CN103301742B - Desulfurizing agent and preparation method thereof - Google Patents
Desulfurizing agent and preparation method thereof Download PDFInfo
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- CN103301742B CN103301742B CN201310256989.8A CN201310256989A CN103301742B CN 103301742 B CN103301742 B CN 103301742B CN 201310256989 A CN201310256989 A CN 201310256989A CN 103301742 B CN103301742 B CN 103301742B
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Abstract
The invention relates to a desulfurizing agent which comprises an Fe-Zn active component and an auxiliary agent, wherein the Fe-Zn active component is prepared by taking foamed sulfur as a raw material. The desulfurizing agent effectively utilizes the foamed sulfur, solves the problem of sewage discharge and is more important to change wastes into valuables. The invention provides a high-sulfur-capacity desulfurizing agent which promotes the technological advance and enhances the economic benefit. Research discovers that a filter cake is obtained by carrying out alkali wash on the foamed sulfur, high porosity is achieved, and the high porosity can be effectively kept by taking silicon sol as an adhesive; Fe<2+> are uniformly dispersed over around Zn<2+> through colloid molecules -Si-O-Si- which are uniformly dispersed in the silicon sol, Fe and Zn can be closely bonded through a roasting process and uniformly distributed in a high-porosity three-dimensional framework formed through the bonding of silicon dioxide to synergically exert desulfurization, and high sulphur capacity is endued to the desulfurizing agent. In addition, the desulfurizing agent disclosed by the invention is simple in preparation process and environmental-friendly and can obtain huge economic benefit.
Description
Technical field
The present invention relates to a kind of Fe-Zn fimily desulfurizing agent, belong to desulfurizing agent technical field.
Background technology
In recent years, methyl alcohol, low-carbon alcohols, dimethyl ether and lower carbon number hydrocarbons etc. are that the Coal Chemical Industry downstream product of raw material is widely used with coal.These Coal Chemical Industry downstream product mainly mainly produce chain with coal gasification → synthesizing of synthesis gas → downstream product, and the synthesis of these downstream product all needs catalyst, meanwhile, these catalyst are all very responsive to sulphur, and trace sulfide just can make catalyst activity Substance Intoxication inactivation.In addition, hydrogen sulfide sulfides contained in the waste water discharged in industrial production or waste gas, if directly discharge also can have a strong impact on environment, even causes person poultry poisoning.
Therefore, researcher is in order to effectively reduce sulfide, and particularly hydrogen sulfide is to the destruction of industrial production and environment, gives enough attention to the research and development of desulfurizing agent.The sulfur method of normal production can be carried out at present, wet method and the large class of dry method two can be divided into.Wet desulphurization is gas liquid reaction, and desulphurization reaction speed is fast, efficiency is high, sorbent utilization is high; When large-scale production, its production cost is low; But there is waste water handling problem, one-time investment is large.Dry desulfurization refers to that application powdery or granular absorbent, adsorbent or catalyst are to remove sulfide, and production technology is simple, and easy to operate, degree of purification is high; The research that domestic and international process is long-term, for dry desulfurization, have developed the serial desulfurizing agents such as active carbon, iron oxide, zinc oxide respectively.
Active carbon desulfurization mainly utilizes catalysis and the suction-operated of active carbon, and hydrogen sulfide is under the catalytic action of active carbon, and with oxygen generation oxidation reaction, the elemental sulfur that reaction generates is adsorbed in activated carbon surface, thus realizes removing of sulfide; When activated carbon desulphurization agent absorption reaches capacity, the absorption duct of activated carbon desulphurization agent is filled by sulphur substantially, and its desulfuration efficiency obviously declines, and adsorbance is limited, and circulation timei is short, is therefore unfavorable for large-scale industrial utilization.
With its degree of purification, good (volume fraction of the sulfur content after purification in material can be less than 0.1 × 10 to Zinc oxide desulfurizer
-6), Sulfur capacity height is famous.Current commodity Zinc oxide desulfurizer mainly contains high temperature modification and low form two kinds, the former serviceability temperature is 350 ~ 400 DEG C, the latter's serviceability temperature is 180 ~ 250 DEG C, desulfurizing agent due to two types all needs to use at a certain temperature, need thermal source, and consume certain energy, limit the use of Zinc oxide desulfurizer to a certain extent.
