CN101898109B - 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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- CN101898109B CN101898109B CN200910086346.7A CN200910086346A CN101898109B CN 101898109 B CN101898109 B CN 101898109B CN 200910086346 A CN200910086346 A CN 200910086346A CN 101898109 B CN101898109 B CN 101898109B
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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 of the repeated regeneration for 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 the waste water that discharges in the industrial production or the waste gas if directly discharging can have a strong impact on environment, causes even the person poultry poisoning.
The researcher for effectively reduce above-mentioned sulfide particularly hydrogen sulfide given enough attention to the destruction of industrial production and environment 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 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 periodic table the 4th, 5,6, the metallic element in 7 cycles, x is selected from 1-3, y is selected from 1-4, in addition, above-mentioned bonding metal oxide also comprises 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 consist of.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 useless agent that desulfurizing agent of the prior art (comprising Fe-series desulfurizing agent) is gone back after ubiquity uses can not be regenerated or regenerate difficult, cause and with the agent landfill that gives up in a large number, not only to waste the efficient resource in the former desulfurizing agent, and to cause new problem of environmental pollution.
The applicant is devoted to the research of amorphous FeOOH desulfurization performance always, the laboratory that just discloses amorphous FeOOH 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) prepares thinking, 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 high, 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; Although the Sulfur capacity of the amorphous FeOOH that prior art is prepared is higher than other desulfurizing agent, but because its preparation is subject to the strong effect 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 (such 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) the present desulfurizing agent of other used type and Fe-series desulfurizing agent can not be regenerated or regeneration cost is high causes and can only with a large amount of useless agent landfill, not only waste the efficient resource in the former desulfurizing agent, and cause 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 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% forms.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% forms.
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: first the filter cake in the step (3) is made into suspension, then passes into air and carry out oxidation, obtain the described material that contains amorphous FeOOH after the filtration.The quality percentage composition of the solid in the described suspension of preparing is 5-30%, preferred 10-15%; In this step, pass into air and carry out oxidation, until in the suspension mass ratio of ferrous ion and ferro element less than 50%, preferably less than 1%; In this step, can the described filter cake in the step (3) be washed with water first, make the mass percentage concentration of ion of IA family in the described filter cake or IIA family element less than 0.5%, and then be made into suspension; In this step, can be to carrying out drying by the filter cake that obtains after the 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, then wash, filter, drying obtains the described material that contains amorphous FeOOH.In this step, filter cake be placed on oxidation in the air until the mass ratio of the ferrous ion in the material and 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 first the filter cake in the step (3) being made into suspension, then pass into air and carry out oxidation, filter, the filter cake that obtains is placed on autoxidation in the air, washes again, filter, be drying to obtain the described material that contains amorphous FeOOH.In this oxidation step, being made into suspension passes into air and carries out oxidation, until in the suspension mass ratio of ferrous ion and ferro element less than 50%, after the filtration filter cake that obtains is placed on oxidation in the air until the mass ratio of the ferrous ion in the material and ferro element less than 1%.
The preparation method of above-mentioned desulfurizing agent, may further comprise the steps: (A) take by weighing on request described material and the organic binder bond that contains amorphous FeOOH, or take by weighing described material, organic binder bond and the additive that contains amorphous FeOOH, then in batch mixer, carry out the mixing of solid material; The described solid material that (B) will mix is molded into bar shaped or ball-type or ball type; (C) above-mentioned article shaped is lower natural drying or namely obtain described desulfurizing agent in 60-90 ℃ of oven dry in-5-45 ℃.
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, passes into 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, pass into air, make described elemental sulfur floating, then the sediment of taking-up container bottom adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive namely make regeneration.
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 floating is told.In described step (II), the quality percentage composition of the solid in the suspension of preparing is 5-30%, preferred 10-15%.In described step (II), described oxygenous gas is air.In described step (III), in described container, add the floating that auxiliary agent is beneficial to described elemental sulfur, described auxiliary agent is waterglass and kerosene.In described step (III), used container is flotation cell.In described step (I), useless agent is ground to 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, passes into 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, with the elemental sulfur in the described solid material of solvent extraction, add the desulfurizing agent after organic binder bond or adding organic binder bond and additive namely make regeneration after the extraction 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 the concentrated elemental sulfur that obtains crystallization.In described step (b), the solid masses percentage composition in the suspension of preparing is 5-30%, preferred 10-15%.In described step (b), described oxygenous gas is air.In described step (c), solvent for use is non-polar 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 of amorphous FeOOH in the material that contains amorphous FeOOH that preparation method of the present invention obtains high, therefore, the Sulfur capacity of desulfurizing agent with described material that contains amorphous FeOOH is high (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, such as wood dust, powdered rice hulls, wheat bran etc., add additive so that the short texture of described desulfurizing agent easily absorbs sulfide; (3) organic binder bond of the present invention is selected one or more in sodium carboxymethylcellulose, sesbania powder, the cellulose powder, these organic binder bonds can not cover the described surface that contains the material of amorphous FeOOH, so can not affect the desulphurizing activated of amorphous FeOOH, thereby make desulfurizing agent of the present invention have high Sulfur capacity; (4) be lower than 90 ℃ by strict 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 the iron such as tri-iron tetroxide, di-iron trioxide, improved 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 the solids in suspension of preparing is fast and can guarantee that the material oxidation is complete at this scope Internal oxidation rate; (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, first filter cake is made into suspension and passes into air oxidation, after the filtration, make again its autoxidation in air obtain the described material that contains amorphous FeOOH, 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 useless agent rapid regeneration of generation after the industrial renovation process of desulfurizing agent of the present invention can make described desulfurizing agent use, material after the regeneration still keeps high Sulfur capacity, namely 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, the utilization of resource is maximized; (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 other impurity that is attached to described useless agent surface in the sweetening process in order to remove, and avoids 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 suspension pass into advantage that air carries out oxidation with above-mentioned (5) identical, the advantage of the preferred 10-15% of described solids in suspension quality percentage composition is also identical with it; (14) the present invention is converted to the desulfurizer regeneration field with the method for floating of mine ore dressing, by passing into air the amorphous FeOOH of described regeneration is separated with elemental sulfur, namely realize the separating-purifying of the amorphous FeOOH of described regeneration by the method for complete physics, therefore had good economic implications and Significance for Environment; (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 is conducive to 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, until Na in the 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 pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 90 ℃-100 ℃ namely 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 same), 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
+The mensuration of 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, the method is the national standard (GB6730.5-86) of analysis of iron ore, and following examples are same.
