CN101219320A - Method for producing iron oxide desulphurizing agent in normal temperature - Google Patents
Method for producing iron oxide desulphurizing agent in normal temperature Download PDFInfo
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- CN101219320A CN101219320A CNA2007100532855A CN200710053285A CN101219320A CN 101219320 A CN101219320 A CN 101219320A CN A2007100532855 A CNA2007100532855 A CN A2007100532855A CN 200710053285 A CN200710053285 A CN 200710053285A CN 101219320 A CN101219320 A CN 101219320A
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Abstract
The invention relates to a production method for a normal temperature iron oxide desulfurizer, which is characterized in that the production method comprises the steps that: 1) the selection of raw materials according to mass percentage is 10-85 percent of ferrous sulfate heptahydrate, 5-80 percent of insoluble carbonate and 0.5-40 percent of metamanganate according to weight percentage, and the ferrous sulfate heptahydrate, the insoluble carbonate and the metamanganate are prepared for spare; 2) mixing: the insoluble carbonate and the metamanganate are mixed for 20-30 minutes inside a premixer, in which the ferrous sulfate heptahydrate is then fed for continuous mixing; meanwhile, the water is sprayed into the premixer for 5-20 minutes, and the quantity added of the water is 2-40 percent of the weight of the ferrous sulfate heptahydrate, the insoluble carbonate and the metamanganate, thus obtaining a mixture A; 3) stationary phase reaction: the mixture A is added into a conical shell of a stationary phase reactor through a solid material feed inlet of the stationary phase reactor and is reacted through stirring and the action of adequate oxygen, thus obtaining a mixture B; 4) the normal temperature iron oxide desulfurizer is obtained through storing, prilling and drying. The method is characterized by environment protection, energy saving, low production cost, etc.; in addition, the desulfurizer has high purifying rate for removing sulfur.
Description
Technical field
The invention belongs to regenerative resource clean utilization field, rural area, relate to a kind of production method of iron oxide desulphurizing agent in normal temperature.
Technical background
The necessity of biogas desulfurization: biogas is a kind of common regenerative resource in rural area.But the production and use of marsh gas is perplexing the utilization of Chinese countryside biogas and the development of biogas as the clean utilization problem of regenerative resource always.Mainly show the unpleasant foul smell of the hydrogen sulfide gas in the biogas, hydrogen sulfide is a kind of pernicious gas of severe toxicity.Hydrogen sulfide is in air and under the wet environment condition, and to pipeline, burner and other combustion apparatus, measuring instrument etc. have strong corrosiveness, generate sulfur dioxide (SO behind the sulfureted hydrogen burning
2), meet water and generate the sulfurous acid molecule, again can corroding metal equipment, contaminated environment, and directly endanger the healthy of people.Have data to show: if contain 0.06% hydrogen sulfide gas in the air, human body respiration will seriously be poisoned in 1 hour, and eye mucosa and respiratory tract can be subjected to grievous injury; If when containing the hydrogen sulfide gas more than 0.2% in the air, the people will be dead in a few minutes.Stipulate in China's environmental health standards: residential neighborhoods Air Hydrogen Sulfide gas content must not surpass 0.01mg/m
3The workshop must not surpass 10mg/m
3, must not surpass 20mg/m in the town gas
3, biogas uses as a kind of energy, wherein the stink damp body burden also must not surpass 20mg/m
3, this index is exactly a biogas desulfurization index before use.
Industrially desulfurized technology is very ripe.Simply the general industry desulfur technology is applied to production and use of marsh gas desulphurization problem, from last century practice process that the eighties is promoted to the production and use of marsh gas technology of today prove difficulty.How towards the vast rural area of China, also not too rich vast farmers, allow their safety, convenient, use desulfur technology economically; It is the key that solves production and use of marsh gas development and clean utilization.
The composition of biogas: biogas is a kind of flammable mist, generally includes methane (CH
4) 60%～70%, carbon dioxide (CO
2) 25%～40% and a spot of ammonia (NH
3), hydrogen (H
2) and carbon monoxide (CO) etc.Simultaneously, also contain hydrogen sulfide (H in the biogas that different material is made
2S), its content is generally about 1～11g/m
3
The classification of sulfur method: biogas desulfurization method, generally being divided into the so-called direct desulfurization methods of direct desulfurization method and indirect desulfurization method two big classes is that the hydrogen sulfide gas that will produce in the biogas is removed, and the indirect desulfurization method is meant by some method, reduce or suppress the generation of hydrogen sulfide gas, thereby reach the purpose of desulfurization, biogas desulfurization is still based on the direct desulfurization method at present.