Fe-series desulfurizing agent is mainly the active component of desulfurizing agent with ferriferous oxide, described ferriferous oxide is mainly tri-iron tetroxide, di-iron trioxide and FeOOH, to have hydrogen sulfide at 20 ~ 110 DEG C and very high remove performance, desulphurizing activated the highest wherein with amorphous FeOOH, receives praises from customers.
Fe-Zn fimily desulfurizing agent then can have the advantage of Fe-series desulfurizing agent and Zinc oxide desulfurizer simultaneously, makes up mutually deficiency when both are used alone.Chinese patent literature CN1183996C discloses a kind of iron oxide compound desulfurizer, and containing iron oxide 30 ~ 70wt%, zinc oxide 5 ~ 30wt% and special auxiliary agent 5 ~ 30wt%, wherein special auxiliary agent is Al
2o
3, SiO
2, attapulgite, diatomite, Al
2o
3-SiO
2in one or more combination; Described iron oxide compound desulfurizer desulfurization precision is high, can realize the moderate temperature desulphurization of about 350 DEG C, and therefore Fe-Zn fimily desulfurizing agent has good development prospect.
Major part in above-mentioned dry-desulphurizer all cannot realize regeneration or regeneration cost high, cause by useless agent landfill in a large number, not only to waste the efficient resource in former desulfurizing agent, and causing new problem of environmental pollution; Therefore, research staff starts the research and development being devoted to desulfurizer regeneration technology.Chinese patent literature CN101898109A discloses a kind of desulfurizing agent repeating regeneration and preparation method thereof and renovation process, described desulfurizing agent is amorphous FeOOH desulfurizer, described renovation process comprises the steps: that the useless agent obtained after described desulfurizing agent uses by (1) grinds to form particle, obtains useless agent powder; (2) described useless agent powder is made into suspension, the gas passed into containing oxygen is oxidized, and makes the iron sulfide in described suspension be converted into amorphous FeOOH and elemental sulfur, forms the slurries containing described amorphous FeOOH and elemental sulfur; (3) filter described slurries and obtain solid material, with the elemental sulfur in solid material described in solvent extraction, in remaining solid, add organic binder bond after extraction or add organic binder bond and additive namely obtain regeneration after desulfurizing agent.
Not only Sulfur capacity is high for desulfurizing agent described in above-mentioned patent document, and use above-mentioned renovation process can make useless agent rapid regeneration, material after regeneration still keeps high Sulfur capacity, can recycle, not only save resource, decrease useless agent and new pollution is caused to environment, and there is great economic implications.But filtration and extraction step can produce a large amount of foam sulphur slurries in above-mentioned steps (3), wherein still a certain amount of amorphous FeOOH can be contained, if directly by wastewater treatment discharge, not only new environmental pollution can be caused, and can greatly waste raw material and the energy.If with foam sulphur for development of raw materials goes out new product, then not only problem of environmental pollution can be solved, can also save mass energy, and create huge economic profit.
Summary of the invention
For this reason, to be solved by this invention is the unserviceable problem of foam sulphur in FeOOH desulfurizer regenerative process in prior art, and providing a kind of is desulfurizing agent of preparing of raw material and preparation method thereof by the foam sulphur containing amorphous FeOOH.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of desulfurizing agent provided by the invention, comprises Fe-Zn active component and auxiliary agent, and described Fe-Zn active component is prepared by following steps:
S11, collect amorphous hydroxyl oxidize iron content and be greater than the foam sulphur slurries containing amorphous FeOOH that the regenerating desulfurization agent of 65wt% produces in oxidative regeneration process, cross leaching solid, with sodium hydrate aqueous solution, 3 times are at least washed to it, more at least wash 3 times with water, obtain foam sulphur filter cake;
S12, filter cake obtained in step S11 to be mixed with the predecessor of Ludox, zinc oxide or zinc oxide, shaping and dry;
S13, by dried article shaped roasting obtained in step S12;
S14, the calcining matter pulverizing will obtained in step S13, obtain Fe-Zn active component.
