CN101767829B - 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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- CN101767829B CN101767829B CN200810247534.9A CN200810247534A CN101767829B CN 101767829 B CN101767829 B CN 101767829B CN 200810247534 A CN200810247534 A CN 200810247534A CN 101767829 B CN101767829 B CN 101767829B
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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 of having good desulfurization performance at chemical field.As β-FeOOH sweetening agent of in Japanese documentation JP5329362A, disclosing a kind of hydrogen sulfide that is used for removing trade effluent and preparation method thereof.In being the article of " different methods prepares the desulphurizing activated research of hydrous iron oxide " (" coal conversion " the 29th volume the 3rd phase), exercise question studied the hydrous iron oxide such as the alpha-feooh of different crystalline state; β-FeOOH; the normal temperature coal gas desulfurization activity of γ-FeOOH and amorphous hydrous iron oxide; 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 technology more complicated; and there is the product structure densification that is generated as oxygenant with hydrogen peroxide; the duct is undeveloped; therefore the shortcoming that Sulfur capacity is not high does not meet requirement of industrialized batch production.In addition, in this article, do not have open can regenerate and the content of renovation process about hydrous iron oxide yet.
In the prior art, especially aspect industrial application, amorphous FeOOH desulfurizer is less, even the so-called amorphous FeOOH desulfurizer of selling on the market, cause is the content very low (being lower than 40%) of amorphous hydrous iron oxide wherein, and the content height of the hydrous iron oxide of the oxide compound of other unrenewable iron such as Z 250, ferric oxide or other crystalline state, 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 prepared in laboratory thinking of amorphous hydrous iron oxide is just disclosed 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), and the Sulfur capacity of resulting amorphous hydrous iron oxide measured, and by experiment data verification described amorphous hydrous iron oxide desulfurization and regenerated reaction mechanism.
Yet, above-mentioned research also is in the laboratory stage of fumbling, the hydrous iron oxide that still contains relatively large Z 250, ferric oxide and other crystalline state in the prepared product, the content of amorphous hydrous iron oxide does not reach the ideal degree, and its renovation process do not carried out systematic study 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 is industrially can produce purity in enormous quantities and high amorphous hydrous iron oxide and the described amorphous hydrous iron oxide of Sulfur capacity uses the back in industrial regeneration in enormous quantities in order to be implemented in, if these 2 can be realized then are great changes for the sweetening agent field, can solve existing following two shortcomings of sweetening agent of the prior art: (1) is because the preparation of hydrous iron oxide is subjected to reaction conditions such as pH value, temperature, the strong influence 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 the content of amorphous hydrous iron oxide low (being lower than 40%) causes its Sulfur capacity low in the prepared material, can not regenerate etc.; (2) sweetening agent of other now used type can not be regenerated or the regeneration cost height, and causing not only to waste the agent landfill that gives up in a large number the efficient resource in the former sweetening agent, and to have caused serious pollution to environment.
Summary of the invention
For this reason, technical problem to be solved by this invention is that amorphous hydroxyl oxidize iron level is low in the material prepared in the 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 repetition regenerated method 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, may further comprise the steps: (1) is mixed with solution for later use with the solid solubility ferrous salt; (2) solid hydroxide is mixed with the solution of step (1) both are reacted, control reaction temperature is no more than 70 ℃; (3) with the resulting material filtering of step (2), filter cake washes with water; (4) filter cake that obtains in the step (3) is made into suspension, feeds oxygenous gas and carry out oxidation, filter then, drying, promptly obtain containing the material of amorphous hydrous iron oxide.
In described step (2), described solid hydroxide is the oxyhydroxide of IA family or IIA family element.In described step (2), the scope of the pH value of solution is 7.5-8.5 during the control reaction end.In described step (3), filter cake washes with water, and the ionic mass percentage concentration that makes IA family in the described filter cake or IIA family element is less than 0.5%.In described step (2), control reaction temperature is no more than 50 ℃.In described step (4), the solid masses percentage composition in the described suspension of being prepared is 5-30%.Solid masses percentage composition in the described suspension of being prepared is 10-15%.In described step (4), described drying temperature is no more than 100 ℃.In described step (4), described oxygenous gas is air.In described step (4), feed oxygenous gas and carry out oxidation, the mass ratio of ferrous ion and ferro element is less than 1% in suspension.The quality percentage composition of amorphous hydrous iron oxide is 65-100% in the prepared material, 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 may further comprise the steps: (a). and the useless agent after the described material that contains amorphous hydrous iron oxide is used as sweetening agent grinds to form particle, obtains useless agent powder; (b). described useless agent powder is made into suspension, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the 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, the extracted residual solid is the material that contains the amorphous hydrous iron oxide of regenerated.
