CN101898109A - Recyclable desulfurizer and preparation method thereof and regeneration method - Google Patents
Recyclable desulfurizer and preparation method thereof and regeneration method Download PDFInfo
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- CN101898109A CN101898109A CN2009100863467A CN200910086346A CN101898109A CN 101898109 A CN101898109 A CN 101898109A CN 2009100863467 A CN2009100863467 A CN 2009100863467A CN 200910086346 A CN200910086346 A CN 200910086346A CN 101898109 A CN101898109 A CN 101898109A
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Abstract
The invention relates to a recyclable dry desulfurizer with high sulfur capacity. The desulfurizer contains not less than 88% of substances containing FeOOH and not less than 7% of organic binders, wherein the organic binder is one or more of sodium carboxymethyl cellulose, sesbania and cellulose powder. The invention further discloses a preparation method of the desulfurizer and a regeneration method of waste agents generated after the desulfurizer is used. The invention solves the following problems in the prior art: the dry-formed desulfurizer has low sulfur capacity, and after the dry-formed desulfurizer is used once, the waste agents can not be regenerated or the regeneration cost is high, so that great amount of waste agents are only buried, thus not only wasting the effective resources in the original desulfurizer but also leading to new environmental pollution problems.
Description
Technical field
The present invention relates to a kind of desulfurizing agent that is used for the repeated regeneration of dry desulfurization, belong to the desulfurizing agent technical field.
Background technology
A lot of occasions in the industrial production all can produce sulfide, as in the production process of producing industrial chemicals with coal or oil and in the waste water or waste gas of industrial production discharging.Wherein, producing with coal or oil in the production process of industrial chemicals, because contain more sulphur-containing substance in the raw material, these sulphur-containing substances react in process of production and discharge hydrogen sulfide, thereby directly cause catalyst activity material poisoning and deactivation in the subsequent production workshop section.In addition, contained hydrogen sulfide sulfides in waste water that discharges in the industrial production or the waste gas if directly discharging can have a strong impact on environment, causes the person poultry poisoning even.
The researcher for reduce effectively above-mentioned sulfide particularly hydrogen sulfide given enough attention to industrial production and environment damage to the research and development of desulfurizing agent.The desulfurizing agent kind that is used for depriving hydrogen sulphide in the prior art is a lot, wherein relatively a tradition and an important class are Fe-series desulfurizing agent, the desulfurizing agent of the type mainly is with the active component of ferriferous oxide as desulfurizing agent, and described ferriferous oxide comprises tri-iron tetroxide, di-iron trioxide and FeOOH (FeOOH).Yet the not high shortcoming of Fe-series desulfurizing agent ubiquity Sulfur capacity of the prior art, as in american documentation literature US6664210A, disclosing a kind of bonding metal oxide, this metal oxide can play the effect that removes hydrogen sulfide, and the bonding metal oxide described in the document comprises that molecular formula is Me
xO
yMetal oxide in one or more, wherein Me is selected from the periodic table metallic element in the 4th, 5,6,7 cycles, x is selected from 1-3, y is selected from 1-4, in addition, above-mentioned bonding metal oxide also comprises the hydrate and the hydrophobic adhesive of above-mentioned metal oxide.Obviously, when Me selected Fe, disclosed bonding metal oxide can be by Fe in this patent documentation
3O
4, Fe
2O
3, Fe
2O
3H
2O and hydrophobic adhesive constitute.This bonding metal oxide is carried out Sulfur capacity test, show that this metal oxide particle can keep the average magnitude of sulphur here and equal 10% of bonding metal oxide particle weight, be more preferably 30%; The amount of holding hydrogen sulfide is that every pound of metal oxide particle holds 0.27 pound, and as seen, the Sulfur capacity of this bonding metal oxide (removing hydrogen sulfide) can only reach 27-30%, so Sulfur capacity is lower, and desulfurized effect is undesirable.
In addition, the difficulty of can not regenerating or regenerate of the useless agent after desulfurizing agent of the prior art (comprising Fe-series desulfurizing agent) is gone back ubiquity and used causes and the agent landfill that gives up in a large number not only can only be wasted the efficient resource in the former desulfurizing agent, and causing new problem of environmental pollution.
The applicant is devoted to the research of amorphous FeOOH desulfurization performance always, the prepared in laboratory thinking of amorphous FeOOH 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 component " (see national gas purification information station 2006 technical conferences collection of thesis the 107th to 111 page), and the Sulfur capacity of resulting amorphous FeOOH measured, and by experiment data verification the reaction mechanism of described amorphous FeOOH desulfurization and regeneration, and prepared amorphous FeOOH is disclosed can oxidation regeneration in air under nature, above-mentioned studies show that, amorphous FeOOH has high desulphurizing activated, but also can regenerate.