Desulfurizing agent according to claim 1, is characterized in that, in described step S12, the weight portion of each component is:
Filter cake 60-80 part;
Ludox 5-15 part;
Predecessor 15-25 part of zinc oxide or zinc oxide.
In Ludox described in described step S12, dioxide-containing silica is 20-40wt%.
In described step S13, sintering temperature is 200 ~ 220 DEG C.
The concentration of NaOH described in described step S11 is 5 ~ 15wt%.
The predecessor of zinc oxide described in described step S12 is one or more the combination in zinc hydroxide, zinc carbonate or basic zinc carbonate.
Described desulfurizing agent is made up of 85-95wt%Fe-Zn active component and 5-15wt% auxiliary agent.
Described auxiliary agent is one or more the combination in binding agent, extrusion aid, pore creating material.
The preparation method of desulfurizing agent of the present invention, comprises the following steps:
S21, take described Fe-Zn active component, described auxiliary agent according to selected parts by weight, and mix;
S22, material obtained in step S21 carried out mediate, shaping, and dry;
S23, the dry thing obtained by step S22 is carried out roasting, obtain described desulfurizing agent.
The temperature of described roasting is 300 ~ 350 DEG C, and the time is 2 ~ 4 hours.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, a kind of desulfurizing agent of the present invention, described desulfurizing agent comprises Fe-Zn active component and auxiliary agent, described Fe-Zn active component is prepared by raw material by the foam sulphur containing amorphous FeOOH, not only effectively make use of the foam sulphur slurries that the regenerating desulfurization agent containing amorphous FeOOH produces in oxidative regeneration process, solve the problem of sewage discharge, the more important thing is and turn waste into wealth, provide a kind of desulfurizing agent of high sulfur capacity, facilitate technological progress, improve economic benefit.The present invention studies discovery, and the foam sulphur filter cake that foam sulphur obtains after alkali cleaning has abundant duct, and porosity is high, is that binding agent effectively can retain high porosity with Ludox; And the colloid molecules-Si-O-Si-of homogeneous dispersion in Ludox makes Fe
2+be evenly dispersed in Zn
2+around, by roasting technique, Fe, Zn can be made to combine closely, and be evenly distributed in the high porosity three-dimensional framework that described foam sulphur filter cake formed by silica-bonded, collaboratively play desulfidation, give described desulfurizing agent high sulfur capacity.
2, a kind of desulfurizing agent of the present invention, the present invention studies and finds that described Fe-Zn active component is made up of with rational weight the predecessor of described filter cake, described Ludox and described zinc oxide or zinc oxide, Fe, Zn reasonable mixture ratio, desulphurizing activated height.
3, the preparation method of a kind of desulfurizing agent of the present invention, technique is simple, and prepared desulfurizing agent has high sulfur capacity.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearly, will be described in further detail embodiments of the present invention below.
Embodiment 1
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and 35g binding agent sodium carboxymethylcellulose.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 5 times of 5wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 5 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 180g, zinc oxide 75g, Ludox (silica quality content 40%) 45g, water 50g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 210 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 35 grams, mixes;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 300 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 2
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component, 7g sodium carboxymethylcellulose and 3.5g citric acid.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 4 times of 10wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 4 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 210g, zinc oxide 60g, Ludox (silica quality content 20%) 30g, water 45g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 200 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, 7g sodium carboxymethylcellulose and 3.5g citric acid, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 310 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 3
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and auxiliary agent sodium carboxymethylcellulose 11g, attapulgite 5.2g, citric acid 6g.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 3 times of 15wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 3 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 240g, zinc hydroxide 45g, Ludox (silica quality content 40%) 15g, water 60g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 220 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 11g, attapulgite 5.2g, citric acid 6g, mixes;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 4
Desulfurizing agent described in the present embodiment is made up of 200gFe-Zn active component and 35.3g binding agent sodium carboxymethylcellulose.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 5 times of 5wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 5 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 180g, zinc oxide 75g, Ludox (silica quality content 30%) 45g, water 50g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 210 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 35.3 grams, mixes;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 320 DEG C of roastings obtained in step S22 3 hours, obtained described desulfurizing agent.