Biogas direct desulfurization method, its principle can be damp process and dry process two classes with reference to the sulfur method of coal gas.Damp process mainly contains WATER-WASHING METHOD, ADA method (anthraquinone disulphonate method), improvement ADA method, arsenic alkaline process, alkyl alcoholamine method, alkaline saline solution method etc.; Dry process mainly contains iron oxide process, activated carbon method etc.
For the desulfurization of the production and use of marsh gas, the method that is fit to desulfurization is the normal temperature oxidation iron processes in the dry process.Dry type normal temperature oxidation iron processes desulfurization principle: as hydrogen sulfide (H
2When S) contacting, generate iron sulfide through chemical reaction with activated ferric oxide.That play desulfidation at normal temperatures mainly is alpha-feooh and two kinds of hydrated ferric oxides of β-FeOOH and moisture γ-Fe
2O
3Wherein the alpha-feooh activity is the highest.The desulphurization reaction formula is:
Fe
2O
3·H
2O+3H
2S-→β-Fe
25
3·H
2O+3H
2O+21.7kJ/mol
Though the normal temperature iron oxide desulfurization is a kind of traditional dry type desulfurizing method,, in the coal gas industry at home and abroad, use till today because it has advantages such as raw material resources are abundant, economical and practical always.Normally used normal temperature iron oxide desulfurizing agent is divided into two types of powdery and graininess.
The raw material of desulfurizer powder has: the cast-iron scrap after the oxidation, marsh iron ore powder, aluminium metallurgy red mud, system waste residue of sulfuric acid and pneumatic steelmaking red mud etc.With particle diameter is that the cast-iron scrap of 0.6～2.4mm and wood chip are even by weight about 1: 1 ratio blending, carries out the artificial oxidation through fully tedding after the watering, generates the hydrated state iron oxide.The white lime that adds then about 0.5% is transferred to meta-alkalescence state between 8～9 with its pH value, adds an amount of water of people, and making its humidity is about 30%, ferric oxide desulfurizer, can case or adorn tower and use.
The desulfurizing agent of moulding is domestic has developed TG-1 type, TG-2 type, TG-3 type series desulfurizing agent product, (claiming ST-801 type normal temperature iron oxide desulfurizing agent on the market) in 1984 by Taiyuan engineering college.Its main component is removed Fe
2O
3, outside the water, charcoal, also have MgO, CaO and Al
2O
3Deng raw material.
TTL-1 type desulfurizing agent also is a kind of shaping desulfurizing agent.It is to be primary raw material with the red mud after the activation processing, adds the additive of some again, through mix, rub up, moulding and oven dry etc. process.
Appointed the love tinkling of pieces of jade to report in 2000: (1) is through the analysis and the selection of several industrial residues, Fe in pyrite cinder, converter red mud, the flat-top stove dirt
2O
3Content is all greater than 50%, and wide material sources, active good, is preparation desulfurizing agent ideal raw material, is equipped with binding agent, perforating agent, active co catalyst, moisture etc. again, can prepare different shaping desulfurizing agents.(2) the desulfurizing agent optimum formula is adhesive 5%～8%, perforating agent 0.08%～0.1%, wood chip 8%～12%, industrial residue 78%～88%, and the optimum temperature of moulding is 150 ℃.
The activation processing of external iron oxide desulphurizing agent has following several situation: handle marsh iron ore a few hours with the sodium hydroxide solution of 1 mol/L, wash with water, dry, fragmentation sieves and obtain high activity α-Fe
2O
3H
2O; Mix with NaOH with aluminium metallurgy accessory substance red mud, in roasting below 600 ℃, the cooling back is broken, promptly gets active red mud with hot-water soak; Levigate troilite drops into after 600-900 ℃ of roasting that cold quenching obtains oxide of high activity iron in the water.Prepared in laboratory α-Fe
2O
3H
2O joins the Fe (OH) that generates behind the aqueous solution of ammoniacal liquor or alkali to molysite aqueous solution
3Gelatinous precipitate is at room temperature more than the slaking 8hr, or makes in heating more than 200 ℃; Or ferric oxalate, ferric nitrate added thermal decomposition more than 200 ℃, perhaps with α-Fe
2O
3H
2O makes it to undergo phase transition 400-700 ℃ of heating.