Yet, above-mentioned research also is in the laboratory stage of fumbling, the FeOOH that still contains relatively large unrenewable tri-iron tetroxide, di-iron trioxide and other crystalline state in the prepared product, the content of amorphous FeOOH does not reach desirable degree, its renovation process is not carried out system research yet, it is not studied at industrial renovation process.
The final purpose that the applicant carries out above-mentioned research be prepare a kind of Sulfur capacity height, can be in industrial production in enormous quantities and after using can industrial regeneration in enormous quantities with the desulfurizing agent of amorphous FeOOH as active component, if above-mentioned purpose can realize that for the desulfurizing agent field be a great change, can solve existing following two shortcomings of desulfurizing agent of the prior art: desulfurizing agent (the comprising Fe-series desulfurizing agent) Sulfur capacity of (1) prior art is lower; Though the Sulfur capacity of the amorphous FeOOH that prior art is prepared is than other desulfurizing agent height, but because its preparation is subjected to the strong influence of reaction condition such as pH value, temperature, oxidant etc., the oxide that different preparation methods will obtain the FeOOH of different crystalline phases or obtain other iron is (as tri-iron tetroxide, di-iron trioxide), so content of amorphous FeOOH low (being lower than 40%) in the prepared amorphous FeOOH material, cause its Sulfur capacity can not reach very high, do not have economic implications but also can not regenerate or regenerate; (2) desulfurizing agent of other now used type and Fe-series desulfurizing agent can not be regenerated or the regeneration cost height causes and useless agent landfill in a large number not only can only be wasted the efficient resource in the former desulfurizing agent, and causing new problem of environmental pollution.
Summary of the invention
For this reason, the desulfurizing agent Sulfur capacity that technical problem to be solved by this invention is to overcome prior art is low, the shortcoming of difficulty of can not regenerating or regenerate, thus it is high and can be at the desulfurizing agent of industrial production in enormous quantities and repeated regeneration to propose a kind of Sulfur capacity.
Another technical problem to be solved by this invention is to propose the preparation method of described desulfurizing agent.
Another technical problem to be solved by this invention is to propose the method that repeats to regenerate of described desulfurizing agent.
Break through following technological difficulties for solving the problems of the technologies described above the present invention: the first, but industrially scalable produce purity and the high material that contains amorphous FeOOH of Sulfur capacity; The second, the recovery of the elemental sulfur that produces in the fast rapid regeneration of the useless agent after described desulfurizing agent uses and the regenerative process; The 3rd, remove the desulfurizing agent that the material of regenerating behind the elemental sulfur can be made the high Sulfur capacity that makes new advances.
For solving the problems of the technologies described above, the present invention a kind of desulfurizing agent that repeats regeneration disclosed, described desulfurizing agent comprises material and the organic binder bond that contains amorphous FeOOH, the wherein said material that contains amorphous FeOOH prepares by following steps, and (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, the control reaction temperature is no more than 90 ℃; (3) the resulting material filtering of step (2) is obtained filter cake; (4) described filter cake is carried out oxidation with oxygenous gas and obtain the described material that contains amorphous FeOOH.
Described desulfurizing agent also comprises additive.
Described desulfurizing agent contains the material of amorphous FeOOH by 88wt%-93wt% described and the described organic binder bond of 7wt%-12wt% is formed.Described desulfurizing agent is by the described material that contains amorphous FeOOH of 88wt%-92wt%, and the described additive of the described organic binder bond of 7wt%-11wt% and 1wt%-5wt% is formed.
Described organic binder bond is one or more in sodium carboxymethylcellulose, sesbania powder, the cellulose powder.
Described additive is one or more in wood dust, powdered rice hulls, the wheat bran.
In described step (2), described solid hydroxide is the hydroxide 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 (2), the control reaction temperature is no more than 70 ℃, preferably is no more than 50 ℃.
Oxidation in the described step (4) realizes in the following manner: earlier the filter cake in the step (3) is made into suspension, bubbling air carries out oxidation then, obtains the described material that contains amorphous FeOOH after the filtration.The quality percentage composition of the solid in the described suspension of being prepared is 5-30%, preferred 10-15%; In this step, bubbling air carries out oxidation, and the mass ratio of ferrous ion and ferro element is less than 50%, preferably less than 1% in suspension; In this step, can the described filter cake in the step (3) be washed with water earlier, the mass percentage concentration of ion that makes IA family in the described filter cake or IIA family element is less than 0.5%, and then is made into suspension; In this step, can be to carrying out drying by the filter cake that obtains after oxidation of suspension blowing air and the filtration, described baking temperature is no more than 100 ℃.