Embodiment 5
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and 15g sodium carboxymethylcellulose, 12g citric acid.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 5 times of 5wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 5 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 210g, basic zinc carbonate 60g, Ludox (silica quality content 20%) 30g, water 45g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 200 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, 15g sodium carboxymethylcellulose, 12g citric acid, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 330 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 6
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and sodium carboxymethylcellulose 9g, attapulgite 4g, citric acid 4g.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 3 times of 15wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 3 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 240g, zinc oxide 20g, zinc hydroxide 25g, Ludox (silica quality content 40%) 15g, water 60g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 220 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 9g, attapulgite 4g, citric acid 4g, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 4 hours, obtained described desulfurizing agent.
Embodiment 7
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and 17g binding agent sodium carboxymethylcellulose.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 5 times of 10wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 5 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 180g, zinc hydroxide 75g, Ludox (silica quality content 20%) 45g, water 50g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 210 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 17g, mixes;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 8
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and 5.5g sodium carboxymethylcellulose, citric acid 5g.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 5 times of 5wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 5 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 210g, zinc carbonate 30g, Ludox (silica quality content 20%) 60g, water 45g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 200 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, 5.5g sodium carboxymethylcellulose, citric acid 5g, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 3 hours, obtained described desulfurizing agent.
Embodiment 9
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and sodium carboxymethylcellulose 13g, attapulgite 8g, citric acid 6g.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 3 times of 5wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 3 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 240g, zinc carbonate 45g, Ludox (silica quality content 30%) 15g, water 60g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 220 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 13g, attapulgite 8g, citric acid 6g, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 10
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component, 17g sodium carboxymethylcellulose and 13g citric acid.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 4 times of 10wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 4 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 210g, zinc oxide 60g, Ludox (silica quality content 20%) 30g, water 45g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 210 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, 17g sodium carboxymethylcellulose and 13g citric acid, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 320 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
Embodiment 11
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component, 14g sodium carboxymethylcellulose and 7g citric acid.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 4 times of 10wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 4 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 210g, zinc oxide 60g, Ludox (silica quality content 30%) 30g, water 45g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 200 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, 14g sodium carboxymethylcellulose and 7g citric acid, mix;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 330 DEG C of roastings obtained in step S22 4 hours, obtained described desulfurizing agent.
Embodiment 12
Desulfurizing agent described in the present embodiment comprises 200gFe-Zn active component and auxiliary agent sodium carboxymethylcellulose 11g, attapulgite 8g, citric acid 9g.
Described Fe-Zn active component preparation method is:
S11, foam sulphur slurries are crossed leaching solid, with the NaOH solution washing 3 times of 15wt%, every 200g foam sulphur solid uses the above-mentioned sodium hydroxide solution washing of 1L at every turn; Wash 3 times again with water, the every 200g foam sulphur solid after sodium hydroxide solution washing uses 1L water washing at every turn, obtains foam sulphur filter cake;
S12, take foam sulphur filter cake 240g, zinc oxide 15g, zinc carbonate 30g, Ludox (silica quality content 40%) 15g, water 60g, stirs, and it is the cylindrical of 4mm that Small-size Twin-Screw Extruders extruder is extruded diameter, 80 DEG C of dry 2h;
S13, by article shaped 220 DEG C of roasting 2h obtained in step S12;
S14, pulverized by calcining matter obtained in step S13,200 orders sieve, and obtain the Fe-Zn active component comprising amorphous FeOOH and zinc oxide.
The preparation method of described desulfurizing agent is:
S21, take Fe-Zn active component 200g, sodium carboxymethylcellulose 11g, attapulgite 5.2g, citric acid 6g, mixes;
S22, mixture obtained in step S21 is extruded the desulfurizing agent that diameter is 4mm on Small-size Twin-Screw Extruders extruder, 80 DEG C of dryings 2 hours;
S23, by dry thing 350 DEG C of roastings obtained in step S22 2 hours, obtained described desulfurizing agent.