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 at small-sized kneader and finishes kneading, extrude the stripe shape desulfurizing agent with the Small-size Twin-Screw Extruders 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).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 10% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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, then pass into air, 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 oven dry under 80 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio sesbania powder and wood chip into, 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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 wood chip in above-mentioned ratio after the oven dry, 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, until K in the 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 pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, filter drying in the time of 100 ℃, namely 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
+The mensuration of content adopts flame spectrometry, and following examples are same.
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, add water at small-sized kneader and finish kneading, be extruded into bar with the Small-size Twin-Screw Extruders extruder again, becoming 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).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 15% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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 reclaim the elemental sulfur that solvent obtains crystallization simultaneously with the method for distilling, and extract is told the material that rear remaining solid is the amorphous FeOOH that contains regeneration.The described material oven dry under 70 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio sesbania powder and powdered rice hulls into, 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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, until Na in the 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 pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 85 ℃ namely 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 in the present embodiment the amount of input solid hydroxide by the pH value of control reaction solution, namely control the feed molar ratio of two kinds of materials, following examples are same.
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 at Chufa-type sugarcoating machine, 90 ℃ of bakings are 4 hours in baking oven, surveying its Sulfur capacity is 56%, is called desulfurizing agent (A).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization reactor, 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, passes into 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, then the iron sulfide in the 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 as flotation aid, then pass into air, 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; Then the described material oven dry under 80 ℃ that contains the amorphous FeOOH of regeneration allocates the sesbania powder 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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 the sesbania powder in above-mentioned ratio after the oven dry, 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 are same.
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, until Cl in the 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 pass into air and carry out oxidation, until Fe
2+/ Fe
AlwaysComplete less than 1% material oxidation, to filter, drying in the time of 70 ℃ namely 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, add water at small-sized kneader and finish kneading, be extruded into bar with the Small-size Twin-Screw Extruders extruder again, becoming 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).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 30% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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, then pass into air, 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 oven dry under 75 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio sodium carboxymethylcellulose (with solvent in advance) 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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, and the washing of gained material is until Na in the material
+Content less than 0.5%, filter, drying in the time of 80 ℃ namely 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 at small-sized kneader and finishes kneading, is extruded into bar with the Small-size Twin-Screw Extruders extruder again, make ball type desulfurizing agent at one-tenth ball machine, 80 ℃ were dried by the fire 4 hours in baking oven, and surveying its Sulfur capacity is 50%, is called desulfurizing agent (A).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 15% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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 reclaim the elemental sulfur that solvent obtains crystallization simultaneously with the method for distilling, and extract is told the material that rear remaining solid is the amorphous FeOOH that contains regeneration.The described material oven dry under 70 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio cellulose powder into, 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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 cellulose 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 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 passes into air and carry 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, and the washing of gained material is until Na in the material
+Content less than 0.5%, filter, drying in the time of 85 ℃ namely 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, add water at small-sized kneader and finish kneading, be extruded into bar with the Small-size Twin-Screw Extruders extruder again, becoming 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).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 30% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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, then pass into air, 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 oven dry under 75 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio sodium carboxymethylcellulose (with solvent in advance) 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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, until in the filter cake content of sodium ion less than 0.5%, then described filter cake is made into the solid masses percentage composition and is 30% water slurry, and pass into air and carry out oxidation, work as Fe
2+/ Fe
AlwaysLess than 15% the time, filter, namely 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, finish kneading at small-sized kneader, be extruded into the bar shaped desulfurizing agent with the Small-size Twin-Screw Extruders machine again, in air, naturally place after 20 hours, check again the content of ferrous ion in the finished product desulfurizing agent, at this moment Fe
2+/ Fe
AlwaysLess than 1%, then change in the baking oven 70 ℃ of bakings 6 hours over to, surveying its Sulfur capacity is 50%, is called desulfurizing agent (A).