Oxidation in the described step (4) realizes in the following manner: by the filter cake in the step (3) is placed on autoxidation in the air, wash then, filter, drying obtains the described material that contains amorphous FeOOH.In this step, filter cake be placed on oxidation in the air in material ferrous ion and the mass ratio of ferro element less than 1%; The mass percentage concentration of the ion of IA family or IIA family element is less than 0.5% in the material in this step after the washing; Baking temperature is no more than 100 ℃.
Oxidation in the described step (4) realizes in the following manner: by earlier the filter cake in the step (3) being made into suspension, bubbling air carries out oxidation then, filter, the filter cake that obtains is placed on autoxidation in the air, washes, filter, be drying to obtain the described material that contains amorphous FeOOH again.In this oxidation step, be made into the suspension bubbling air and carry out oxidation, the mass ratio of ferrous ion and ferro element is less than 50% in suspension, after the filtration filter cake that obtains is placed on oxidation in the air in material ferrous ion and the mass ratio of ferro element less than 1%.
The preparation method of above-mentioned desulfurizing agent, may further comprise the steps: (A) take by weighing described material and the organic binder bond that contains amorphous FeOOH on request, or take by weighing described material, organic binder bond and the additive that contains amorphous FeOOH, in batch mixer, carry out the mixing of solid material then; (B) the described solid material that will mix is molded into bar shaped or ball-type or ball type; (C) above-mentioned article shaped is promptly obtained described desulfurizing agent in-5-45 ℃ following air dry or in 60-90 ℃ of oven dry.
The regeneration of described desulfurizing agent is actually the contained regeneration that contains the amorphous FeOOH in the amorphous FeOOH material, and the principle of amorphous FeOOH desulfurization and regeneration is: 2FeOOH+3H
2S=Fe
2S
3H
2O+3H
2O, Fe
2S
3H
2O+3/2O
2=2FeOOH+3S.
Process for cyclically regenerating after described desulfurizing agent uses is characterized in that may further comprise the steps: the useless agent that obtains after (I) described desulfurizing agent being used 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 FeOOH and elemental sulfur, form the slurries that contain described amorphous FeOOH and elemental sulfur; (III) place container with described slurries or with the solid material that obtains behind the described dope filtration, bubbling air, make described elemental sulfur come-up, the sediment of taking-up container bottom adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive promptly make regeneration then.
In described step (I) before, also comprise a 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 quality percentage composition of the solid 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 waterglass 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, preferred 200 purpose particles.
Process for cyclically regenerating after described desulfurizing agent uses may further comprise the steps: the useless agent that obtains after (a) described desulfurizing agent being used 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 FeOOH and elemental sulfur, form the slurries that contain described amorphous FeOOH and elemental sulfur; (c) the described slurries of filtration obtain solid material, and with the elemental sulfur in the described solid material of solvent extraction, the extraction back adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive promptly make regeneration in remaining solid.
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 is through concentrating the elemental sulfur that obtains crystallization.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 solven.Described non-polar solven is carbon tetrachloride or carbon disulfide.In described step (a), useless agent is ground to 100-400 purpose particle, is preferably 200 orders.
Technique scheme of the present invention compared with prior art has the following advantages: (1) desulfurizing agent of the present invention comprises material and the organic binder bond that contains amorphous FeOOH, wherein use the content height of amorphous FeOOH in the material that contains amorphous FeOOH that preparation method of the present invention obtains, therefore, the Sulfur capacity height of desulfurizing agent with described material that contains amorphous FeOOH is (under oxygen free condition, the disposable Sulfur capacity that penetrates can reach 56%), and regeneration is easily; (2) can also add additive in the desulfurizing agent of the present invention,, add additive and make and the short texture of described desulfurizing agent easily absorb sulfide as wood dust, powdered rice hulls, wheat bran etc.; (3) organic binder bond of the present invention is selected one or more in sodium carboxymethylcellulose, sesbania powder, the cellulose powder for use, these organic binder bonds can not cover the described surface that contains the material of amorphous FeOOH, so can not influence the desulphurizing activated of amorphous FeOOH, thereby make desulfurizing agent of the present invention have high Sulfur capacity; (4) be lower than 90 ℃ by strictness control reaction temperature in the method for the described material that contains amorphous FeOOH of preparation of the present invention and (preferably be lower than 70 ℃, more preferably less than 50 ℃), thereby the final main amorphous FeOOH that generates behind the assurance material reaction, and mainly do not generate the oxide of other iron of the FeOOH of other crystalline phase or iron such as tri-iron tetroxide, di-iron trioxide, improved the stability and the purity of producing amorphous FeOOH; (5) in the method for the described material that contains amorphous FeOOH of preparation of the present invention, filter cake is made into suspension carries out oxidation with air, the advantage of this method for oxidation is that oxidizing process can be controlled, speed is fast, oxidation effectiveness is good, in addition, the preferred 10-15% of quality percentage composition of solid in the suspension of being prepared, oxidation rate is fast and can guarantee that the material oxidation is complete in this scope; (6) in the method for the described material that contains amorphous FeOOH of preparation of the present invention, filter cake is placed on carries out autoxidation in the air, the advantage of this method for oxidation is that cost is low; (7) in the method for the described material that contains amorphous FeOOH of preparation of the present invention, earlier filter cake is made into the oxidation of suspension bubbling air, after the filtration, make its autoxidation in air