CN101767828B - Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same - Google Patents
Method for preparing material containing amorphous iron oxide hydroxide and methods for regenerating the same Download PDFInfo
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- CN101767828B CN101767828B CN200810247533.4A CN200810247533A CN101767828B CN 101767828 B CN101767828 B CN 101767828B CN 200810247533 A CN200810247533 A CN 200810247533A CN 101767828 B CN101767828 B CN 101767828B
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Abstract
The invention relates to a method for preparing a material containing amorphous iron oxide hydroxide and two methods for regenerating the same after being used as desulfurizer. The content of the amorphous iron oxide hydroxide in the material prepared by the invention is as high as 65% to 100%, so the sulfur capacity of the material is high; and the desulfurizer in the prior art is non-regenerative or costly for regeneration, so that the desulfurizer in a large amount cannot but be dumped as waste liquid in landfills, while the amorphous iron oxide hydroxide in the material of the invention can be repeatedly regenerated and reused after the material is used as the desulfurizer, thereby solving the problems of the waste of effective resources in the original desulfurizer and the severe environmental pollution.
Description
Technical field
Renovation process after preparation method and the prepared material that contains amorphous hydrous iron oxide that the present invention relates to a kind of material that contains amorphous hydrous iron oxide with high Sulfur capacity uses as sweetening agent belongs to the sweetening agent technical field.
Background technology
Hydrous iron oxide (FeOOH) is widely used as sweetening agent because of having good desulfurization performance at chemical field.Like β-FeOOH sweetening agent of in Japanese documentation JP5329362A, disclosing a kind of hydrogen sulfide that is used for removing trade effluent and preparation method thereof., exercise question studied the hydrous iron oxide such as the alpha-feooh of different crystalline state in being the article of " different methods prepares the desulphurizing activated research of hydrous iron oxide " (" coal conversion " the 29th volume the 3rd phase); β-FeOOH, the normal temperature coal gas desulfurization of γ-FeOOH and amorphous hydrous iron oxide is active, and wherein amorphous hydrous iron oxide has higher desulphurizing activated; Yet this article has mainly been inquired into desulphurizing activated with the resulting different crystalline state hydrous iron oxides of different preparing methods; Research can stably not obtain the method for the amorphous hydrous iron oxide material of higher degree, and on the other hand, the method for the amorphous hydrous iron oxide of disclosed preparation is laboratory method; Need nitrogen protection; The technology more complicated, and fine and close with the ydrogen peroxide 50 product structure that existence is generated as oxygenant, the duct is undeveloped; Therefore the shortcoming that Sulfur capacity is not high does not meet requirement of industrialized batch production.In addition, in this article, do not have open can regenerate and the content of renovation process about hydrous iron oxide yet.
In the prior art; Especially aspect industrial application; Amorphous FeOOH desulfurizer is less, even sell on the market so-called amorphous FeOOH desulfurizer is arranged, because of the content very low (being lower than 40%) of amorphous hydrous iron oxide wherein; And the content of the hydrous iron oxide of the oxide compound of other unrenewable iron such as Z 250, red oxide of iron or other crystalline state is high; Not only desulfurization performance is poor to cause these amorphous oxidation iron sweetening agent products, and the regeneration difficulty, even regeneration does not have practical value yet.
The applicant is devoted to the research of amorphous hydrous iron oxide desulfurization performance always; The prepared in laboratory thinking of amorphous hydrous iron oxide is just disclosed in the article of the exercise question of delivering in 2006 for " a kind of sign of high Sulfur capacity ferric oxide desulfurizer active ingredient " (see national gas sweetening information station 2006 technical conferences collection of thesis the 107th to 111 page); And the Sulfur capacity of resulting amorphous hydrous iron oxide measured, and said amorphous hydrous iron oxide desulfurization and regenerated reaction mechanism have been verified through experimental data.
Yet; Above-mentioned research also is in the laboratory stage of fumbling; Still contain the hydrous iron oxide of more a large amount of Z 250s, red oxide of iron and other crystalline state in the prepared product, the content of amorphous hydrous iron oxide does not reach the ideal degree, and its renovation process is not carried out systematic study yet; Only disclosing the prepared product that contains amorphous hydrous iron oxide can oxidation regeneration in air under state of nature, and its renovation process in industry is not studied.