The regeneration of described material is actually the regeneration of contained amorphous hydrous iron oxide, and amorphous hydrous iron oxide desulfurization and regenerated principle are: 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 the extraction obtains the crystalline elemental sulfur through concentrating.In described step (b), the solid masses percentage composition in the suspension of being prepared is 5-30%, preferred 10-15%.In described step (b), described oxygenous gas is air.In described step (c), solvent for use is a 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 may further comprise the steps: the useless agent after (I) described 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, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the 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) place container with described slurries or with the solid materials that obtains behind the described dope filtration, bubbling air makes described elemental sulfur come-up, and the throw out of container bottom is the amorphous hydrous iron oxide of regenerated.
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 come-up is told.In described step (II), the solid masses percentage composition in the suspension of being prepared is 5-30%, preferred 10-15%.In described step (II), described oxygenous gas is air.In described step (III), in described container, add the come-up that auxiliary agent is beneficial to described elemental sulfur.Described auxiliary agent is water glass and kerosene.In described step (III), used container is a flotation cell.In described step (I), useless agent is ground and is 100-400 purpose particle.It is 200 purpose particles that the agent of will giving up is ground.
Sauerstoffatom in the 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, the two has formed ownership and has been the unordered structure of short range order long-range on one-piece construction, this structure has extremely strong and sulphur atom bonded stability, so the Sulfur capacity height, 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 height (65-100%) of amorphous hydrous iron oxide, Sulfur capacity height (can reach 62%) in the material of being produced, the difficult problem of the amorphous hydrous iron oxide that having solved in the prior art can not be stably, mass industrialized production purity and desulfurization performance are good; (2) through studying for a long period of time, the present invention is lower than 70 ℃ (preferably being lower than 50 ℃) by strict control reaction temperature, thereby the amorphous hydrous iron oxide of final generation behind the assurance material reaction, and mainly do not generate the oxide compound of other iron of the hydrous iron oxide of other crystalline phase or iron such as Z 250, ferric oxide, 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 the oxidising process may command, oxidation effectiveness is good, in addition, the preferred 10-15% of solid quality percentage composition in the suspension of being prepared, oxidation rate is fast and can guarantee that the material oxidation is complete in this scope; (4) preparation of the present invention contains in the method for material of amorphous hydrous iron oxide, the PH of control reaction end solution is 7.5-8.5, preferred PH is 8, the firstth, precipitate fully in order to guarantee the ferrous ion in the solution, second, under this alkaline condition, ferrous ion is oxidized to iron ion easily, 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 fast rapid regeneration of useless agent that can make described material use the back to produce as sweetening agent, described material after the regeneration still keeps high Sulfur capacity, and can also regenerate after the use of the material after the 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 obtaining the amorphous hydrous iron oxide of regenerated, can also obtain the crystalline elemental sulfur, make the utilization of resource obtain maximization; (8) before the regeneration step of two kinds of renovation process of the present invention, can comprise a step that washes described useless agent with water, this step is in order to remove in the sweetening process attached to other impurity on described useless agent surface, to avoid described impurity that the subsequent regeneration step is caused detrimentally affect; (9) in two kinds of renovation process of the present invention, will give up the agent powder be made into suspension feed advantage that oxygenous gas carries out oxidation with above-mentioned (3) identical, the advantage of the preferred 10-15% of solid masses percentage composition is also identical with it in the described suspension; (10) the present invention is with the method for floating of the mine ore dressing sweetening agent regeneration field of migrating, by bubbling air the amorphous hydrous iron oxide of described regenerated is separated with elemental sulfur, promptly realized the separation purification of the omnidirectional hydrous iron oxide of described regeneration, therefore had good economic implications and Significance for Environment by the method for complete physics; (11) in two kinds of renovation process of the present invention, the agent of will giving up grinds to form 100-400 purpose particle (preferred 200 orders), and such granularity helps the oxidation of described useless agent, also helps 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 to any other field except the sweetening agent field in the prior art.