obtain the described material that contains amorphous FeOOH again, the advantages of such method for oxidation the advantage of aforementioned two kinds of method for oxidation, improved production efficiency; (8) in the method for the described material that contains amorphous FeOOH of preparation of the present invention, 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, 9) in the method for the described material that contains amorphous FeOOH of preparation of the present invention, it is at high temperature to generate di-iron trioxide for fear of contained amorphous FeOOH that the control baking temperature is no more than 100 ℃; (10) the industrial renovation process of desulfurizing agent of the present invention can make the fast rapid regeneration of useless agent that described desulfurizing agent uses the back to produce, material after the regeneration still keeps high Sulfur capacity, promptly generate new desulfurizing agent after adding organic binder bond or adding organic binder bond and additive, after using, new desulfurizing agent can also regenerate, so recycle, not only save resource, reduced useless agent pollution on the environment, and had great economic implications; (11) use two kinds of renovation process of the present invention except the amorphous FeOOH that obtains regeneration, can also obtain the elemental sulfur of crystallization, make the utilization of resource obtain maximization; (12) 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 harmful effect; (13) in two kinds of renovation process of the present invention, will give up the agent powder be made into advantage that the suspension bubbling air carries out oxidation with above-mentioned (5) identical, the advantage of the preferred 10-15% of solid masses percentage composition is also identical with it in the described suspension; (14) the present invention is with the method for floating of the mine ore dressing desulfurizing agent regeneration field of migrating, separate with elemental sulfur by the amorphous FeOOH of bubbling air described regeneration, promptly realized the separation purification of the amorphous FeOOH of described regeneration, therefore had good economic implications and Significance for Environment by the method for complete physics; (15) 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.
The specific embodiment
Embodiment 1
Contain the preparation of the material of amorphous FeOOH:
With 3040 gram FeSO
47H
2O is made into the aqueous solution and places reactor, drops into 900 gram solid NaOH under stirring condition, makes reaction temperature be no more than 90 ℃ by the charging 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 15% water slurry, and bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 90 ℃-100 ℃ promptly obtains containing the material of amorphous FeOOH, and the quality percentage composition of amorphous FeOOH 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 adjacent luxuriant and rich with fragrance sound of vomiting quinoline AAS, Na
+Determination on content adopts flame spectrometry, the content of amorphous FeOOH is measured by titanium trichloride-potassium bichromate titrimetric method in the described material that contains amorphous FeOOH, this method is the national standard (GB6730.5-86) that iron ore is analyzed, and following examples together.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 500 grams, granularity is for passing through 100 orders, sesbania powder 40 grams, wood chip 10 grams, mixing adds suitable quantity of water and finishes kneading on small-sized kneader, extrude the stripe shape desulfurizing agent with the small capacity double screw extruder again, 70 ℃ were dried by the fire 6 hours in baking oven, and surveying its Sulfur capacity is 50%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 10% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, formation contains the slurries of described amorphous FeOOH and elemental sulfur, described slurries are placed flotation cell, add entry, bubbling air then, elemental sulfur, additive and binding agent overflow groove with air, and then the sediment of container bottom is the material of the amorphous FeOOH that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; The described material that contains the amorphous FeOOH of regeneration is dried down at 80 ℃, allocates sesbania powder and wood chip then according to the above ratio into, and by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B) again, and the Sulfur capacity of desulfurizing agent (B) is 47.5%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), the oven dry back is allocated sesbania powder and wood chip in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 45%.
Repeating above-mentioned circulation, is 40.5% through the Sulfur capacity of the 5th time desulfurizing agent (e) obtaining behind four circular regenerations.
Embodiment 2
Contain the preparation of the material of amorphous FeOOH:
With 1270 gram FeCl
24H
2O is made into the aqueous solution and places reactor, drops into 730 gram solid KOHs under stirring condition, makes reaction temperature be no more than 50 ℃ by the charging 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% water slurry, 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 FeOOH, the quality percentage composition of amorphous FeOOH 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 spectrometry, and following examples together.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 400 grams, granularity is for passing through 100 orders, sesbania powder 48 grams, powdered rice hulls 5 grams, mixing, on small-sized kneader, add water and finish kneading, be extruded into bar with the small capacity double screw extruder again, becoming on the ball machine to make ball type desulfurizing agent, 60 ℃ were dried by the fire 7 hours in baking oven, surveying its Sulfur capacity is 48.5%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 15% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, forms the slurries that contain described amorphous FeOOH and elemental sulfur, filters, and uses CS
2The material that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaims the elemental sulfur that solvent obtains crystallization simultaneously with the method for distilling, and extract is told the material that the remaining solid in back is the amorphous FeOOH that contains regeneration.The described material that contains the amorphous FeOOH of regeneration is dried down at 70 ℃, allocates sesbania powder and powdered rice hulls then according to the above ratio into, and by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B) again, and the Sulfur capacity of desulfurizing agent (B) is 46%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), allocate sesbania powder and powdered rice hulls in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 43.5%.