The final purpose that the applicant carries out above-mentioned research is can produce purity and high amorphous hydrous iron oxide and the said amorphous in enormous quantities regeneration of hydrous iron oxide use back in industry of Sulfur capacity in the industry in enormous quantities in order to be implemented in; If these 2 can be realized then are great changes for the sweetening agent field; Can solve existing following two shortcomings of sweetening agent of the prior art: (1) is because the preparation of hydrous iron oxide receives the strong influence of reaction conditions such as pH value, temperature, oxygenant etc.; The oxide compound that different preparation will obtain the hydrous iron oxide of different crystalline phases or obtain other iron is (like Z 250; Red oxide of iron); So the content of amorphous hydrous iron oxide low (less than 40%) in the prepared material, cause its Sulfur capacity low, can not regenerate etc.; (2) sweetening agent of other now used type can not be regenerated or the regeneration cost height, and causing not only to waste the agent landfill that gives up in a large number the efficient resource in the former sweetening agent, and to have caused serious pollution to environment.
Summary of the invention
For this reason, technical problem to be solved by this invention is that amorphous hydroxyl oxidize iron level is low in the material prepared in the prior art, thereby proposes a kind of method that can in industry, in enormous quantities, stably produce the high material of amorphous hydroxyl oxidize iron level.
Another technical problem to be solved by this invention is to provide the repetition regenerated method after the said material that contains amorphous hydrous iron oxide uses as sweetening agent.
For solving the problems of the technologies described above, a kind of preparation method who contains the material of amorphous hydrous iron oxide of the present invention may further comprise the steps: (1) with solid solubility ferrous salt and solid hydroxide, is to mix in 1: 2 to 1: 3 by iron and mol ratio hydroxy; (2) step (1) gained mixture is accomplished reaction through mixing to pinch, in said kneading process, the control temperature of charge is no more than 70 ℃; (3) step (2) gained reaction product is dried in air; (4) with resulting material washing of step (3) and filtration; (5), promptly obtain containing the material of amorphous hydrous iron oxide with step (4) gained solid seasoning or oven dry.
In said step (1), said solid hydroxide is the oxyhydroxide of IA family.In said step (2), said mixing pinched through the kneader completion, and the mixed time of pinching was at least 15 minutes.The said mixed time of pinching is 15-30 minute.In said step (2), the control material temperature is no more than 50 ℃.In said step (5), the temperature of seasoning is-5-45 ℃, if oven dry, then bake out temperature is no more than 100 ℃, preferred 80-100 ℃.The main active ingredient of said sweetening agent is amorphous hydrous iron oxide, and the content of said amorphous hydrous iron oxide is 65.0-100wt%, and all the other components are water and byproduct of reaction.The main active ingredient of said sweetening agent is amorphous hydrous iron oxide, and the content of said amorphous hydrous iron oxide is 95.0-97.0wt%, and all the other components are water and byproduct of reaction.
Renovation process after the said material that contains amorphous hydrous iron oxide uses as sweetening agent may further comprise the steps: (a). and the useless agent after the said material that contains amorphous hydrous iron oxide is used as sweetening agent grinds to form particle, obtains useless agent powder; (b). said useless agent powder is made into suspension-s, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the said suspension-s be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; (c). filter said slurries and obtain solid materials, with the elemental sulfur in the said solid materials of SX, the extracted residual solid is the material that contains the amorphous hydrous iron oxide of regenerated.
The regeneration of said material is actually the regeneration of contained amorphous hydrous iron oxide, and amorphous hydrous iron oxide desulfurization and regenerated principle are: 2FeOOH+3H
2S=Fe
2S
3H
2O+3H
2O, Fe
2S
3H
2O+3/2O
2=2FeOOH+3S.
In said step (a) before, also comprise a step with the said useless agent of water washing.In said step (c), the solution of telling after the extraction obtains the crystalline elemental sulfur through concentrating.In said step (b), the solid masses percentage composition in the suspension-s of being prepared is 5-30%, preferred 10-15%.In said step (b), said oxygenous gas is air.In said step (c), solvent for use is a non-polar solvent.Said non-polar solvent is tetracol phenixin or dithiocarbonic anhydride.In said step (a), useless agent is ground to 100-400 purpose particle, is preferably 200 orders.
Renovation process after the said material that contains amorphous hydrous iron oxide uses as sweetening agent may further comprise the steps: the useless agent after (I) said amorphous hydrous iron oxide being used as sweetening agent grinds to form particle, obtains useless agent powder; (II) said useless agent powder is made into suspension-s, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the said suspension-s be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; (III) said slurries maybe will be filtered the solid materials that said slurries obtain and place container, bubbling air makes said elemental sulfur come-up, and the throw out of container bottom is the amorphous hydrous iron oxide of regenerated.
In said step (I) before, also comprise step with the said useless agent of water washing.In said step (III) afterwards, also comprise the step that the elemental sulfur of said come-up is told.In said step (II), the solid masses percentage composition in the suspension-s of being prepared is 5-30%, preferred 10-15%.In said step (II), said oxygenous gas is air.In said step (III), in said container, add the come-up that auxiliary agent is beneficial to said elemental sulfur.Said auxiliary agent is water glass and kerosene.In said step (III), used container is a flotation cell.In said step (I), useless agent is ground and is 100-400 purpose particle.It is 200 purpose particles that the agent of will giving up is ground.