The iron oxide ambient temperature desulfuration agent that above method obtains has 5 features: to H
2The first order reaction of S; The irreversibility of process; Liquid phase load (SLP) absorption property; The stage of process; The self-catalysis of process.
SW type desulfurizing agent is to be main component with the pyrite cinder, is mixed with the spheric granules of different-grain diameter in proportion with wood chip, activator, bonding agent etc.
Xing Tongchun once pointed out to have only α, γ type iron oxide to be only the active ingredient in the desulfurizing agent, i.e. activated ferric oxide.The activity problems of exhaling moral dragon, Ma Fengmei to study iron oxide points out in several forms of iron oxide, to have only α-Fe
2O
3, γ-Fe
2O
3Active higher; They have also compared the activity of various ferric oxide desulfurizers, think and use red mud as desulfurizing agent, and active iron content is very high, and the life-span is more much longer than marsh iron ore and artificial ferric oxide, if its active iron content is few, can improve by the artificial oxidation.Li Yanxu, Tian Qingping, Deng pointing out, the reduction and the sulfuration dynamic behavior available equivalents particle model that with the red mud are the iron oxide desulfurizing agent for high-temp gas of primary raw material preparation are characterized, reduction and sulfidation all exist by the dynamics transfer process of surface chemical reaction to DIFFUSION CONTROLLED, and diffusion activation energy is greater than the activation energy of surface reaction process.
Single Fe-series desulfurizing agent is not widely used because its desulfuration efficiency is low, now replaced by the desulfurizing agent that is composited with other metallic compound gradually, domestic Liu's generation is refined, Liu Zuyu has studied with the ferriferous oxide is main active, and (main component is Fe to make composite type metallic oxide consubstantiality particle desulfurizing agent with addition of other transition metal oxide
2O
3, TiO
2), characteristics such as that this kind desulfurizing agent has is active high, Sulfur capacity is big and renewable repeated use, sulfur removal technology be simple.External Sere etc. has developed and has contained Fe oxide+ZnO (5%～40%), SiO
2(5%～2O%) and TiO
2Or ZrO
2The desulfurizing agent of (35%～85%), desulfurizing agent at high temperature show high Sulfur capacity.
The Fe-series desulfurizing agent of domestic industry moulding has TG type normal temperature iron oxide desulfurizing agent, SN-1 type desulfurizing agent, AS type desulfurizing agent, SW type desulfurizing agent, PM type desulfurizing agent, NF type desulfurizing agent, EF-2 type iron oxide fine desulfurizer.
NT705 type desulfurizing agent is the novel desulfurizing agent of the common exploitation of China Petrochemical Industry's Research Institute of Nanjing Chemical Industry Group and Anqing research institute of company of China Petrochemical Industry, and it is based on iron oxide, and zinc oxide is auxilliary, and the interpolation a little auxiliary makes through compression molding.
Iron oxide desulphurizing agent is to be main component with the activated ferric oxide, adds a spot of alkaline matter, binding agent, perforating agent, structural type co-catalyst etc. in addition.Foreign study is found: during constant temperature fine desulfurizing, desulphurizing activated composition mainly is alpha-feooh, γ-FeOOH and γ-Fe in the iron oxide
2O
3If the characteristic of utilizing the iron oxide crystalline form to transform mutually after the activated processing of low activity iron oxide, just can improve its desulfurization performance, also can enlarge the use of iron oxide resource.The method of low activity iron oxide activation processing has alkali treatment activation, acidolysis activation, high temperature alkali iron processes, reduction-oxidation activation, mechanical lapping activation, cold quenching activation etc.
The Zhang Peifang of Xi'an University of Architecture and Technology's environment and municipal works institute, yellow-study is quick with Ca (OH)
2, gypsum, flyash and Fe
2O
3Powder is mixing by a certain percentage, add the water stirring and evenly mixing after, put into press-forming machine, make granular desulfuration agent, amount of water should be determined according to each composition humidity, be about 1/4 of gross weight.After placing the 90min typing, through steam activation, put into oven for drying again, bake out temperature is 105～110 ℃.The granular desulfuration agent of making is put into fixed bed after screening is weighed.