Embodiment 3
Contain the preparation of the material of amorphous FeOOH:
With solid Fe (NO
3)
26H
2O is made into the aqueous solution and places reactor, drops into solid NaOH under stirring condition, makes reaction temperature remain on 30-40 ℃ by the charging 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% water slurry, and bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 85 ℃ promptly obtains containing the material of amorphous FeOOH, and the quality percentage composition of amorphous FeOOH is 99% in the described material, and all the other components are water, and the Sulfur capacity of described material is 59%.Control the amount of input solid hydroxide in the present embodiment by the pH value of control reaction solution, just control the feed molar ratio of two kinds of materials, following examples together.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 1000 grams, granularity is for passing through 100 orders, sesbania powder 80 grams, abundant mixing on batch mixer rolls out the ball-type desulfurizing agent of Φ 3-5 on water chestnut formula sugar coating machine, 90 ℃ of bakings are 4 hours in baking oven, surveying its Sulfur capacity is 56%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, treats H
2After S penetrated, the agent of will giving up drew off, and after washing with water, band water grinds to form 400 purpose particles in wet ball mill, obtains useless agent powder; It is 5% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, formation contains the slurries of described amorphous FeOOH and elemental sulfur, described slurries are placed flotation cell, add entry, and in described flotation cell, add waterglass and kerosene, then bubbling air as flotation aid, elemental sulfur and binding agent overflow groove with air, and then the sediment of container bottom is the material of the amorphous FeOOH that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; The described material that contains the amorphous FeOOH of regeneration is dried down at 80 ℃, allocates the sesbania powder then according to the above ratio into, and by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B) again, and the Sulfur capacity of desulfurizing agent (B) is 54%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), the oven dry back is allocated the sesbania powder in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 52.5%.
Repeating above-mentioned circulation, is 47% through the Sulfur capacity of the 5th time desulfurizing agent (e) obtaining behind four circular regenerations.
The effect of described flotation aid is better for the separating effect that makes described amorphous FeOOH and elemental sulfur, and following examples together.
Embodiment 4
Contain the preparation of the material of amorphous FeOOH:
With solid FeCl
24H
2O is made into the aqueous solution and places reactor, drops into solid Ca (OH) under stirring condition
2, by control solid Ca (OH)
2Charging rate make reaction temperature 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% water slurry, 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 FeOOH, and the quality percentage composition of amorphous FeOOH is 92% in the described material, and all the other components are CaCl
2And water, the Sulfur capacity of described material is 57%, wherein C1
-Content measure by the mercuric thiocyanate colorimetric method.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 500 grams, granularity is for passing through 100 orders, sanlose (with solvent in advance) 45 grams, wheat bran powder 10 grams, mixing, on small-sized kneader, add water and finish kneading, be extruded into bar with the small capacity double screw extruder again, becoming on the ball machine to make the ball-type desulfurizing agent, 75 ℃ were dried by the fire 5 hours in baking oven, surveying its Sulfur capacity is 54%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 30% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, formation contains the slurries of described amorphous FeOOH and elemental sulfur, filter described slurries and obtain solid material, described solid material is placed flotation cell, add entry, and in described flotation cell, add waterglass and kerosene as flotation aid, bubbling air then, elemental sulfur, additive and binding agent overflow groove with air, and then the sediment of container bottom is the material of the amorphous FeOOH that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; The described material that contains the amorphous FeOOH of regeneration is dried down at 75 ℃, allocate sodium carboxymethylcellulose (with solvent in advance) then according to the above ratio into, the wheat bran powder, again by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B), and the Sulfur capacity of desulfurizing agent (B) is 50%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), allocate sanlose and wheat bran powder in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 46.5%.
Repeat above-mentioned circulation, the Sulfur capacity of the 5th time the desulfurizing agent (e) that obtains behind four circular regenerations is 42%.