Sauerstoffatom in the amorphous hydrous iron oxide of the present invention is the cubic close packing structure; Iron ion is arranged in tetrahedron or the octahedral voids that Sauerstoffatom forms; The two has formed ownership and has been the unordered structure of short range order long-range on one-piece construction; This structure has extremely strong and sulphur atom bonded stability, so Sulfur capacity is high, desulfurization effect.
Technique scheme of the present invention compared with prior art has the following advantages: the method that (1) preparation of the present invention contains the material of amorphous hydrous iron oxide is not limited to the laboratory; Can in industry, produce in enormous quantities; And the content of amorphous hydrous iron oxide high (65-100%) in the material of being produced, Sulfur capacity high (can up to 62%), the difficult problem of the amorphous hydrous iron oxide that having solved in the prior art can not be stably, mass industrialized production purity and desulfurization performance are good; (2) through studying for a long period of time; The present invention adopts dry method, pinches solid solubility ferrous salt and solid hydroxide through mixing, thereby accomplishes above-mentioned reaction between the two; Preparation contains the material of amorphous hydrous iron oxide; In this preparation process,, avoid the two reaction to generate Fe (OH) through the ratio between the control raw material
2And Fe (OH)
2Colloid, further avoided owing to above-mentioned colloidal produces the filtration colloidal subsequent disposal problem of bringing; In addition; The present invention is lower than 70 ℃ (preferably being lower than 50 ℃) through strict control reaction temperature; Thereby the final main amorphous hydrous iron oxide that generates behind the assurance material reaction; And mainly do not generate the oxide compound of other iron of hydrous iron oxide or the iron such as Z 250, red oxide of iron of other crystalline phase, improved the stability of producing amorphous hydrous iron oxide; (3) the present invention adopts dried preparation to contain the material of amorphous hydrous iron oxide, has avoided preparing the further technological problems of handling of follow-up waste liquid needs that amorphous FeOOH desulfurizer brings through solution reaction, and is environmentally friendly; In addition; In the process of the amorphous hydrous iron oxide of above-mentioned dried preparation; Through utilizing the thermopositive reaction between solid solubility ferrous salt and the solid hydroxide, realized said two devices being mixed in the process of pinching, thereby practiced thrift the energy the making full use of of above-mentioned energy; (4) preparation method who contains the material of amorphous hydrous iron oxide of the present invention only needs disposable feeding intake can realize promptly mixing of solid solubility ferrous salt and solid hydroxide that this method simply is convenient to operate, and is particularly suitable for large-scale industrial production; (5) preparation of the present invention contains in the method for amorphous hydrous iron oxide, and control seasoning or bake out temperature are at high temperature to generate more red oxide of iron for fear of said amorphous hydrous iron oxide; (6) with the inventive method prepared material that contains amorphous hydrous iron oxide and two kinds of renovation process of the present invention; The fast rapid regeneration of useless agent that can make said material use the back to produce as sweetening agent, the said material after the regeneration still keeps high Sulfur capacity, and can also regenerate after the use of the material after the regeneration; So recycle; Not only practice thrift resource, reduced useless agent and can not use pollution on the environment, and had great economic implications; (7) use two kinds of renovation process of the present invention except obtaining the amorphous hydrous iron oxide of regenerated, can also obtain the crystalline elemental sulfur, make the utilization of resource obtain maximization; (8) before the regeneration step of two kinds of renovation process of the present invention, can comprise a step with the said useless agent of water washing; This step is in order to remove in the sweetening process other impurity attached to said useless agent surface, to avoid said impurity that the subsequent regeneration step is caused detrimentally affect; (9) the agent powder that in two kinds of renovation process of the present invention, will give up is made into suspension-s and feeds oxygenous gas and carry out oxidation; The advantage of this method for oxidation is the oxidising process may command; Oxidation effectiveness is good; In addition, the preferred 10-15% of solid quality percentage composition in the suspension-s of being prepared, oxidation rate is fast and can guarantee that the material oxidation is complete in this scope; (10) the present invention is with the method for floating of the mine ore dressing sweetening agent regeneration field of migrating; Through bubbling air the amorphous hydrous iron oxide of said regenerated is separated with elemental sulfur; Promptly realized the separation purification of the omnidirectional hydrous iron oxide of said regeneration, therefore had good economic implications and Significance for Environment through the method for complete physics; (11) in two kinds of renovation process of the present invention, the agent of will giving up grinds to form 100-400 purpose particle (preferred 200 orders), and such granularity helps the oxidation of said useless agent, also helps follow-up extraction step or flotation step; (12) use the prepared material that contains amorphous hydrous iron oxide of the inventive method, also be applicable to any other field except the sweetening agent field in the prior art.
