved the stability of producing amorphous hydrous iron oxide.(3) the present invention prepares in the method for the material that contains amorphous hydrous iron oxide, filter cake is made into suspension carries out oxidation with air, the advantage of this method for oxidation is that oxidising process can be controlled, oxidation effectiveness is good, in addition, the preferred 10-15% of quality percentage composition of the solids in suspension of preparing is fast and can guarantee that the material oxidation is complete at this scope Internal oxidation rate.(4) preparation of the present invention contains in the method for material of amorphous hydrous iron oxide, the PH that controls reaction end solution is 7.5-8.5, preferred PH is 8, the firstth, precipitate fully in order to guarantee the ferrous ion in solution, second, under this alkaline condition, ferrous ion easily is oxidized to iron ion, and can not generate Z 250.(5) preparation of the present invention contains in the method for amorphous hydrous iron oxide, and it is at high temperature to generate more ferric oxide for fear of described amorphous hydrous iron oxide that the control drying temperature is no more than 100 ℃.(6) with the inventive method prepared material that contains amorphous hydrous iron oxide and two kinds of renovation process of the present invention, the useless agent rapid regeneration that produces after described material is used as sweetening agent, described material after regeneration still keeps high Sulfur capacity, and can also regenerate after the use of the material after regeneration, so recycle, not only save resource, reduced useless agent and can not use pollution on the environment, and had great economic implications.(7) use two kinds of renovation process of the present invention except the amorphous hydrous iron oxide that obtains regeneration, can also obtain the elemental sulfur of crystallization, the utilization of resource is maximized.(8) can comprise a step that washes described useless agent with water before the regeneration step of two kinds of renovation process of the present invention, this step is other impurity that is attached to described useless agent surface in sweetening process in order to remove, and avoids described impurity to cause detrimentally affect to the subsequent regeneration step.(9) will give up in two kinds of renovation process of the present invention the agent powder be made into suspension pass into advantage that oxygenous gas carries out oxidation with above-mentioned (3) identical, the advantage of the preferred 10-15% of described solids in suspension quality percentage composition is also identical with it; (10) the present invention is converted to the desulfurizer regeneration field with the method for floating of mine ore dressing, by passing into air, the amorphous hydrous iron oxide of described regeneration is separated with elemental sulfur, namely realize the separating-purifying of the amorphous hydrous iron oxide of described regeneration by the method for complete physics, therefore had good economic implications and Significance for Environment; (11) in two kinds of renovation process of the present invention, the agent of giving up grinds to form 100-400 purpose particle (preferred 200 orders), and such granularity helps the oxidation of described useless agent, also is conducive to follow-up extraction step or flotation step; (12) use the prepared material that contains amorphous hydrous iron oxide of the inventive method, also be applicable in prior art any other field except the sweetening agent field.
Embodiment
Embodiment 1
Contain the preparation of the material of amorphous hydrous iron oxide:
With 152 gram FeSO
47H
2O is made into the aqueous solution and is placed in reactor, adds under agitation condition by 58 gram solid Na
2CO
3The aqueous solution that is made into transfers to 8 with pH of mixed at last, reacts after 0.5 hour, filters, and filter cake washes with water, until Na in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 30% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 100 ℃ namely obtains containing the material of amorphous hydrous iron oxide, and in described material, the quality percentage composition of amorphous hydrous iron oxide is 85%, and all the other components are Na
2SO
4, water and TiO
2(TiO
2Be industrial FeSO
47H
2Impurity in O, following examples are same), the Sulfur capacity of described material is 53%.Said Fe in embodiment
AlwaysRefer to the total content of ferro element, Fe
2+/ Fe
AlwaysMensuration adopt phenanthroline spectrophotometry, Na
+The mensuration of content adopts flame photometry, and following examples are same.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 100 purpose particles in wet-type ball mill, obtained useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CCl
4Extract the elemental sulfur in described solid materials, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 51%; The Sulfur capacity of the material after regeneration is 48% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 46%, the four material after regeneration is 44% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 100 purpose particles in wet-type ball mill, obtained useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, filter described slurries and obtain solid materials, described solid materials is placed in flotation cell, adds entry, pass into air, described elemental sulfur overflows because having hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 52%; The Sulfur capacity of material after regeneration is that the Sulfur capacity of 50%, the four material after regeneration is that the Sulfur capacity of 48%, the four material after regeneration is 46% for the second time.