The nanometer alpha-feooh catalyst one-stage process that the Gao Zhihua of Institutes Of Technology Of Taiyuan, Li Chunhu etc. carry out removes COS and H
2The research of S performance has been opened up frontier for the normal temperature iron oxide fine desulfurization.This research tentatively shows: with the nanometer alpha-feooh is that the catalyst that active component prepares also can remove H effectively in catalysis COS hydrolysis
2S.
Gong Zhijian, Tian Yuanyu, Li Wenhua, propositions such as Xu Zhengang: at FeCl
2-NH
4The OH system, adopt different alkali ratio (n=1,0.8), different throughput (1.25L/min and 1.5L/min) prepared a plurality of FeOOH samples with different method for oxidation, to sample carry out TEM, XRD, TG characterizes explanation, oxidation rate reduces and easily generates low desulphurizing activated Fe
3O
4Or γ-FeOOH, alpha-feooh and Fe
3O
4The mixing phase, improve air mass flow, or add oxidant and accelerate oxidation rate, can generate desulphurizing activated higher FeOOH.
Gong Zhijian waits also and has reported: adopts FeSO
4-NaOH and FeCl
2-Ca (OH)
2Reaction system and different alkali ratio have prepared a plurality of FeOOHs, and to its crystal formation, pattern, specific area, specific pore volume and desulphurizing activated the sign.The result shows, FeSO
4-NaOH system acid system synthesizes FeOOH, increase desulphurizing activated increasing with the alkali ratio, and the synthetic result of alkaline process is just the opposite.And FeCl
2-Ca (OH)
2System alkali ratio is 1, and acid system makes amorphous FeOOH and has very high desulphurizing activatedly, and the thermogravimetric sulfuration conversion ratio FeOOH perfect than crystallization improves 31%.FeOOH is desulphurizing activated not only relevant with crystalline phase, and with crystalline form, particle diameter great relation is arranged.
Gong Zhijian studies show that: the preparation of FeOOH is subjected to the strong influence of preparation condition or environment, and different preparation methods will obtain the product of different structure and characteristic, as the isomr of different crystal forms different-shape or phase isomorphism different-shape.In order to prepare highly active normal temperature gas desulfurizer, adopt the synthetic respectively a plurality of FeOOHs of two-step method, quick oxidizing process, forced hydrolysis method and neutralisation, and prepared sample has been carried out rerum natura sign and desulphurizing activated research.Add H
2O
2The quick amorphous FeOOH that makes of oxidation has desulphurizing activatedly preferably, and saturated sulfuration rate of body weight gain is 66.0%, and 100min simulation Texaco coal gas thermogravimetric sulfuration conversion ratio reaches 69.03%.
Gong Zhijian is at FeSO
4In the mother liquor, than n=0.8, add the synthetic respectively a plurality of FeOOH samples of multiple different precipitating reagent with alkali; Adopt identical precipitating reagent, two kinds of ferrous salts, promptly different anion environment synthesizes a plurality of samples, and these samples have been carried out crystal formation, pattern, specific area, sign such as desulphurizing activated, and the result shows by NH
4HCO
3The spindle nanometer Fe OOH of precipitation has very high desulphurizing activated.
It is primary raw material that Liu Zhenyi, Liu Fengren have introduced with ferrous sulfate and NaOH, adopts intermediate processing, after filtration, washing, oven dry obtain a kind of unformed FeOOH, uses anaerobic H
2S standard gas is measured it and is penetrated Sulfur capacity greater than 50, is a kind of active component of high Sulfur capacity desulfurizing agent, is used for removing the H of gas or liquid material
2S.
Lan Changyun has introduced: the main component of desulfurizing agent is Fe
2O
3H
2O in order to bring into play the principal component effect, adds auxiliary agent and perforating agent.General co-catalyst itself has desulfidation preferably, joins Fe
2O
3H
2Play synergy among the O, help improving desulfurized effect.Perforating agent is the porosity that is used for increasing desulfurizing agent, specific area, to increase H
2S and Fe
2O
3H
2O contacts opportunity, improves Fe
2O
3H
2The O desulfuration efficiency.By test that multiple auxiliary agent and perforating agent are carried out relatively, the co-catalyst and the perforating agent that help to improve desulfurized effect have been selected.The result shows that selecting with the zinc salt is auxiliary agent, NH
4HCO
3Be perforating agent, the desulfurized effect of prepared desulfurizing agent can be better by a certain percentage to add a kind of base agent simultaneously.