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 places reactor, drops into 45 gram solid NaOH under agitation condition, makes temperature of reaction be no more than 70 ℃ by the feed rate of controlling solid NaOH, after reaction finishes, filters, and filter cake washes with water, 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 bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 90 ℃ promptly obtains containing the material of amorphous hydrous iron oxide, and the quality percentage composition of amorphous hydrous iron oxide is 85% in the described material, and all the other components are Na
2SO
4, water and TiO
2(TiO
2Be industrial FeSO
47H
2Impurity among the O, following examples are together), the Sulfur capacity of described material is 53%.Said Fe among the embodiment
AlwaysRefer to the total content of ferro element, Fe
2+/ Fe
AlwaysMensuration adopt phenanthroline spectrophotometry, Na
+Determination on content adopts flame photometry, and following examples together.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after washing with water, band water grinds to form 100 purpose particles in wet-type ball mill, obtains useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, feeds 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 the then useless agent 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 reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the described drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of described material is 50%; The Sulfur capacity of the material after the regeneration is 48% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 46%, the four material after the regeneration is 44% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after washing with water, band water grinds to form 100 purpose particles in wet-type ball mill, obtains useless agent powder; It is 5% aqeous suspension that described useless agent powder is made into the solid masses percentage composition, feeds 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, iron sulfide in the then useless agent 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 flotation cell, add entry, then bubbling air, described elemental sulfur overflows because of it has hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.The described elemental sulfur that overflows can be purified through extraction or other method; Can be used as sweetening agent again behind the described drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of described material is 52%; The Sulfur capacity of the material after the regeneration is 50% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 48%, the four material after the regeneration is 46% for the third time.
Embodiment 2
Contain the preparation of the material of amorphous hydrous iron oxide:
With 127 gram FeCl
24H
2O is made into the aqueous solution and places reactor, drops into 75 gram solid KOHs under agitation condition, makes temperature of reaction be no more than 50 ℃ by the feed rate of controlling solid KOH, after reaction finishes, filters, and filter cake washes with water, 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 bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, filter drying in the time of 100 ℃, promptly obtain containing the material of amorphous hydrous iron oxide, the quality percentage composition of amorphous hydrous iron oxide is 80% in the described material, and all the other components are KCl, water and unknown impuritie, the Sulfur capacity of described material are 50%.K wherein
+Determination on content adopts flame photometry, and following examples together.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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 the then useless agent 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 reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the described drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of described material is 48%; The Sulfur capacity of the material after the regeneration is 46% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 44.5%, the four material after the regeneration is 42% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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, iron sulfide in the then useless agent 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 flotation cell, add entry, and in described flotation cell, add water glass and kerosene, then bubbling air as flotation aid, described elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of described material is 48%; The Sulfur capacity of the material after the regeneration is 46.5% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 45%, the four material after the regeneration is 44% for the third time.
The effect of described flotation aid is better for the separating effect that makes described amorphous hydrous iron oxide and elemental sulfur, and following examples together.
Embodiment 3
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid Fe (NO
3)
26H
2O is made into the aqueous solution and places reactor, drops into solid NaOH under agitation condition, makes temperature of reaction remain on 30-40 ℃ by the feed rate of controlling solid NaOH, and the PH=7.5 of control solution during reaction end, filter described solution, filter cake washes with water, Na 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 bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 80 ℃ promptly obtains containing the material of amorphous hydrous iron oxide, and the quality percentage composition of amorphous hydrous iron oxide is 100% in the described material, and the Sulfur capacity of described material is 62%.
Control the amount of input solid hydroxide in the present embodiment by the pH value of control reaction soln, just control the feed molar ratio of two kinds of materials, following examples together.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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 the then useless agent 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 material that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again after the described material iron oven dry and use, the Sulfur capacity of described material is 59%; The Sulfur capacity of the material after the regeneration is 58% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 56%, the four material after the regeneration is 54% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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, iron sulfide in the then useless agent 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 flotation cell, add entry, and in described flotation cell, add water glass and kerosene as flotation aid, bubbling air then, because of the hydrophobic nature of elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated, can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of the amorphous hydrous iron oxide of described regenerated is 59%; The Sulfur capacity of the material after the regeneration is 58% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 56%, the four material after the regeneration is 54% for the third time.