Embodiment 5
Contain the preparation of the material of amorphous FeOOH:
With solid FeSO
47H
2O is made into the aqueous solution and places reactor, under stirring condition, drop into solid NaOH, charging rate by control solid NaOH makes reaction temperature remain on 60-70 ℃, and the PH=8.5 of control solution during reaction end, filter described solution, resulting filter cake is put into the air autoxidation, Fe in material
2+/ Fe
AlwaysLess than 1%, oxidation finishes, the washing of gained material, Na in material
+Content less than 0.5%, filter, drying in the time of 80 ℃ promptly obtains containing the material of amorphous FeOOH, the quality percentage composition of amorphous FeOOH is 83% in the described material, all the other components are Na
2SO
4, water, TiO
2And tri-iron tetroxide, the Sulfur capacity of described material is 52%.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 500 grams, granularity is for passing through 100 orders, cellulose powder 50 grams, mixing adds water and finishes kneading on small-sized kneader, be extruded into bar with the small capacity double screw extruder again, becoming on the ball machine to make ball type desulfurizing agent, 80 ℃ were dried by the fire 4 hours in baking oven, and surveying its Sulfur capacity is 50%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 15% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, forms the slurries that contain described amorphous FeOOH and elemental sulfur, filters, and uses CCl
4The material that extraction obtains after filtering, coextraction three times, combining extraction liquid reclaims the elemental sulfur that solvent obtains crystallization simultaneously with the method for distilling, and extract is told the material that the remaining solid in back is the amorphous FeOOH that contains regeneration.The described material that contains the amorphous FeOOH of regeneration is dried down at 70 ℃, allocates cellulose powder then according to the above ratio into, and by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B) again, and the Sulfur capacity of desulfurizing agent (B) is 46%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, handle by above-mentioned renovation process equally, obtain the regenerative agent of desulfurizing agent (B), allocate cellulose powder into, again by above-mentioned forming method in above-mentioned ratio, preparation process and controlled condition are made new desulfurizing agent (C), and the Sulfur capacity of desulfurizing agent (C) agent is 43.5%.
Embodiment 6
Contain the preparation of the material of amorphous FeOOH:
With solid Fe (NO
3)
26H
2O is made into the aqueous solution and places reactor, under stirring condition, drop into solid NaOH, charging rate by control solid NaOH makes reaction temperature remain on 70 ℃, and the PH=8.0 of control solution during reaction end, filtration obtains filter cake, it is 15% water slurry that described filter cake is made into the solid masses percentage composition, and bubbling air carries out oxidation, until Fe
2+/ Fe
AlwaysBe 30%, filter, the filter cake that obtains is placed on autoxidation in the air, Fe in filter cake
2+/ Fe
AlwaysLess than 1%, oxidation finishes, the washing of gained material, Na in material
+Content less than 0.5%, filter, drying in the time of 85 ℃ promptly obtains containing the material of amorphous FeOOH, the quality percentage composition of amorphous FeOOH is 82% in the described material, all the other components are water, the Sulfur capacity of described material is 51%.
The preparation of desulfurizing agent and regeneration:
Take by weighing the above-mentioned material that contains amorphous FeOOH of 500 grams, granularity is for passing through 100 orders, sanlose (with solvent in advance) 45 grams, wheat bran powder 10 grams, mixing, on small-sized kneader, add water and finish kneading, be extruded into bar with the small capacity double screw extruder again, becoming on the ball machine to make the ball-type desulfurizing agent, 75 ℃ were dried by the fire 5 hours in baking oven, surveying its Sulfur capacity is 48%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 30% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, formation contains the slurries of described amorphous FeOOH and elemental sulfur, filter described slurries and obtain solid material, described solid material is placed flotation cell, add entry, and in described flotation cell, add waterglass and kerosene as flotation aid, bubbling air then, elemental sulfur, additive and binding agent overflow groove with air, and then the sediment of container bottom is the material of the amorphous FeOOH that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; The described material that contains the amorphous FeOOH of regeneration is dried down at 75 ℃, allocate sodium carboxymethylcellulose (with solvent in advance) then according to the above ratio into, the wheat bran powder, again by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B), and the Sulfur capacity of desulfurizing agent (B) is 46.5%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), allocate sanlose and wheat bran powder in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 44.5%.
Repeat above-mentioned circulation, the Sulfur capacity of the 5th time the desulfurizing agent (e) that obtains behind four circular regenerations is 38%.
Embodiment 7
Contain the preparation of the material of amorphous FeOOH:
With solid FeSO
47H
2O is made into the aqueous solution and places reactor, under stirring condition, drop into solid NaOH, charging rate by control solid NaOH remains on about 60 ℃ reaction temperature, and the PH=7.5 of control solution during reaction end, filtering described solution, filter cake washes with water, the content of sodium ion is less than 0.5% in filter cake, then described filter cake is made into the solid masses percentage composition and is 30% water slurry, and bubbling air carries out oxidation, work as Fe
2+/ Fe
AlwaysLess than 15% o'clock, filter, promptly obtain containing the material of amorphous FeOOH.