Behind desulfurizing agent work certain hour, the activity of desulfurizing agent descends gradually, and desulfurized effect is variation gradually.During generally with the conventional type ferric oxide desulfurizer, when desulfurizer outlet hydrogen sulfide in methane content surpasses 20mg/m
3, and the desulfurizing agent sulfur capacity does not reach at 30% o'clock, desulfurizing agent can be regenerated, and when the desulfurizing agent sulfur capacity is above above 30%, will more renew desulfurizing agent.
Summary of the invention
The object of the present invention is to provide the production method of a kind of environmental protection, energy-conservation, iron oxide desulphurizing agent in normal temperature that production cost is low.
To achieve these goals, technical solution of the present invention is: a kind of production method of iron oxide desulphurizing agent in normal temperature is characterized in that it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 10～85%, insoluble carbonate 5～80%, mangaic acid 0.5～40% partially, choose ferrous sulfate heptahydrate, insoluble carbonate and mangaic acid partially, standby;
2) mix: insoluble carbonate, inclined to one side mangaic acid were mixed in the premix machine 20～30 minutes, dropping into ferrous sulfate heptahydrate continues to mix, sprayed into water with 5～20 minutes simultaneously, the addition of water is 2～40% of ferrous sulfate heptahydrate, insoluble carbonate and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 5min～1000min, gets compound B;
4) deposit, granulation, drying: compound B stacked 0.5～10 hour; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 70～230 ℃ scope.
Described insoluble carbonate is calcium carbonate or dolomite.
Described calcium carbonate can be the powder of natural limestone by machining, also can be that natural limestone carries out the light calcium carbonate powder that chemical treatment obtains after burning; Described powder diameter is 100 orders～400 orders.
Characteristics of the present invention:
1, selected a kind of do not allow acid carbonate (calcium carbonate) and ferrous sulfate heptahydrate reaction for use, obtained to have desulphurizing activated FeOOH product.What acid carbonate was not allowed in employing also has a following advantage: 1), shortened production process, 2), reduced the discharging of technique waste water, 3), reduced production cost.
2, the application of solid phase reactor makes course of reaction become very simple, the air injector head is established in the bottom of the conical shell of existing cone-type mixer, improvement should be as the solid phase reactor of ferrous sulfate and calcium carbonate reaction, because bubbling air in the conical shell, provide oxygen for reaction on the one hand, strengthened mixed effect on the other hand; This solid phase reactor has fully the low characteristics that mix, consume energy, and material can be oxidized fully.
3, the cost of material consumption rate of product is lower, and production cost of products is low; The desulfurizing and purifying rate height of product.
4, the effect of mangaic acid partially:
1), the function of acceleration low price iron to the conversion of high price iron arranged in course of reaction.Shortened oxidation time.Mangaic acid is the catalyst of course of reaction partially.
2), as the desulfurizing agent component.Generate salt with the hydrogen sulfide effect, it is blocked that the transfer function of this salt in micropore makes that the micropore of desulphurization catalyst is difficult for.
The present invention and existing manufacturing technique relatively have following beneficial effect:
1, the desulfurizing agent of producing with raw material such as waste residue of sulfuric acid relatively, old technology activity sweetening component is low.Unit of the present invention iron oxide content is 57.3 grams/100 gram iron oxide (active sweetening component height) to the contribution calculation of desulfurization; The sulphur purifying rate height that desulfurizing agent takes off.
2, with use FeSO
47H
2The O desulfurizing agent compares, the soluble carbon hydrochlorate of old process using, and production technology produces a large amount of waste water, can cause the phenomenon of contaminated environment to take place.The present invention is insoluble calcium carbonate and uses FeSO
47H
2O carries out solid phase reaction, the discharging of no waste residue, waste liquid, and more environmental protection more economizes on resources.
3, traditional ferric oxide desulfurizer all experiences and adds water preparation slip, then the technical process of the dry reactivation of unnecessary water, but need consume more energy to these moisture dryings.The present invention is energy-conservation.
4, compare with existing production method, production equipment of the present invention is simpler.
5, outstanding feature be the iron oxide desulphurizing agent in normal temperature of explained hereafter of the present invention when being applied to production and use of marsh gas desulfurization, the content of the hydrogen sulfide in methane after the desulfurization of experiment test proof is lower than 0.1ppm; And the content of the hydrogen sulfide in methane after the desulfurization of general desulphurization catalyst can only reach 20ppm.This desulfurization granularity be other iron oxide desulphurization catalyst can not compare.