The industrial chemicals such as the NaOH used in above-described embodiment, attapulgite, sodium carboxymethylcellulose, citric acid, Ludox, zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate are commercially available.
Foam sulphur slurries described in above-described embodiment, obtain by following methods: S1, choose the regenerating desulfurization agent that amorphous FeOOH mass content is about 72%, are placed in desulfurization reactor desulfurization, treat H
2after S penetrates, useless agent is drawn off, the preparation method of described regenerating desulfurization agent as described in comparative example 1, with reference to the embodiment 1 of Chinese patent CN1018988109A; S2, useless agent is washed with water after, in wet ball mill, be with water to grind to form 100 object particles, obtain useless agent powder; S3, described useless agent powder is made into the water slurry that solid masses percentage composition is 10%, passes into compressed air, sample after reaction a period of time, as the sample taken out and hydrochloric acid reaction not regeneration H
2stop during S passing into compressed air; S4, the slurries of formation are placed in flotation cell, add water, pass into air, floatingly select elemental sulfur and amorphous FeOOH; S5, collect the waste liquid produced in residue slurries in step S4 and elemental sulfur purification process, be foam sulphur slurries.
As convertible embodiment of the present invention, the foam sulphur slurries containing amorphous FeOOH that the regenerating desulfurization agent that amorphous hydroxyl oxidize iron content is greater than 65wt% produces in oxidative regeneration process all can as the raw material of desulfurizing agent of the present invention.
Comparative example 1
This comparative example provides a kind of regenerating desulfurization agent, and embodiment, with the embodiment 1 of Chinese patent CN1018988109A, is specially: by 3040 grams of FeSO
47H
2o is made into the aqueous solution and is placed in reactor, dropping into 900 grams of solid NaOH under agitation, by controlling the charging rate of solid NaOH, making reaction temperature be no more than 90 DEG C, after reaction terminates, filtration, filter cake wash with water, until sodium ions content is less than 0.5% in filter cake, then described filter cake are made into the water slurry that solid masses percentage composition is 15%, and pass into air and be oxidized, filter after oxidation completely, 90-100 DEG C of drying, namely obtain the material containing amorphous FeOOH.
Take 500 grams of above-mentioned materials, granularity is by 100 orders, and 40 grams, sesbania powder, wood chip 10 grams, mixing, small-sized kneader adds suitable quantity of water and completes kneading, then extrude bar shaped desulfurizing agent with Small-size Twin-Screw Extruders machine extruder, and 70 DEG C are dried 6 hours in an oven.
Described in above-described embodiment and comparative example, a working sulfur capacity assay method of desulfurizing agent is: unstripped gas volume content is the standard H of 4%
2s gas (spirit to be volume content be 20% CO
2, all the other are high-purity N
2), air speed is set as 300h
-1, reaction temperature 25 DEG C, normal pressure (environmental pressure is generally 1 atmospheric pressure).Desulfurizing agent loadings 0.3 milliliter, reactive desulfurizing agent terminal outlet tail gas sulfur content controls as 0.001ppm, and in tail gas, sulfur content adopts chromatography analysis to measure.
Carry out radial anti-crushing power according to examination criteria HG/T2782-93 to desulfurizing agent prepared in above-described embodiment and comparative example to test.By nitrogen adsorption specific surface area measuring instrument (model is JW-BK400, and precise and tiny Gao Bo science and technology Co., Ltd produces by Beijing), the porosity of desulfurizing agent prepared in above-described embodiment and comparative example is tested; And bulk density test is carried out to desulfurizing agent prepared in above-described embodiment.Test result is as shown in the table:
As can be seen from upper table data, embodiment 1-12 and the desulfurizing agent described in comparative example 1 compare, and the radial anti-crushing power of desulfurizing agent described in embodiment 1-12 slightly declines compared with comparative example 1, but still is all greater than 90N/cm, mechanical strength is high, has higher quality stability; The bulk density of desulfurizing agent described in embodiment 1-12 is about 0.100kg/L, and light weight, density are little, is convenient to filling and the use of described desulfurizing agent; The porosity of the desulfurizing agent described in embodiment 1-12 is higher, and Fe, Zn can be made to be evenly distributed in the three-dimensional framework of high porosity, and collaborative performance desulfidation, gives described desulfurizing agent high sulfur capacity; A working sulfur capacity of the desulfurizing agent described in embodiment 1-12 has certain decline compared with comparative example 1, but all can keep more than 39.18%, and desulfurized effect is good, has high using value.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among protection scope of the present invention.