The preparation of desulfurizing agent and regeneration:
Taking by weighing the actual amount of solid of deduction behind the moisture is the above-mentioned materials that contain amorphous FeOOH of 500 grams, sesbania powder 40 grams, wood chip 10 grams, on small-sized kneader, finish kneading, be extruded into the bar shaped desulfurizing agent with small-sized dual-screw-stem machine again, in air, place after 20 hours naturally, check the content of ferrous ion in the finished product desulfurizing agent again, at this moment Fe
2+/ Fe
AlwaysLess than 1%, change in the baking oven 70 ℃ of bakings 6 hours then over to, surveying its Sulfur capacity is 50%, is called desulfurizing agent (A).
(A) is contained in desulfurization in the desulfurization reactor with desulfurizing agent, 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 ball mill, obtains useless agent powder; It is 10% water slurry that described useless agent powder is made into the solid masses percentage composition, feeds compressed air, and inspection by sampling after reaction a period of 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 FeOOH and elemental sulfur fully, formation contains the slurries of described amorphous FeOOH and elemental sulfur, described slurries are placed flotation cell, add entry, bubbling air then, elemental sulfur, additive and binding agent overflow groove with air, and then the sediment of container bottom is the material of the amorphous FeOOH that contains regeneration.The described elemental sulfur that overflows can be purified through extraction or other method; The described material that contains the amorphous FeOOH of regeneration is dried down at 80 ℃, allocates sesbania powder and wood chip then according to the above ratio into, and by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (B) again, and the Sulfur capacity of desulfurizing agent (B) is 47.5%.
(B) is contained in the desulfurization reactor desulfurization with desulfurizing agent, treats H
2After S penetrates, (B) agent is drawn off, same by above-mentioned renovation process processing, obtain the regenerative agent of desulfurizing agent (B), the oven dry back is allocated sesbania powder and wood chip in above-mentioned ratio, by above-mentioned forming method, preparation process and controlled condition are made new desulfurizing agent (C) again, and the Sulfur capacity of desulfurizing agent (C) agent is 45%.
In the present embodiment, in the preparation method of the material that contains amorphous FeOOH, earlier filter cake being made into that suspension is oxidized to a certain degree (is Fe in the suspension after the oxidation
2+/ Fe
AlwaysLess than 50% greater than 1%), after the filtration the resulting material that contains amorphous FeOOH is mixed with binding agent, additive, extruded moulding, the described material that contains amorphous FeOOH reaches in the process that is being placed on air at said process and continues oxidation, therefore the content height of amorphous FeOOH in the desulfurizing agent that finally makes, such method has been saved the production time, has improved the efficient of producing described desulfurizing agent.
Embodiment 8
Take by weighing desulfurizing agent (e) 400 grams after embodiment 1 regeneration and the material that contains amorphous FeOOH 100 grams of freshly prepd embodiment 1, granularity is by 100 orders, sesbania powder 35 grams, and wood chip 20 restrains mixing.Adding suitable quantity of water on small-sized kneader fully mediates.Extrude the stripe shape desulfurizing agent with the small capacity double screw extruder again, air dry is 10 hours in air, and surveying its Sulfur capacity is 43%.
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 pressure is generally 1 atmospheric pressure), 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 to be noted; as long as desulfurizing agent of the present invention comprises the material that contains amorphous FeOOH prepared with method of the present invention and binding agent and can realize the purpose of the high and repeated regeneration of Sulfur capacity of the present invention; no matter and whether add other composition, as long as the desulfurizing agent that therefore comprises described material that contains amorphous FeOOH and binding agent is promptly in protection scope of the present invention.In addition, preparation of the present invention is described to be contained in the method for material of amorphous FeOOH, and used soluble ferrite is not limited among the embodiment employed, 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, 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 (22)
1. desulfurizing agent that can repeat regeneration, it is characterized in that: described desulfurizing agent comprises material and the organic binder bond that contains amorphous FeOOH, the wherein said material that contains amorphous FeOOH prepares by following 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, the control reaction temperature is no more than 90 ℃;
(3) the resulting material filtering of step (2) is obtained filter cake;
(4) described filter cake is carried out oxidation with oxygenous gas and obtain the described material that contains amorphous FeOOH.
2. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: described desulfurizing agent also comprises additive.
3. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: described desulfurizing agent contains the material of amorphous FeOOH by 88wt%-93wt% described and the described organic binder bond of 7wt%-12wt% is formed.
4. the desulfurizing agent that repeats regeneration according to claim 2, it is characterized in that: described desulfurizing agent is by the described material that contains amorphous FeOOH of 88wt%-92wt%, and the described additive of the described organic binder bond of 7wt%-11wt% and 1wt%-5wt% is formed.