The present invention is applied to production and use of marsh gas desulfurization.
Description of drawings
Fig. 1 is the structural representation of solid phase reactor
Fig. 2 is the A portion enlarged drawing of Fig. 1
Among the figure: 1-motor, 2-first reductor, 3-second reductor, 4-deduster interface, 5-solid material charging aperture, the 6-arm that revolves round the sun, 7-be from pivoted arm, 8-spiral blade, 9-discharging opening, 10-air injector head, the 11-reinforcement, 12-conical shell, 13-air guide hole, 14-transmission mechanism.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of production method of iron oxide desulphurizing agent in normal temperature, it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 10%, calcium carbonate 80%, mangaic acid 10% is chosen ferrous sulfate heptahydrate, calcium carbonate and mangaic acid partially partially, and is standby;
2) mixing: calcium carbonate, inclined to one side mangaic acid were mixed 20 minutes in the premix machine, drop into ferrous sulfate heptahydrate and continue to mix, sprayed into water with 5 minutes simultaneously, the addition of water is 2% of ferrous sulfate heptahydrate, calcium carbonate and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 5min, gets compound B;
4) deposit, granulation, drying: compound B stacked 2 hours; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 70 ℃ scope.
Described calcium carbonate can be the powder of natural limestone by machining, also can be that natural limestone carries out the light calcium carbonate powder that chemical treatment obtains after burning.Described powder diameter is 100 orders～400 orders.
Embodiment 2:
A kind of production method of iron oxide desulphurizing agent in normal temperature, it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 50%, calcium carbonate 45%, mangaic acid 5% is chosen ferrous sulfate heptahydrate, calcium carbonate and mangaic acid partially partially, and is standby;
2) mixing: calcium carbonate, inclined to one side mangaic acid were mixed 25 minutes in the premix machine, drop into ferrous sulfate heptahydrate and continue to mix, sprayed into water with 15 minutes simultaneously, the addition of water is 5% of ferrous sulfate heptahydrate, calcium carbonate and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 50mi, gets compound B;
4) deposit, granulation, drying: compound B stacked 8 hours; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 100 ℃ scope.
Described calcium carbonate can be the powder of natural limestone by machining, also can be that natural limestone carries out the light calcium carbonate powder that chemical treatment obtains after burning.
Embodiment 3:
A kind of production method of iron oxide desulphurizing agent in normal temperature, it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 85%, calcium carbonate 5%, mangaic acid 10% is chosen ferrous sulfate heptahydrate, calcium carbonate and mangaic acid partially partially, and is standby;
2) mixing: calcium carbonate, inclined to one side mangaic acid were mixed 30 minutes in the premix machine, drop into ferrous sulfate heptahydrate and continue to mix, sprayed into water with 20 minutes simultaneously, the addition of water is 8% of ferrous sulfate heptahydrate, calcium carbonate and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 1000mi, gets compound B;
4) deposit, granulation, drying: compound B stacked 10 hours; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 230 ℃ scope.
Described calcium carbonate can be the powder of natural limestone by machining, also can be that natural limestone carries out the light calcium carbonate powder that chemical treatment obtains after burning.
Embodiment 4:
A kind of production method of iron oxide desulphurizing agent in normal temperature, it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 60.5%, dolomite 39%, mangaic acid 0.5% is chosen ferrous sulfate heptahydrate, dolomite and mangaic acid partially partially, and is standby;
2) mixing: dolomite, inclined to one side mangaic acid were mixed 25 minutes in the premix machine, drop into ferrous sulfate heptahydrate and continue to mix, sprayed into water with 15 minutes simultaneously, the addition of water is 5% of ferrous sulfate heptahydrate, dolomite and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 500mi, gets compound B;
4) deposit, granulation, drying: compound B stacked 8 hours; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 130 ℃ scope.
Embodiment 5:
A kind of production method of iron oxide desulphurizing agent in normal temperature, it comprises the steps:
1) choosing of raw material: be: ferrous sulfate heptahydrate (FeSO by mass percent
47H
2O) 30%, dolomite 30%, mangaic acid 40% is chosen ferrous sulfate heptahydrate, dolomite and mangaic acid partially partially, and is standby;
2) mixing: dolomite, inclined to one side mangaic acid were mixed 25 minutes in the premix machine, drop into ferrous sulfate heptahydrate and continue to mix, sprayed into water with 20 minutes simultaneously, the addition of water is 40% of ferrous sulfate heptahydrate, dolomite and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 1000min, gets compound B;
4) deposit, granulation, drying: compound B stacked 0.5 hour; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is delivered to band drier and is carried out drying, and the oven dry activation gets iron oxide desulphurizing agent in normal temperature (product) in 110 ℃ scope.