Desulfurizing agent (A) is contained in desulfurization in the desulfurization 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 ball mill, obtains useless agent powder; It is 10% water slurry that described useless agent powder is made into the solid masses percentage composition, passes into 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, then the iron sulfide in the 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, then pass into air, 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 oven dry under 80 ℃ that contains the amorphous FeOOH of regeneration, then allocate according to the above ratio sesbania powder and wood chip into, 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%.
Desulfurizing agent (B) is contained in the desulfurization reactor desulfurization, 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 wood chip in above-mentioned ratio after the oven dry, 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, first 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 of amorphous FeOOH is high 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 at small-sized kneader fully mediates.Extrude the stripe shape desulfurizing agent with the Small-size Twin-Screw Extruders extruder again, in air natural drying 10 hours, surveying its Sulfur capacity was 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 Gases of 40000ppm carries out evaluation test.Instrument is that the comprehensive Microcoulomb instrument of domestic WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) detects, and the detection limit of this instrument is 0.2ppm.
It is 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 the described material that contains amorphous FeOOH and binding agent is namely 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, such as FeSO
47H
2O, FeCl
24H
2O, Fe (NO
3)
26H
2O etc.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (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 ℃, and the scope of the pH value of solution is 7.5-8.5 during the control reaction end; Described solid hydroxide is the hydroxide of IA family or IIA family element;
(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, it 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% forms.
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% forms.
5. the described desulfurizing agent that repeats regeneration of any one according to claim 1-4 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, it is characterized in that: the oxidation in the described step (4) is by first the filter cake in the step (3) being made into suspension; Then pass into air and carry out oxidation, obtain the described material that contains amorphous FeOOH after the filtration.
8. the desulfurizing agent that repeats regeneration according to claim 1, it 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; Then wash, 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 first the filter cake in the step (3) being made into suspension, then pass into air and carry out oxidation, filter, the filter cake that obtains is placed on autoxidation in the air, washes again, filter, be drying to obtain the described material that contains amorphous FeOOH.
10. the desulfurizing agent that repeats regeneration according to claim 1 is characterized in that: in described step (2), control reaction temperature and be 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: pass into that air carries out oxidation until in the suspension mass ratio of ferrous ion and ferro element less than 50%.
14. the desulfurizing agent that repeats regeneration according to claim 13 is characterized in that: pass into that air carries out oxidation until in the suspension mass ratio of ferrous ion and ferro element less than 1%.
15. the preparation method of the described desulfurizing agent of any one among the claim 1-14 is characterized in that may further comprise the steps:
(A) take by weighing on request described material and the organic binder bond that contains amorphous FeOOH, or take by weighing described material, organic binder bond and the additive that contains amorphous FeOOH, then in batch mixer, carry out the mixing of solid material;
The described solid material that (B) will mix is molded into bar shaped, ball-type or ball type;
(C) above-mentioned article shaped is natural drying or namely obtain described desulfurizing agent in 60-90 ℃ of oven dry.
16. the process for cyclically regenerating after the described desulfurizing agent of any one 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, passes into 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, pass into air, make described elemental sulfur floating, then the sediment of taking-up container bottom adds the desulfurizing agent after organic binder bond or adding organic binder bond and additive namely make regeneration.
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.
The process for cyclically regenerating after 18. desulfurizing agent according to claim 16 uses, it is characterized in that: in described step (II), the quality percentage composition of the solid in the suspension of preparing 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 after the described desulfurizing agent of any one uses according to claim 16-19 is characterized in that: in described step (III), in described container, add the floating that auxiliary agent is beneficial to described elemental sulfur.
The process for cyclically regenerating after 21. desulfurizing agent according to claim 20 uses, it is characterized in that: used container is flotation cell.
22. the process for cyclically regenerating after the described desulfurizing agent of any one 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, passes into 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, with the elemental sulfur in the described solid material of solvent extraction, add the desulfurizing agent after organic binder bond or adding organic binder bond and additive namely make regeneration after the extraction in remaining solid.
Priority Applications (6)
| 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 |
| 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 |
| 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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| CN107537291A (en) * | 2017-08-10 | 2018-01-05 | 黑豹防水建材（新丰）有限公司 | A kind of calcium-based desulfurization additive and the desulfurization absorbent containing the additive |
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| CN1312132A (en) * | 2001-02-21 | 2001-09-12 | 马伟栋 | Normal temperature iron oxide fine desulfurizer |
| CN101134918A (en) * | 2006-08-28 | 2008-03-05 | 北京三聚环保新材料有限公司 | Desulfurizer active component having high sulfur-content and preparation method thereof |
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| CN1312132A (en) * | 2001-02-21 | 2001-09-12 | 马伟栋 | Normal temperature iron oxide fine desulfurizer |
| CN101134918A (en) * | 2006-08-28 | 2008-03-05 | 北京三聚环保新材料有限公司 | Desulfurizer active component having high sulfur-content and preparation method thereof |
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