Embodiment
Embodiment 1
Contain the preparation of the material of amorphous hydrous iron oxide:
32g ferrous sulfate powder and 12g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.8; The said mixture material is put into kneader, pinch 3h and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards, be beneficial to the abundant completion of above-mentioned reaction thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 80 ℃, and drying time is 3h, can make the material A that contains amorphous hydrous iron oxide of the present invention.In this material A, contain the amorphous hydrous iron oxide of 97.0wt%, surplus is sodium sulfate and water, surveying its Sulfur capacity is 52%.
Renovation process 1:
Said material A is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, band water grinds to form 300 purpose particles in wet-type ball mill, obtains useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, and use CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 48% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 45%, the four material after the regeneration is 43% for the third time.
Renovation process 2:
Said material A is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 300 purpose particles, obtained useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; Said slurries are placed flotation cell; And in said flotation cell, add entry, add water glass and kerosene again as flotation aid, then bubbling air; Elemental sulfur is bubbled through the water column because of its hydrophobic nature and is overflowed; Then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated, can be used as sweetening agent behind the said drying materials again and uses, and the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 49% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 47%, the four material after the regeneration is 45% for the third time.
The effect of said flotation aid is better for the separating effect that makes said amorphous hydrous iron oxide and elemental sulfur, and following examples together.
Embodiment 2
Contain the preparation of the material of amorphous hydrous iron oxide:
64g ferrous sulfate powder and 21.2g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.4; The said mixture material is put into kneader, pinch 0.5h and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is-5 ℃, and be 10h time of drying, can make the material B that contains amorphous hydrous iron oxide of the present invention.In this material B, contain the amorphous hydrous iron oxide of 95.8wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 51.8%.
Renovation process 1:
Said material B is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 49%; The Sulfur capacity of the material after the regeneration is 47% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 46%, the four material after the regeneration is 43% for the third time.
Renovation process 2:
Said material B is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; Filter said slurries and obtain solid materials; Said solid materials is placed flotation cell, add entry, then bubbling air; So because of the hydrophobic nature of said elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.The said effusive elemental sulfur that overflows can be purified through extraction or other method; Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 47% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 46%, the four material after the regeneration is 45% for the third time.
Embodiment 3
Contain the preparation of the material of amorphous hydrous iron oxide:
34.2g Iron nitrate powder and 23.4g Pottasium Hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.0; The said mixture material is put into kneader, pinch 1.0h and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is 45 ℃, and drying time is 3h; Can make the material C that the present invention contains amorphous hydrous iron oxide; In this sweetening agent C, contain the amorphous hydrous iron oxide of 96.1wt%, surplus is saltpetre and water.Surveying its Sulfur capacity is 51.3%.
Renovation process 1:
Said material C is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 48% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 47%, the four material after the regeneration is 45% for the third time.
Renovation process 2:
Said material C is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, because of the hydrophobic nature of said elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 49% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 47%, the four material after the regeneration is 45% for the third time.
Embodiment 4
Contain the preparation of the material of amorphous hydrous iron oxide:
64g ferrous sulfate powder and 22g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.5; The said mixture material is put into kneader, pinch 15min and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 90 ℃, and drying time is 3h, can make the present invention and contain amorphous hydrous iron oxide material D.In this material D, contain the amorphous hydrous iron oxide of 95.6wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 51.3%.
Renovation process 1:
Said material D is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 48% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 47%, the four material after the regeneration is 45% for the third time.
Renovation process 2:
Said material D is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; Filter said slurries and obtain solid materials, said solid materials is placed flotation cell, add entry; Add water glass and kerosene again as flotation aid; Bubbling air then, elemental sulfur overflows because of it has hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 49% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 47%, the four material after the regeneration is 45% for the third time.
Embodiment 5
Contain the preparation of the material of amorphous hydrous iron oxide:
64g ferrous sulfate powder and 22g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.5; The said mixture material is put into kneader, pinch 2.0h and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is 30 ℃, and be 1h time of drying, can make the material E that the present invention contains amorphous hydrous iron oxide.In this material E, contain the amorphous hydrous iron oxide of 95.2wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 51.0%.
Renovation process 1:
Said material E is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 49%; The Sulfur capacity of the material after the regeneration is 47% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 45%, the four material after the regeneration is 44% for the third time.
Renovation process 2:
The said material that contains amorphous hydrous iron oxide is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, because of the hydrophobic nature of elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 50%; The Sulfur capacity of the material after the regeneration is 48% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 46%, the four material after the regeneration is 44% for the third time.
Embodiment 6
Contain the preparation of the material of amorphous hydrous iron oxide:
64g ferrous sulfate powder and 22g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.5; The said mixture material is put into kneader, pinch 25min and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is 30 ℃, and be 1h time of drying, can make the material F that contains amorphous hydrous iron oxide of the present invention.In this material F, contain the amorphous hydrous iron oxide of 95.3wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 50.8%.