Embodiment 2
Contain the preparation of the material of amorphous hydrous iron oxide:
With 88 gram solid K
2CO
3Be made into the aqueous solution and be placed in reactor, add under agitation condition by 127 gram FeCl
2The aqueous solution that is made into transfers to 8.0 with pH of mixed, reacts after 0.5 hour, filters, and filter cake washes with water, until K in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 15% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, filter, drying in the time of 90 ℃, namely obtain containing the material of amorphous hydrous iron oxide, in described material, the quality percentage composition of amorphous hydrous iron oxide is 81%, and all the other components are KCl, moisture content, Z 250 and unknown impuritie, the Sulfur capacity of described material are 50.2%.K wherein
+The mensuration of content adopts flame photometry, and following examples are same.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 200 purpose particles in wet-type ball mill, obtains useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 48%; The Sulfur capacity of the material after regeneration is 46% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 44.5%, the four material after regeneration is 42% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 200 purpose particles in wet-type ball mill, obtains useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, described slurries are placed in flotation cell, add entry, and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, described elemental sulfur overflows because of hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 48%; The Sulfur capacity of the material after regeneration is 46.5% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 45%, the four material after regeneration is 44% for the third time.
Described flotation aid is conducive to the floating of elemental sulfur, the better effects if that described amorphous hydrous iron oxide is separated with elemental sulfur, and following examples are same.
Embodiment 3
Contain the preparation of the material of amorphous hydrous iron oxide:
With 152 gram FeSO
47H
2O is made into the aqueous solution and is placed in reactor, adds under agitation condition by 92 gram solid NaHCO
3The aqueous solution that is made into transfers to 8.5 with pH value of solution after mixing, reacts after 0.5 hour, filters, and filter cake washes with water, until Na in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 30% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 45 ℃ namely obtains containing the material of amorphous hydrous iron oxide, and in described material, the quality percentage composition of amorphous hydrous iron oxide is 80%, and all the other components are Na
2SO
4, water and TiO
2, the Sulfur capacity of described material is 49.6%.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 100 purpose particles in wet-type ball mill, obtained useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CCl
4Therefore extract the material that pushes away that obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 48.5%; The Sulfur capacity of the material after regeneration is 46.0% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 44.8%, the four material after regeneration is 42.4% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 100 purpose particles in wet-type ball mill, obtained useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, described slurries are placed in flotation cell, add entry, pass into air, described elemental sulfur overflows because of hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 48.0%; The Sulfur capacity of the material after regeneration is 44.5% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 43.1%, the four material after regeneration is 42.4% for the third time.
Embodiment 4
Contain the preparation of the material of amorphous hydrous iron oxide:
With 128 gram solid K HCO
3Be made into the aqueous solution and be placed in reactor, add under agitation condition by 127 gram FeCl
2The aqueous solution that is made into transfers to 8.0 with pH value of solution after mixing, reacts after 1.5 hours, filters, and filter cake washes with water, until K in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 10% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, filter drying in the time of 30 ℃, namely obtain containing the material of amorphous hydrous iron oxide, in described material, the quality percentage composition of amorphous hydrous iron oxide is 88%, and all the other components are KCl, water and unknown impuritie, the Sulfur capacity of described material are 54.6%.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 200 purpose particles in wet-type ball mill, obtained useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after the drying materials of the described amorphous hydrous iron oxide that contains regeneration and use, the Sulfur capacity of described material is 52.8%; The Sulfur capacity of the material after regeneration is 49.2% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 47.9%, the four material after regeneration is 46.0% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 200 purpose particles in wet-type ball mill, obtains useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, filter described slurries and obtain solid materials, described solid materials is placed in flotation cell, add entry, and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, described elemental sulfur overflows because of hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 52.8%; The Sulfur capacity of the material after regeneration is 49.0% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 47.8%, the four material after regeneration is 45.8% for the third time.