Embodiment 4
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid FeCl
2Be made into the aqueous solution and place reactor, under agitation condition, drop into solid Ca (OH)
2, by control solid Ca (OH)
2Feed rate make temperature of reaction remain on 40-50 ℃, and the PH=8 of control solution during reaction end filters described solution, filter cake washes with water, Cl 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 bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 70 ℃ promptly obtains containing the material of amorphous hydrous iron oxide, and the quality percentage composition of amorphous hydrous iron oxide is 92% in the described material, and all the other components are CaCl
2And water, the Sulfur capacity of described material is 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 the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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 the then useless agent 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 reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of described material is 55%; The Sulfur capacity of the material after the regeneration is 53% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 50%, the four material after the regeneration is 48% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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, iron sulfide in the then useless agent 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 flotation cell, add entry, and in described flotation cell, add water glass and kerosene, then bubbling air as flotation aid, because of the hydrophobic nature of elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of described material is 55%; The Sulfur capacity of the material after the regeneration is 54% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 52%, the four material after the regeneration is 50% for the third time.
Embodiment 5
Contain the preparation of the material of amorphous hydrous iron oxide:
With solid FeSO
47H
2O is made into the aqueous solution and places reactor, drops into solid NaOH under agitation condition, makes temperature of reaction remain on 60-70 ℃ by the feed rate of controlling solid NaOH, and the PH=8.5 of control solution during reaction end, filter described solution, filter cake washes with water, 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 bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 60 ℃ promptly obtains containing the material of amorphous hydrous iron oxide, and the quality percentage composition of amorphous hydrous iron oxide is 88% in the described material, and all the other components are Na
2SO
4, water, TiO
2And Z 250, the Sulfur capacity of described material is 55%.
Renovation process 1:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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 the then useless agent 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 reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of described material is 53%; The Sulfur capacity of the material after the regeneration is 51% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 48%, the four material after the regeneration is 46% for the third time.
Renovation process 2:
The described material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will 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, feeds 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, iron sulfide in the then useless agent 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 flotation cell, add entry, and in described flotation cell, add water glass and kerosene as flotation aid, bubbling air then, elemental sulfur overflows because of it has hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the described drying materials again and use, the Sulfur capacity of described material is 53%; The Sulfur capacity of the material after the regeneration is 51% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 49%, the four material after the regeneration is 48% for the third time.
Sulfur capacity among the above embodiment is measured by the following method: under normal temperature (finger ring border temperature is generally-5 ℃ to 45 ℃) normal pressure (environmental stress is generally 1 normal atmosphere), with containing H
2S is that the standard gas of 40000ppm carries out evaluation test.Used instrument is that the comprehensive Microcoulomb instrument of homemade WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) detects, and the lowest detection amount 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, used soluble ferrite is not limited among the embodiment employed, 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, the foregoing description only is for example clearly is described, and is not the qualification 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 exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (11)
1. preparation method who contains the material of amorphous hydrous iron oxide is characterized in that may further comprise the steps:
(1) the solid solubility ferrous salt is mixed with solution for later use;
(2) solid hydroxide is mixed with the solution of step (1) both are reacted, control reaction temperature is no more than 70 ℃;
(3) with the resulting material filtering of step (2), filter cake washes with water;
(4) filter cake that obtains in the step (3) is made into suspension, feeds oxygenous gas and carry out oxidation, filter then, drying, promptly obtain containing the material of amorphous hydrous iron oxide;
In described step (2), described solid hydroxide is the oxyhydroxide of IA family or IIA family element;
In described step (2), the scope of the pH value of solution is 7.5-8.5 during the control reaction end.
2. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (2), control reaction temperature is no more than 50 ℃.
3. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1, it is characterized in that: in described step (3), filter cake washes with water, and the ionic mass percentage concentration that makes IA family in the described filter cake or IIA family element is less than 0.5%.
4. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (4), the solid masses percentage composition in the described suspension of being prepared is 5-30%.
5. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 4 is characterized in that: the solid masses percentage composition in the described suspension of being prepared is 10-15%.
6. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (4), described drying temperature is no more than 100 ℃.
7. according to any described preparation method who contains the material of amorphous hydrous iron oxide among the claim 1-6, it is characterized in that: in described step (4), described oxygenous gas is air.
8. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in described step (4), feed oxygenous gas and carry out oxidation, the mass ratio of ferrous ion and ferro element is less than 1% in suspension.
9. the resulting material that contains amorphous hydrous iron oxide of any described preparation method among the claim 1-8, it is characterized in that: wherein the quality percentage composition of amorphous hydrous iron oxide is 65-100%, all the other components are water and byproduct of reaction.
10. the renovation process after the resulting material that contains amorphous hydrous iron oxide of any described preparation method uses as sweetening agent among the claim 1-8 is characterized in that may further comprise the steps:
(a). the useless agent after the described material that contains amorphous hydrous iron oxide used as sweetening agent grinds to form particle, obtains useless agent powder;
(b). described useless agent powder is made into suspension, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the 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, the extracted residual solid is the material that contains the amorphous hydrous iron oxide of regenerated.
11. the renovation process after the resulting material that contains amorphous hydrous iron oxide of any described preparation method uses as sweetening agent among the claim 1-8 is characterized in that may further comprise the steps:
(I). the useless agent after the described material that contains amorphous hydrous iron oxide used as sweetening agent grinds to form particle, obtains useless agent powder;
(II). described useless agent powder is made into suspension, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the 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). place container with described slurries or with the solid materials that obtains behind the described dope filtration, bubbling air makes described elemental sulfur come-up, and the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810247534.9A CN101767829B (en) | 2008-12-30 | 2008-12-30 | Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same |
| EA201170904A EA023776B1 (en) | 2008-12-30 | 2009-12-30 | Method for preparing a composition comprising amorphous iron oxyhydroxide |
| EP09838075.1A EP2383227B1 (en) | 2008-12-30 | 2009-12-30 | Preparation of material containing amorphous iron oxyhydroxide |
| PCT/CN2009/001596 WO2010081288A1 (en) | 2008-12-30 | 2009-12-30 | Preparation and repeated regeneration of material containing amorphous iron oxyhydroxide, desulfurization agents containing the material and preparation and repeated regeneration thereof |
| DK09838075.1T DK2383227T3 (en) | 2008-12-30 | 2009-12-30 | PREPARATION OF MATERIALS CONTAINING AMORPH IRON OXIDE HYDROXIDE |
| US13/174,743 US8652427B2 (en) | 2008-12-30 | 2011-06-30 | Preparation and repeated regeneration of material containing amorphous iron oxide hydroxide, desulfurization agents containing the material, and preparation and repeated regeneration thereof |
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| CN200810247534.9A CN101767829B (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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| CN103183387B (en) * | 2011-12-29 | 2016-04-13 | 北京三聚环保新材料股份有限公司 | A kind of method preparing amorphous hydrous iron oxide |
| CN103183388B (en) | 2011-12-29 | 2016-01-06 | 北京三聚环保新材料股份有限公司 | A kind of method preparing magnetic oxide |
| CN103468326B (en) * | 2012-06-08 | 2015-11-25 | 北京三聚环保新材料股份有限公司 | A kind of combined desulfurization deamination technique for coke-oven gas |
| CN103468325B (en) * | 2012-06-08 | 2015-11-25 | 北京三聚环保新材料股份有限公司 | A kind of technique for coke oven gas desulfurization, deamination |
| CN103468327B (en) * | 2012-06-08 | 2015-11-25 | 北京三聚环保新材料股份有限公司 | A kind of combining deamination and desulfurization technique for coke-oven gas |
| CN103991909B (en) * | 2013-02-20 | 2016-04-13 | 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 high sulfur capacity |
| CN104548934B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of oxidation desulfuration process of desulfurizing agent continuous reproducible |
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| 刘振义 等.一种高硫容氧化铁脱硫剂活性组分的表征.《全国气体净化信息站2006年技术交流会论文集》.2006,第107-111页. * |
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