Renovation process 1:
Said material F is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 300 purpose particles, obtained useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again after the said material iron oven dry and use, the Sulfur capacity of said material is 48%; The Sulfur capacity of the material after the regeneration is 46% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 44%, the four material after the regeneration is 42% for the third time.
Renovation process 2:
Said material F is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 300 purpose particles, obtained useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated; Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 49%; The Sulfur capacity of the material after the regeneration is 47% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 45%, the four material after the regeneration is 43% for the third time.
Embodiment 7
Contain the preparation of the material of amorphous hydrous iron oxide:
64g ferrous sulfate powder and 20g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.3; The said mixture material is put into kneader, pinch 30min and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 100 ℃, and drying time is 1h, can make the material G that contains amorphous hydrous iron oxide of the present invention.In this sweetening agent G, contain the amorphous hydrous iron oxide of 95.6wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 50.2%.
Renovation process 1:
Said material G is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 47.5%; The Sulfur capacity of the material after the regeneration is 45% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 43%, the four material after the regeneration is 41% for the third time.
Renovation process 2:
Said material G is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry; Bubbling air is so because of the hydrophobic nature of said elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.The said effusive elemental sulfur that overflows can be purified through extraction or other method; Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 48%; The Sulfur capacity of the material after the regeneration is 46% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 44%, the four material after the regeneration is 42% for the third time.
Embodiment 8
Contain the preparation of the material of amorphous hydrous iron oxide:
92g ferrous sulfate powder and 28g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 2.2; The said mixture material is put into kneader, pinch 30min and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is 45 ℃, and be 1h time of drying, can make the amorphous hydrous iron oxide material H that contains of the present invention.In this material H, contain the amorphous hydrous iron oxide of 96.5wt%, surplus is sodium sulfate and water.Surveying its Sulfur capacity is 49.5%.
Renovation process 1:
Said material H is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering; Coextration three times; Combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, and remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards; Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 46%; The Sulfur capacity of the material after the regeneration is 44% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 42%, the four material after the regeneration is 40% for the third time.
Renovation process 2:
Said material H is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, because of the hydrophobic nature of said elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 47.5%; The Sulfur capacity of the material after the regeneration is 45% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 43%, the four material after the regeneration is 42% for the third time.
Embodiment 9
Contain the preparation of the material of amorphous hydrous iron oxide:
20.9g iron protochloride powder and 21.7g sodium hydroxide are mixed, and wherein, iron and mol ratio hydroxy are 1: 3.0; The said mixture material is put into kneader, pinch 30min and accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards thereby mix.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is carried out seasoning, and drying temperature is 45 ℃, and be 1h time of drying, can make the material I that contains amorphous hydrous iron oxide of the present invention.In this material I, contain the amorphous hydrous iron oxide of 95.0wt%, surplus is sodium-chlor and water.Surveying its Sulfur capacity is 48.0%.
Renovation process 1:
Said material I is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The material that extraction obtains after filtering; Coextration three times; Combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, and remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards; Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 46%; The Sulfur capacity of the material after the regeneration is 44.2% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 42%, the four material after the regeneration is 40% for the third time.
Renovation process 2:
Said material I is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; Filter said slurries and obtain solid materials, said solid materials is placed flotation cell, add entry; Add water glass and kerosene again as flotation aid; Bubbling air then, because of the hydrophobic nature of elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 47%; The Sulfur capacity of the material after the regeneration is 46% for the second time, and the Sulfur capacity of the material after the regeneration is that the Sulfur capacity of 44%, the four material after the regeneration is 42% for the third time.
In the foregoing description 1～9, employed ferrous sulfate powder is FeSO
47H
2O content is the industrial raw material of 88～90wt%; In the sodium hydroxide in the content of NaOH or the Pottasium Hydroxide content of KOH be 90～93wt%;
FeSO in following examples
47H
2O, FeNO
36H
2O, FeCl
24H
2The amount of O, NaOH and KOH is 100% to calculate by its purity all, no matter and its actual purity, its actual amount can be calculated according to the difference of material purity separately in concrete application process.
Embodiment 10
Contain the preparation of the material of amorphous hydrous iron oxide:
With 32 gram FeSO
47H
2O powder and 12 gram NaOH mix, and wherein, iron ion and mol ratio hydroxy are 1: 2.6; The said mixture material is put into kneader, mix and to pinch 15 minutes, the control temperature of charge is 30-40 ℃, mix pinch completion after, above-mentioned reaction product is placed in the air dries, be beneficial to the abundant completion of above-mentioned reaction.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 95 ℃, and drying time is 3 hours, promptly obtains containing the material J of amorphous hydrous iron oxide, and the content of amorphous hydrous iron oxide is 85% in the said material, and all the other components are Na
2SO
4And water, the Sulfur capacity of said material is 45%.