As shown in Figure 1 and Figure 2, solid phase reactor, it comprises conical shell, spiral agitator, bleeder valve, air injector head 12, conical shell 12 is turbinations, in the conical shell is cavity, and the upper surface of conical shell is provided with solid material charging aperture 5, deduster interface 4, is discharging opening 9 at the bottom of the conical shell, the discharging opening place is provided with bleeder valve, and the upper surface of conical shell is provided with reinforcement 11; Spiral agitator comprises motor 1, first reductor 2, second reductor 3, transmission mechanism 14, gyratory shaker structure, the gyratory shaker structure comprise the revolution arm 6, from pivoted arm 7, be provided with spiral blade 8 from pivoted arm, the revolution arm 6, in pivoted arm 7 lays respectively at the cavity of conical shell, can rotation and can revolve round the sun from pivoted arm, motor 1, first reductor 2, second reductor 3 are located at that (detailed structure of spiral agitator please refer to existing cone-type mixer on the upper surface of conical shell; Motor also can be 2, drives 2 reductors respectively).The bottom of conical shell has the air feed mouth, is provided with air injector head 10 in the air feed mouth, and the air guide hole 13 on the air injector head is positioned at the cavity of conical shell.
The upper surface of described conical shell (at the bottom of the awl) diameter is 0.3～10 meter, and the height of conical shell is 0.5～10 meter.
Described air feed mouth be positioned at conical shell from bottom to up the conical surface locate below 1/3rd.
Described air feed mouth be shaped as circle, ellipse or polygon.
Described air feed mouth is 1-1000 (determining as required).
The area of described air feed mouth is 1cm
2～5000cm
2
The area in described air guide hole 13 is 1cm
2～300cm
2
Described air guide hole 13 be shaped as circle, ellipse or polygon.
The perforate direction in described air guide hole 13 is the directions along the revolution arm rotation of spiral agitator.
The angle on the normal at the geometric center place in described air guide hole 13 and spiral agitator revolution plane is a negative value, is-50 °～0 °.
The spiral agitator revolution speed is controlled at 2～10 commentaries on classics/min, and the spiral agitator rotational velocity is controlled at 20～80 commentaries on classics/min.
Claims (4)
1. the production method of an iron oxide desulphurizing agent in normal temperature is characterized in that it comprises the steps:
1) choosing of raw material: be by mass percent: ferrous sulfate heptahydrate 10～85%, insoluble carbonate 5～80%, inclined to one side mangaic acid 0.5～40% are chosen ferrous sulfate heptahydrate, insoluble carbonate and inclined to one side mangaic acid, and be standby;
2) mix: insoluble carbonate, inclined to one side mangaic acid were mixed in the premix machine 20～30 minutes, dropping into ferrous sulfate heptahydrate continues to mix, sprayed into water with 5～20 minutes simultaneously, the addition of water is 2～40% of ferrous sulfate heptahydrate, insoluble carbonate and an inclined to one side mangaic acid quality, gets compound A;
3) solid phase reaction: compound A is joined in the conical shell of solid phase reactor from the solid material charging aperture of solid phase reactor, react under the oxygen effect of stirring and abundance, the reaction time is controlled at 5min～1000min, gets compound B;
4) deposit, granulation, drying: compound B stacked 0.5～10 hour; The comminutor granulation of compound after the stacking, granularity is controlled at the scope of 12～8mm * 2～10mm; The material that granulation is good is dried activation in 70～230 ℃ scope, get iron oxide desulphurizing agent in normal temperature.
2. the production method of a kind of iron oxide desulphurizing agent in normal temperature according to claim 1, it is characterized in that: described insoluble carbonate is calcium carbonate or dolomite.
3. the production method of a kind of iron oxide desulphurizing agent in normal temperature according to claim 2, it is characterized in that: described calcium carbonate is the powder of natural limestone by machining, or natural limestone carries out the light calcium carbonate powder dolomite powder that chemical treatment obtains after burning.
4. the production method of a kind of iron oxide desulphurizing agent in normal temperature according to claim 3, it is characterized in that: described powder diameter is 100 orders～400 orders.
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