Embodiment 5
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid Fe (NO
3)
2Be made into the aqueous solution and be placed in reactor, drop into by solid (NH under agitation condition
4)
2CO
3The aqueous solution that is made into, and the PH=7.5 of solution when controlling reaction end filter described solution, and filter cake washes with water, until NH in filter cake
4 +Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 10% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 80 ℃ namely obtains containing the material of amorphous hydrous iron oxide, and in described material, the quality percentage composition of amorphous hydrous iron oxide is 100%, and the Sulfur capacity of described material is 62%.Wherein, NH
4 +Content adopt the Nessler's reagent analysis.
Control input (NH by the pH value of controlling reaction soln in the present embodiment
4)
2CO
3Amount, namely control the feed molar ratio of two kinds of materials, following examples roughly the same.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 300 purpose particles in wet-type ball mill, obtains useless agent powder; It is 15% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described material iron oven dry and use, the Sulfur capacity of described material is 59%; The Sulfur capacity of the material after regeneration is 58% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 56%, the four material after regeneration is 54% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 300 purpose particles in wet-type ball mill, obtained useless agent powder; It is 15% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, described slurries are placed in flotation cell, add entry and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, elemental sulfur overflows because of hydrophobic nature, the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration, can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 59%; The Sulfur capacity of the material after regeneration is 58% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 56%, the four material after regeneration is 54% for the third time.
Embodiment 6
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid NaHCO
3Be made into the aqueous solution and be placed in reactor, add by solid FeCl under agitation condition
2The aqueous solution that is made into, when controlling reaction end, the PH=8 of solution, filter described solution, and filter cake washes with water, until Na in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 5% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, filter drying in the time of 70 ℃, namely obtain containing the material of amorphous hydrous iron oxide, in described material, the quality percentage composition of amorphous hydrous iron oxide is 92%, and all the other components are NaCl, water and unknown impuritie, the Sulfur capacity of described material are 57%, wherein Cl
-Content measure by the pharaoh's serpents colorimetric method.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 400 purpose particles in wet-type ball mill, obtained useless agent powder; It is 30% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CS
2Therefore extract the material that pushes away that obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 55%; The Sulfur capacity of the material after regeneration is 53% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 50%, the four material after regeneration is 48% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 400 purpose particles in wet-type ball mill, obtained useless agent powder; It is 30% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, described slurries are placed in flotation cell, add entry, and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, elemental sulfur overflows because of hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 55%; The Sulfur capacity of the material after regeneration is 54% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 52%, the four material after regeneration is 50% for the third time.
Embodiment 7
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid FeSO
47H
2O and solid K HCO
3Be made into respectively the aqueous solution, the described FeSO that then will prepare
4Solution and described KHCO
3Solution and stream mix, and react in reactor, and when controlling reaction end, the PH=8.5 of solution, filter described solution, and filter cake washes with water, until K in filter cake
+Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 5% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 60 ℃ namely obtains containing the material of amorphous hydrous iron oxide, and in described material, the quality percentage composition of amorphous hydrous iron oxide is 89%, and all the other components are K
2SO
4, water and unknown impuritie, the Sulfur capacity of described material are 55%.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 400 purpose particles in wet-type ball mill, obtains useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully; Filter, and, form the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filter described slurries and obtain solid materials, use CS
2The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 53%; The Sulfur capacity of the material after regeneration is 51% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 48%, the four material after regeneration is 46% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, band water grinds to form 400 purpose particles in wet-type ball mill, obtains useless agent powder; It is 30% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, described slurries are placed in flotation cell, add entry, and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, elemental sulfur overflows because of hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 53%; The Sulfur capacity of the material after regeneration is 51% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 49%, the four material after regeneration is 48% for the third time.