Renovation process 1:
Said material J is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 43%; Sulfur capacity after the regeneration is 42% for the second time, and the Sulfur capacity after the regeneration is that 40%, the four Sulfur capacity after the regeneration is 39% for the third time.
Renovation process 2:
Said material J is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 100 purpose particles, obtained useless agent powder; It is 5% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry; Bubbling air again is so because of the hydrophobic nature of said elemental sulfur overflows, then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.The said effusive elemental sulfur that overflows can be purified through extraction or other method; Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material is 44%; Sulfur capacity after the regeneration is 43.2% for the second time, and the Sulfur capacity after the regeneration is that 41.4%, the four Sulfur capacity after the regeneration is 40% for the third time.
Embodiment 11
Contain the preparation of the material of amorphous hydrous iron oxide:
With 64g FeSO
47H
2O powder and 21.2g NaOH mix, and wherein, iron ion and mol ratio hydroxy are 1: 2.3; The said mixture material is put into kneader, mix and to pinch 20 minutes, the control temperature of charge is 40-50 ℃, mix pinch completion after, above-mentioned reaction product is placed in the air dries.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 85 ℃, and be 6h time of drying, promptly obtains containing the material K of amorphous hydrous iron oxide, and the content of amorphous hydrous iron oxide is 80% in the said material, and all the other components are Na
2SO
4And water, the Sulfur capacity of said material is 43%.
Renovation process 1:
Said material K is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again behind the said drying materials that contains the amorphous hydrous iron oxide of regenerated and use, the Sulfur capacity of said material does
41.8%Sulfur capacity after the regeneration does for the second time
39.6%, the Sulfur capacity after the regeneration does for the third time
37.3%, the Sulfur capacity after the 4th regeneration does
35.2%
Renovation process 2:
Said material K is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 200 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, said elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material does
42%Sulfur capacity after the regeneration does for the second time
41.4%, the Sulfur capacity after the regeneration is 39.2 for the third time
%, the Sulfur capacity after the 4th regeneration does
37%
Embodiment 12
Contain the preparation of the material of amorphous hydrous iron oxide:
With 34.2g FeNO
36H
2O powder and 16.9g Pottasium Hydroxide mix, and wherein, iron ion and mol ratio hydroxy are 1: 2.0; The said mixture material is put into kneader, mix and pinch 1.0h and control temperature of charge, thereby accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards at 50-60 ℃.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 50 ℃, and drying time is 4h, promptly obtains containing the material L of amorphous hydrous iron oxide, and the content of amorphous hydrous iron oxide is 76% in the said material, and all the other components are KNO
3And water, the Sulfur capacity of said material is 41.0%.
Renovation process 1:
Said material L is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 300 purpose particles, obtained useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CCl
4The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent again after the said material iron oven dry and use, the Sulfur capacity of said material is 40%; Sulfur capacity after the regeneration is 38% for the second time, and the Sulfur capacity after the regeneration is that 36%, the four Sulfur capacity after the regeneration is 34.4% for the third time.
Renovation process 2:
Said material L is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 300 purpose particles, obtained useless agent powder; It is 15% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated; Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of the amorphous hydrous iron oxide of said regenerated is 40%; Sulfur capacity after the regeneration is 38.5% for the second time, and the Sulfur capacity after the regeneration is that 37.2%, the four Sulfur capacity after the regeneration is 36% for the third time.
Embodiment 13
Contain the preparation of the material of amorphous hydrous iron oxide:
With 64gFeSO
47H
2O powder and 22g sodium hydroxide mix, and wherein, iron and mol ratio hydroxy are 1: 2.4; The said mixture material is put into kneader, mix that to pinch 15min and control temperature of charge be 60-70 ℃, thereby accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 60 ℃, and drying time is 3h, promptly obtains containing the material M of amorphous hydrous iron oxide, and the content of amorphous hydrous iron oxide does in the said material
68%, all the other components are Na
2SO
4, water and Z 250, the Sulfur capacity of said material are 39.8%.
Renovation process 1:
Said material M is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The solid materials that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 38.9%; Sulfur capacity after the regeneration is 36.0% for the second time, and the Sulfur capacity after the regeneration is that 35.2%, the four Sulfur capacity after the regeneration is 33.0% for the third time.
Renovation process 2:
Said material M is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur; Filter said slurries and obtain solid materials, said solid materials is placed flotation cell, add entry; Add water glass and kerosene again as flotation aid; Bubbling air then, elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 38.0%; Sulfur capacity after the regeneration is 36.2% for the second time, and the Sulfur capacity after the regeneration is that 35.4%, the four Sulfur capacity after the regeneration is 33.2% for the third time.
