CN104307318A - Preparation method of zinc oxide normal-temperature desulfurizing agent - Google Patents
Preparation method of zinc oxide normal-temperature desulfurizing agent Download PDFInfo
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Abstract
The invention provides a preparation method of zinc oxide normal-temperature desulfurizing agent. The method comprises the following steps: firstly forming respective unstable precipitate of partial zinc salt and copper salt; and then completely translating residual zinc salt and copper salt not participating the precipitation in a bipyramid rotary vacuum reaction kettle and above unstable precipitates into stable zinc hydroxide and copper hydroxide, roasting to obtain compound powder of zinc oxide and copper oxide, and then preparing the zinc oxide normal temperature desulfurizing agent. The preparation method of the zinc oxide normal temperature desulfurizing agent provided by the invention has a simple process step, and less requirements on condition control and equipment operation, and the sulfur capacity of the prepared zinc oxide normal temperature desulfurizing agent at normal temperature reaches up to 20.3% and more; and therefore, the preparation method provided by the invention is suitable for large-scale production, and has high actual application value.
Description
Technical field
The present invention relates to a kind of preparation method of desulfurizing agent, be specifically related to a kind of preparation method of zinc oxide ambient temperature desulfuration agent, belong to desulfurizing agent technical field.
Technical background
Desulfurizing agent can be divided into high temperature desulfuration agent, middle low-temp desulfurization agent and ambient temperature desulfuration agent according to application of temperature, and in recent years, from Appropriate application heat energy, energy-saving and cost-reducing angle is set out, both at home and abroad all in the developmental research being devoted to low temperature and ambient temperature desulfuration agent.But because reactant under normal temperature condition is difficult to break through energy barrier, the material only possessing special physico-chemical performance just can reach the object of normal temperature desulfurization, and the desulfurizing agent desulfurization performance under normal temperature condition developed at present for middle high temperature can even be lost in remarkable decline, therefore, the research and development of ambient temperature desulfuration agent have been become to a study hotspot of this area.
In the dry-desulphurizer of all multiple types, Zinc oxide desulfurizer is high, easy to use, stable and reliable for performance and in occupation of critical role with its desulfurization precision.Zinc oxide desulfurizer is a kind of is key component with zinc oxide, add the fine desulfurizing agent of the adhesive such as promoter and alumina, cement, cellulose such as magnesia, cupric oxide, manganese dioxide, alchlor and gas generation agent, the conventional serviceability temperature of this type of desulfurizing agent is generally more than 200 DEG C, when desulfurization temperature reduces, although the desulfurization precision of Zinc oxide desulfurizer can be improved, but reaction speed also can be made to slow down and cause Sulfur capacity to reduce, Sulfur capacity under domestic Zinc oxide desulfurizer normal temperature generally only has 0.36-7.86%, is difficult to meet Production requirement.
For solving the problems of the technologies described above, Chinese patent literature CN101485954A discloses a kind of desulfurizing agent, and comprise nano zine oxide that weight percentage is 40-90%, weight percentage is the cupric oxide of 5-50%, weight percentage is the binding agent of 0-20%.Nano zine oxide, cupric oxide, binding agent, pore creating material and water carry out being mixed to form mixture by the preparation method of this desulfurizing agent, then this mixture is carried out mediating, shaping after obtain article shaped, finally this article shaped is obtained desulfurizing agent after super-dry, roasting.Although this desulfurizing agent has high Sulfur capacity, high accuracy desulfurization can be realized at a lower temperature, but the deficiency that above-mentioned prior art still exists is: this desulfurizing agent is greater than 24wt% at the working sulfur capacity of 200-250 DEG C, but the working sulfur capacity at 30 DEG C only has 15.5wt%, still can not satisfy the demands, this may be due to active component nano zine oxide and cupric oxide caused by the mixing in kneaded and formed preparation process not evenly.
Be evenly distributed to enable nano zine oxide and cupric oxide, another section of Chinese document " preparation of nano-zinc oxide composite material and photocatalytic applications research " (Liu Ziling, University Of Xiangtan's master thesis, on May 20th, 2009) report the preparation method of cupric oxide/zinc oxide nanometer composite material, concrete technology flow process is: metallic copper and zinc oxide are joined in the beaker that carbonic hydroammonium saturated solution is housed, ammoniacal liquor is added under stirring, under room temperature, reaction is until metallic copper and zinc oxide solid dissolve completely, obtain blue complex solution, joined in a certain amount of distilled water again, be heated to occur a large amount of light blue turbid solution at 60 DEG C after, centrifugation, obtain light blue precipitation, vacuum drying at being deposited in 60 DEG C, obtain light-blue powder shape predecessor, dried predecessor powder is placed in Muffle furnace, calcine certain hour at a certain temperature, obtain fine and smooth uniform nano cupric oxide/zinc oxide product.But above-mentioned processing step is loaded down with trivial details, there is very high requirement, once fluctuation of service to the control of condition and the operation of equipment, degree of crystallinity will be caused poor, make the particle diameter of nano particle bigger than normal, therefore, the coprecipitation technology of prior art still can not be applicable to large-scale production.In this case, how to be improved to meet suitability for industrialized production to the zinc oxide/preparation technology of cupric oxide nano composite, and can prepare the desulfurizing agent with high sulfur capacity, this is the still unsolved difficult problem in this area.