Claims (10)
1. a desulfurizing agent, is characterized in that, described desulfurizing agent comprises Fe-Zn active component and auxiliary agent, and described Fe-Zn active component is prepared by following steps:
S11, collect amorphous hydroxyl oxidize iron content and be greater than the foam sulphur slurries containing amorphous FeOOH that the regenerating desulfurization agent of 65wt% produces in oxidative regeneration process, cross leaching solid, with sodium hydrate aqueous solution, 3 times are at least washed to it, more at least wash 3 times with water, obtain foam sulphur filter cake;
S12, filter cake obtained in step S11 to be mixed with the predecessor of Ludox, zinc oxide or zinc oxide, shaping and dry;
S13, by dried article shaped roasting obtained in step S12;
S14, the calcining matter pulverizing will obtained in step S13, obtain Fe-Zn active component.
2. desulfurizing agent according to claim 1, is characterized in that, in described step S12, the weight portion of each component is:
Filter cake 60-80 part;
Ludox 5-15 part;
Predecessor 15-25 part of zinc oxide or zinc oxide.
3. desulfurizing agent according to claim 2, is characterized in that, in Ludox described in described step S12, dioxide-containing silica is 20-40wt%.
4. desulfurizing agent according to claim 3, is characterized in that, in described step S13, sintering temperature is 200 ~ 220 DEG C.
5. desulfurizing agent according to claim 3, is characterized in that, the concentration of NaOH described in described step S11 is 5 ~ 15wt%.
6. desulfurizing agent according to claim 3, is characterized in that, the predecessor of zinc oxide described in described step S12 is one or more the combination in zinc hydroxide, zinc carbonate or basic zinc carbonate.
7., according to the arbitrary described desulfurizing agent of claim 1-6, it is characterized in that, described desulfurizing agent is made up of 85-95wt%Fe-Zn active component and 5-15wt% auxiliary agent.
8. desulfurizing agent according to claim 7, is characterized in that, described auxiliary agent is one or more the combination in binding agent, extrusion aid, pore creating material.
9. the preparation method of the arbitrary described desulfurizing agent of claim 1-8, is characterized in that, comprise the following steps:
S21, take described Fe-Zn active component, described auxiliary agent according to selected parts by weight, and mix
Evenly;
S22, material obtained in step S21 carried out mediate, shaping, and dry;
S23, the dry thing obtained by step S22 is carried out roasting, obtain described desulfurizing agent.
10. the preparation method of desulfurizing agent according to claim 9, is characterized in that, the temperature of described roasting is 300 ~ 350 DEG C, and the time is 2 ~ 4 hours.
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| CN105692685A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Zinc oxide desulphurizer and preparing method thereof |
| CN107684819B (en) * | 2017-09-27 | 2019-10-01 | 北京三聚环保新材料股份有限公司 | A kind of compound Fe-series desulfurizing agent and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4941914A (en) * | 1989-05-18 | 1990-07-17 | Elkem Metals Company | Desulfurization agent |
| CN1354037A (en) * | 2001-10-30 | 2002-06-19 | 南化集团研究院 | Iron oxide compound desulfurizer and its preparation method |
| CN101898110A (en) * | 2009-05-31 | 2010-12-01 | 北京三聚环保新材料股份有限公司 | Recyclable desulfurizer and preparation method thereof and regeneration method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4941914A (en) * | 1989-05-18 | 1990-07-17 | Elkem Metals Company | Desulfurization agent |
| CN1354037A (en) * | 2001-10-30 | 2002-06-19 | 南化集团研究院 | Iron oxide compound desulfurizer and its preparation method |
| CN101898110A (en) * | 2009-05-31 | 2010-12-01 | 北京三聚环保新材料股份有限公司 | Recyclable desulfurizer and preparation method thereof and regeneration method |
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