Embodiment 14
Contain the preparation of the material of amorphous hydrous iron oxide:
With 64gFeSO
47H
2O powder and 22g sodium hydroxide mix, and wherein, iron and mol ratio hydroxy are 1: 2.4; The said mixture material is put into kneader, mix that to pinch 2.0h and control the material reaction temperature be 25-30 ℃, thereby accomplish the solid state reaction between the above-mentioned reactant, above-mentioned reaction product is placed in the air dries afterwards.Material after will drying adds water earlier and stirs, and repetitive scrubbing to gained is filtrated till the sulfate radical-free (checking with bariumchloride usually), uses whizzer that above-mentioned washings is filtered.Above-mentioned solid behind washing and filtering is dried, and bake out temperature is 70 ℃, and be 1h time of drying, promptly obtains containing the material N of amorphous hydrous iron oxide, and the content of amorphous hydrous iron oxide is 100% in the said material, and the Sulfur capacity of said material is 62%.
Renovation process 1:
Said material N is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 10% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S, the iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, filters said slurries and obtains solid materials, uses CS
2The material that extraction obtains after filtering, coextration three times, combining extraction liquid reclaims solvent with the distillatory method and obtains the crystalline elemental sulfur simultaneously, remaining solid is the material that contains the amorphous hydrous iron oxide of regenerated and extraction liquid is told afterwards.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 60%; Sulfur capacity after the regeneration is 48.2% for the second time, and the Sulfur capacity after the regeneration is that 47.1%, the four Sulfur capacity after the regeneration is 46.0% for the third time.
Renovation process 2:
Said material N is contained in desulfurization in the desulphurization reactor, treats H
2After S penetrated, the agent of will giving up drew off, and after water washing, in wet-type ball mill, ground to form 400 purpose particles, obtained useless agent powder; It is 30% aqeous suspension that said useless agent powder is made into the solid masses percentage composition, feeds pressurized air, and inspection by sampling after reaction for some time is when the sample and the hydrochloric acid reaction that take out do not generate H
2During S; Iron sulfide in the then useless agent is converted into amorphous hydrous iron oxide and elemental sulfur fully, forms the slurries that contain said amorphous hydrous iron oxide and elemental sulfur, and said slurries are placed flotation cell; Add entry and in said flotation cell, add water glass and kerosene as flotation aid; Bubbling air then, elemental sulfur overflows because of hydrophobic nature, and then the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.Can be used as sweetening agent behind the said drying materials again and use, the Sulfur capacity of said material is 60.2%; Sulfur capacity after the regeneration is 58.4% for the second time, and the Sulfur capacity after the regeneration is that 56.1%, the four Sulfur capacity after the regeneration is 54.0% for the third time.
The activity rating example
Get each 5g of sweetening agent A～N that the foregoing description 1 to embodiment 14 prepares, under normal temperature (finger ring border temperature is generally-5 ℃ to 45 ℃) normal pressure (environmental stress is generally 1 normal atmosphere), with containing H
2S is that the standard gas of 40000ppm carries out evaluation test.Wherein, qualitative detection, but autogamy 1% silver nitrate solution detects outlet sulphur; Detection by quantitative can adopt the comprehensive Microcoulomb instrument of homemade WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) to detect, and the lowest detection amount of this instrument is 0.2ppm.
Can find out that from above-mentioned test result the material that contains amorphous hydrous iron oxide with high Sulfur capacity of the present invention uses at normal temperatures and pressures, its Sulfur capacity can be up to 62.0%.
In the foregoing description, baking step carries out in electric drying oven with forced convection; The model of employed kneader is the polyfunctional catalyst shaper of CD4 * 1TS, and certainly, any commercially available kneader that can realize the object of the invention all goes for the present invention.
Obviously, the foregoing description only be for explanation clearly done for example, and be not qualification to embodiment.For the those of ordinary skill in affiliated field, can also make other multi-form variation or change on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (11)
1. preparation method who contains the material of amorphous hydrous iron oxide is characterized in that may further comprise the steps:
(1), be to mix in 1: 2 to 1: 3 by iron and mol ratio hydroxy with solid solubility ferrous salt and solid hydroxide;
(2) step (1) gained mixture is accomplished reaction through mixing to pinch, in said kneading process, the control temperature of charge is no more than 50 ℃;
(3) step (2) gained reaction product is dried in air;
(4) with resulting material washing of step (3) and filtration;
(5), promptly obtain containing the material of amorphous hydrous iron oxide with step (4) gained solid seasoning or oven dry.
2. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in said step (1), said solid hydroxide is sodium hydroxide or Pottasium Hydroxide.