5. according to any described desulfurizing agent that repeats regeneration among the claim 1-4, it is characterized in that: described organic binder bond is one or more in sodium carboxymethylcellulose, sesbania powder, the cellulose powder.
6. according to claim 2 or the 4 described desulfurizing agents that repeat regeneration, it is characterized in that: described additive is one or more in wood dust, powdered rice hulls, the wheat bran.
7. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: the oxidation in the described step (4) is by earlier the filter cake in the step (3) being made into suspension; Bubbling air carries out oxidation then, obtains the described material that contains amorphous FeOOH after the filtration.
8. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: the oxidation in the described step (4) is by the filter cake in the step (3) is placed on autoxidation in the air; Wash then, filter, drying obtains the described material that contains amorphous FeOOH.
9. the desulfurizing agent that repeats regeneration according to claim 1, it is characterized in that: the oxidation in the described step (4) is by earlier the filter cake in the step (3) being made into suspension, bubbling air carries out oxidation then, filter, the filter cake that obtains is placed on autoxidation in the air, washes, filter, be drying to obtain the described material that contains amorphous FeOOH again.
10. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: in described step (2), the control reaction temperature is no more than 70 ℃.
11. the desulfurizing agent that repeats regeneration according to claim 10 is characterized in that: the control reaction temperature is no more than 50 ℃.
12. according to claim 7 or the 9 described desulfurizing agents that repeat regeneration, it is characterized in that: the quality percentage composition of the solid in the described suspension is 5-30%.
13. the desulfurizing agent that repeats regeneration according to claim 7 is characterized in that: bubbling air carries out the mass ratio of oxidation ferrous ion and ferro element in suspension less than 50%.
14. the desulfurizing agent that repeats regeneration according to claim 13 is characterized in that: bubbling air carries out the mass ratio of oxidation ferrous ion and ferro element in suspension less than 1%.
15. the preparation method of any described desulfurizing agent among the claim 1-14 is characterized in that may further comprise the steps:
(A) take by weighing described material and the organic binder bond that contains amorphous FeOOH on request, or take by weighing described material, organic binder bond and the additive that contains amorphous FeOOH, in batch mixer, carry out the mixing of solid material then;
(B) the described solid material that will mix is molded into bar shaped, ball-type or ball type;
(C) promptly obtain described desulfurizing agent with above-mentioned article shaped air dry or in 60-90 ℃ of oven dry.
16. the process for cyclically regenerating after any described desulfurizing agent uses among the claim 1-14 is characterized in that may further comprise the steps:
(I) the useless agent that obtains after the described desulfurizing agent use is ground to form particle, obtain 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 FeOOH and elemental sulfur, form the slurries that contain described amorphous FeOOH and elemental sulfur;
(III) place container with described slurries or with the solid material that obtains behind the described dope filtration, bubbling air, make described elemental sulfur come-up, the sediment of taking-up container bottom adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive promptly make regeneration then.
17. the process for cyclically regenerating after desulfurizing agent according to claim 16 uses is characterized in that: in described step (I) before, also comprise a step that washes described useless agent with water.
18. the quality percentage composition of the solid in the suspension of preparing according to claim 16 is 5-30%.
The process for cyclically regenerating after 19. desulfurizing agent according to claim 18 uses, it is characterized in that: the quality percentage composition of the solid in the described suspension is 10-15%.
20. the process for cyclically regenerating according to after any described desulfurizing agent uses among the claim 16-19 is characterized in that: in described step (III), add the come-up that auxiliary agent is beneficial to described elemental sulfur in described container.
The process for cyclically regenerating after 21. desulfurizing agent according to claim 20 uses, it is characterized in that: used container is a flotation cell.
22. the process for cyclically regenerating after any described desulfurizing agent uses among the claim 1-14 is characterized in that may further comprise the steps:
(a) the useless agent that obtains after the described desulfurizing agent use is ground to form particle, obtain 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 FeOOH and elemental sulfur, form the slurries that contain described amorphous FeOOH and elemental sulfur;
(c) the described slurries of filtration obtain solid material, and with the elemental sulfur in the described solid material of solvent extraction, the extraction back adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive promptly make regeneration in remaining solid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910086346.7A CN101898109B (en) | 2009-05-31 | 2009-05-31 | Recyclable desulfurizer and preparation method thereof and regeneration method |
| EA201170904A EA023776B1 (en) | 2008-12-30 | 2009-12-30 | Method for preparing a composition comprising amorphous iron oxyhydroxide |
| DK09838075.1T DK2383227T3 (en) | 2008-12-30 | 2009-12-30 | PREPARATION OF MATERIALS CONTAINING AMORPH IRON OXIDE HYDROXIDE |
| 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 |
| EP09838075.1A EP2383227B1 (en) | 2008-12-30 | 2009-12-30 | Preparation of material containing amorphous iron oxyhydroxide |
| 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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