Embodiment 8
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid FeSO
47H
2O and solid NH
4HCO
3Be made into respectively the aqueous solution, the described FeSO that then will prepare
4Solution and NH
4HCO
3Solution and stream mix, and react in reactor, and when controlling reaction end, the PH=8 of solution, filter described solution, and filter cake washes with water, until NH in filter cake
4 +Content less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 15% aqeous suspension, and pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of-5 ℃ namely obtains containing the material of amorphous hydrous iron oxide, and in described material, the quality percentage composition of amorphous hydrous iron oxide is 80%, and all the other components are (NH
4)
2SO
4, water and Z 250, the Sulfur capacity of described material are 49.6%.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 400 purpose particles in wet-type ball mill, obtained useless agent powder; It is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur, filters described slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 48.1%; The Sulfur capacity of the material after regeneration is 44.3% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 42.5%, the four material after regeneration is 41.0% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 400 purpose particles in wet-type ball mill, obtained useless agent powder; It is 30% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, formation contains the slurries of described amorphous hydrous iron oxide and elemental sulfur, filter described slurries and obtain solid materials, described solid materials is placed in flotation cell, add entry, and add water glass and kerosene as flotation aid in described flotation cell, then pass into air, because the hydrophobic nature of elemental sulfur overflows, the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.Can be used as again sweetening agent after described drying materials and use, the Sulfur capacity of described material is 47.9%; The Sulfur capacity of the material after regeneration is 44.5% for the second time, and the Sulfur capacity of the material after regeneration is that the Sulfur capacity of 42.7%, the four material after regeneration is 41.2% for the third time.
Sulfur capacity in above embodiment is measured by the following method: under normal temperature (finger ring border temperature, be generally-5 ℃ to 45 ℃) normal pressure (environmental stress is generally 1 normal atmosphere), with containing H
2S is that the Standard Gases of 40000ppm carries out evaluation test.Instrument is that the comprehensive Microcoulomb instrument of domestic WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) detects, and the detection limit of this instrument is 0.2ppm.
It is pointed out that in the method for the described amorphous hydrous iron oxide of preparation of the present invention, soluble ferrite used is not limited to be used in embodiment, and other soluble ferrite also can realize purpose of the present invention, as FeSO
47H
2O, FeCl
24H
2O, Fe (NO
3)
26H
2O etc.
Obviously, above-described embodiment is only for example clearly is described, 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 need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (12)
1. preparation method who contains the material of amorphous hydrous iron oxide is characterized in that comprising the following steps:
(1) solid solubility ferrous salt and solid dissolvable acid carbonate or solid solubility acid carbonate are mixed with respectively solution for later use;
(2) solution of described solid solubility ferrous salt is mixed with the solution of described solid dissolvable acid carbonate or solid solubility acid carbonate both are reacted;
(3) with the resulting material filtering of step (2), the soluble salt that elimination generates, and wash resulting filter cake with water;
(4) described filter cake is made into suspension, passes into oxygenous gas and carry out oxidation, then filter, drying, namely obtain containing the material of amorphous hydrous iron oxide.
2. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1, it is characterized in that: described solid dissolvable acid carbonate is Na
2CO
3, (NH
4)
2CO
3Or K
2CO
3, described solid solubility acid carbonate is NaHCO
3, NH
4HCO
3Or KHCO
3
3. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (2), when controlling reaction end, the scope of the pH value of solution is 7.5-8.5.
4. according to claim 2 or 3 described preparation methods that contain the material of amorphous hydrous iron oxide, it is characterized in that: in described step (3), filter cake washes with water, makes Na in described filter cake
+, K
+Or NH
4 +Mass percentage concentration less than 0.5%.
5. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1, it is characterized in that: in described step (4), the solid masses percentage composition in the described suspension of preparing is 5-30%.
6. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 5, it is characterized in that: the solid masses percentage composition in the described suspension of preparing is 10-15%.
7. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1, it is characterized in that: in described step (4), drying temperature is no more than 100 ℃.
8. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 7, it is characterized in that: described drying temperature is 80 ℃ to 100 ℃.
9. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1, it is characterized in that: in described step (4), described oxygenous gas is air.
10. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (4), pass into oxygenous gas and carry out oxidation, until in suspension the mass ratio of ferrous ion and ferro element less than 1%.
11. the renovation process after in claim 1-10, the resulting material that contains amorphous hydrous iron oxide of the described preparation method of any one uses as sweetening agent is characterized in that comprising the following steps:
(a). the described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 200 purpose particles in wet-type ball mill, obtained useless agent powder;
(b). it is 10% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur;
(c). filter described slurries and obtain solid materials, use CS
2The solid materials that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaim with the method for distilling the elemental sulfur that solvent obtains crystallization simultaneously, and extraction liquid is told the material that rear remaining solid is the amorphous hydrous iron oxide that contains regeneration.
12. the renovation process after in claim 1-10, the resulting material that contains amorphous hydrous iron oxide of the described preparation method of any one uses as sweetening agent is characterized in that comprising the following steps:
(I). the described material that contains amorphous hydrous iron oxide is contained in desulfurization in desulphurization reactor, treats H
2After S penetrated, the agent of giving up drew off, and after washing with water, ground to form 100 purpose particles in wet-type ball mill, obtained useless agent powder;
(II). it is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, passes into pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in aqeous suspension is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain described amorphous hydrous iron oxide and elemental sulfur;
(III). filter described slurries and obtain solid materials, described solid materials is placed in flotation cell, adds entry, pass into air, described elemental sulfur overflows because having hydrophobic nature, and the throw out of container bottom is the material of the amorphous hydrous iron oxide that contains regeneration.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810247537.2A CN101767832B (en) | 2008-12-30 | 2008-12-30 | Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same |
| EP09838074.4A EP2384814B1 (en) | 2008-12-30 | 2009-12-30 | Method for preparing materials containing amorphous iron oxyhydroxide |
| EA201170903A EA023831B1 (en) | 2008-12-30 | 2009-12-30 | Method for preparing a composition comprising amorphous iron oxyhydroxide |
| DK09838074.4T DK2384814T3 (en) | 2008-12-30 | 2009-12-30 | PROCEDURE FOR MANUFACTURING MATERIALS CONTAINING AMORPH IRON OXIDE HYDROXIDE |
| PCT/CN2009/001595 WO2010081287A1 (en) | 2008-12-30 | 2009-12-30 | Methods for preparing and regenerating materials containing amorphous iron oxyhydroxide and desulfurizer comprising the same |
| EA201592237A EA033886B1 (en) | 2008-12-30 | 2009-12-30 | Method for preparing a composition containing amorphous iron oxide hydroxide |
| US13/174,728 US8647600B2 (en) | 2008-12-30 | 2011-06-30 | Methods for preparing and regenerating materials containing amorphous iron oxide hydroxide and desulfurizer comprising the same |
| US14/147,007 US9283539B2 (en) | 2008-12-30 | 2014-01-03 | Methods for preparing and regenerating materials containing amorphous iron oxide hydroxide and desulfurizer comprising the same |
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| CN200810247537.2A CN101767832B (en) | 2008-12-30 | 2008-12-30 | Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same |
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| CN103663565B (en) * | 2012-09-24 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of amorphous hydrous iron oxide of coproduction of ammonia sulfate |
| CN103990458B (en) * | 2013-02-19 | 2016-08-03 | 北京宝塔三聚能源科技有限公司 | A kind of heat from hydrogenation decomposition catalyst and use the heat from hydrogenation decomposition method of this catalyst |
| CN108579764B (en) * | 2018-03-28 | 2020-10-23 | 北京三聚环保新材料股份有限公司 | Hydrogenation catalyst, preparation method and application |
| CN110975614B (en) * | 2019-12-30 | 2020-11-20 | 山东海嘉石油化工有限公司 | System and method for recycling and utilizing iron oxyhydroxide desulfurizer |
| CN116354326A (en) * | 2023-02-28 | 2023-06-30 | 中南大学 | Preparation method of lithium ion battery anode material lithium iron phosphate |
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