3. the preparation method who contains the material of amorphous hydrous iron oxide according to claim 1 is characterized in that: in said step (2), said mixing pinched through the kneader completion, and the mixed time of pinching was at least 15 minutes.
4. preparation method according to claim 3 is characterized in that: the said mixed time of pinching is 15-30 minute.
5. preparation method according to claim 1 is characterized in that: in said step (5), the temperature of seasoning is-and 5-45 ℃.
6. preparation method according to claim 1 is characterized in that: in said step (5), bake out temperature is no more than 100 ℃.
7. preparation method according to claim 1 is characterized in that: in said step (5), bake out temperature is 80-100 ℃.
8. utilize the material that contains amorphous hydrous iron oxide that any preparation method prepares among the claim 1-7; It is characterized in that: less than 100wt%, all the other components are water and byproduct of reaction to the content of wherein said amorphous hydrous iron oxide more than or equal to 65.0wt%.
9. the material that contains amorphous hydrous iron oxide that utilizes the said preparation method of claim 1 to prepare is characterized in that: the content of wherein said amorphous hydrous iron oxide is 95.0-97.0wt%, and all the other components are water and byproduct of reaction.
10. the renovation process after the resulting material that contains amorphous hydrous iron oxide of any described preparation method uses as sweetening agent among the claim 1-7 is characterized in that may further comprise the steps:
(a). the useless agent after the said material that contains amorphous hydrous iron oxide used as sweetening agent grinds to form particle, obtains useless agent powder;
(b). said useless agent powder is made into suspension-s, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the said suspension-s be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain said amorphous hydrous iron oxide and elemental sulfur;
(c). filter said slurries and obtain solid materials, with the elemental sulfur in the said solid materials of SX, the extracted residual solid is the material that contains the amorphous hydrous iron oxide of regenerated.
11. the renovation process after the resulting material that contains amorphous hydrous iron oxide of any described preparation method uses as sweetening agent among the claim 1-7 is characterized in that may further comprise the steps:
(I). the useless agent after the said material that contains amorphous hydrous iron oxide used as sweetening agent grinds to form particle, obtains useless agent powder;
(II). said useless agent powder is made into suspension-s, feeds oxygenous gas and carry out oxidation, make the iron sulfide in the said suspension-s be converted into amorphous hydrous iron oxide and elemental sulfur, form the slurries that contain said amorphous hydrous iron oxide and elemental sulfur;
(III). said slurries maybe will be filtered the solid materials that said slurries obtain place container, bubbling air makes said elemental sulfur come-up, and the throw out of container bottom is the material that contains the amorphous hydrous iron oxide of regenerated.
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| CN101898108B (en) * | 2009-05-31 | 2013-10-16 | 北京三聚环保新材料股份有限公司 | Recyclable desulfurizer and preparation method thereof and regeneration method |
| US8603215B2 (en) | 2006-08-28 | 2013-12-10 | Beijing Sanju Environmental Protection and New Material Co., Ltd. | Composition of amorphous iron oxide hydroxide, desulfurizer comprising the same, and methods for preparing and regenerating the desulfurizer |
| WO2010081287A1 (en) | 2008-12-30 | 2010-07-22 | 北京三聚环保新材料股份有限公司 | Methods for preparing and regenerating materials containing amorphous iron oxyhydroxide and desulfurizer comprising the same |
| EP2383227B1 (en) | 2008-12-30 | 2018-01-24 | Beijing Sanju Environmental Protection and New Material Co., Ltd. | Preparation of material containing amorphous iron oxyhydroxide |
| EA023777B1 (en) | 2008-12-30 | 2016-07-29 | Беиджинг Санджу Энвиронмент Протекшин Энд Нью Материал Ко., Лтд. | Method for regenerating amorphous iron oxyhydroxide and desulfurizer containing amorphous iron oxyhydroxide as active component |
| CN101766946B (en) | 2008-12-30 | 2012-11-28 | 北京三聚环保新材料股份有限公司 | Technology for removing hydrogen sulfide in gas at room temperature |
| CN103418230B (en) * | 2012-05-17 | 2017-01-18 | 北京三聚环保新材料股份有限公司 | Supported amorphous ferric hydroxide desulfurizer and preparation method thereof |
| CN103991909B (en) * | 2013-02-20 | 2016-04-13 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of amorphous hydrous iron oxide of high sulfur capacity |
| CN104071850B (en) * | 2013-03-25 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of iron oxide black |
| CN108483407B (en) * | 2018-03-28 | 2020-10-27 | 北京三聚环保新材料股份有限公司 | Method for recovering sulfur on iron oxyhydroxide and application of iron oxyhydroxide with sulfur removed |
| CN113106433B (en) * | 2021-03-11 | 2022-07-05 | 同济大学 | Modification method for promoting iron ions to rapidly form gamma-FeOOH layer on iron chip surface |
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