Summary of the invention
What the present invention solved is the defect that the preparation technology of zinc oxide of the prior art/cupric oxide nano composite is difficult to meet suitability for industrialized production, and then provides a kind of preparation method that can realize large-scale production, that can obtain high sulfur capacity zinc oxide ambient temperature desulfuration agent.
The technical scheme that the present invention solves the problems of the technologies described above employing is:
A preparation method for zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc salt, add the first precipitating reagent, the mol ratio of described zinc salt and described first precipitating reagent is 1: (0.5-0.8), stirs and reacts, obtain the first slurries at 55-60 DEG C;
(2) in the aqueous solution of mantoquita, add the first precipitating reagent, stir at 55-60 DEG C and react, obtain the second slurries; Wherein, the mol ratio of described mantoquita and described zinc salt is 1: (15-18), and the mol ratio of described mantoquita and described first precipitating reagent is 1: (0.5-0.8);
Described in above-mentioned steps (1) and (2), the first precipitating reagent is respectively any one in solid sodium carbonate, solid carbonic acid potassium, aqueous sodium carbonate, wet chemical;
(3) described first slurries and described second slurries are mixed, and add the second precipitating reagent under vacuum, stir at 60-70 DEG C and react, obtain presoma slurries, the mol ratio of wherein said second precipitating reagent and described zinc salt is (5-5.5): 1, and described second precipitating reagent is any one in solid sodium hydroxide, solid potassium hydroxide, sodium hydrate aqueous solution, potassium hydroxide aqueous solution;
(4) centrifugal treating is carried out to described presoma slurries, collecting precipitation thing, described sediment is washed successively, dry, roasting, obtain the composite granule of zinc oxide and cupric oxide;
(5) composite granule of described zinc oxide and cupric oxide, binding agent, pore creating material and water are carried out being mixed to form mixture, described mixture are mediated successively, shaping, dry, calcination process, obtain described zinc oxide ambient temperature desulfuration agent.
In step (1), described zinc salt is one or more in zinc nitrate, zinc chloride, zinc sulfate, zinc acetate.
In step (2), described mantoquita is one or more in copper nitrate, copper chloride, copper sulphate, Schweinfurt green.
The reaction time of step (1) is 20-40min, and the reaction time of step (2) is 20-40min.
Step (3), in bipyramid rotary vacuum reaction still, mixes described first slurries and described second slurries.
The vacuum of step (3) is-(0.07-0.09) Mpa, and the reaction time is 1h.
In step (4), the temperature of described drying is 100-120 DEG C; The temperature of described roasting is 350-380 DEG C, and the time of described roasting is 3-4h.
In step (4), the average grain diameter of the composite granule of described zinc oxide and cupric oxide is 20-40nm.
In step (5), the composite granule of described zinc oxide and cupric oxide is 80-95 weight portion; Described binding agent is 0.5-5 weight portion; Described pore creating material is 0.5-5 weight portion; Described water is 0.5-5 weight portion.
Described binding agent is one or more in kaolin, attapulgite, sheep liver soil, alumino-silicate cement, molecular screen primary powder; Described pore creating material is one or more in cellulose powder, sesbania powder, activated carbon powder, carbonic hydroammonium.
The preparation method of zinc oxide ambient temperature desulfuration agent of the present invention, first precipitating reagent sodium carbonate, potash or its aqueous solution join in the aqueous solution of zinc salt by step (1) to react, and the mol ratio limiting described zinc salt and described first precipitating reagent is 1: (0.5-0.8), this rate of charge makes the zinc ion in zinc salt solution not to be fully formed precipitation, simultaneously containing zinc carbonate precipitation and the zinc ion having neither part nor lot in precipitation reaction in the first slurries therefore obtained; Similarly, first precipitating reagent sodium carbonate, potash or its aqueous solution join in the aqueous solution of mantoquita by step (2) to react, and the mol ratio limiting described mantoquita and described first precipitating reagent is 1: (0.5-0.8), this rate of charge makes in the second slurries prepared simultaneously containing basic copper carbonate precipitation, Kocide SD precipitation and the copper ion having neither part nor lot in precipitation reaction; After described first slurries and the second slurries mix by step of the present invention (3) in bipyramid rotary vacuum reaction still, add the second precipitating reagent NaOH, potassium hydroxide or its aqueous solution under vacuum and carry out coprecipitation reaction, the rotating vacuum condition of the present invention, on the one hand the zinc ion having neither part nor lot in reaction is fully contacted with hydroxide ion respectively with copper ion, thus be fully formed zinc hydroxide and Kocide SD precipitation; Also make on the other hand zinc carbonate and basic copper carbonate and hydroxide ion occur to precipitate and transform, generate more stable zinc hydroxide respectively and Kocide SD precipitates; And because the product of reaction in step of the present invention (1) has been containing sedimentary slurries, mixed in bipyramid rotary vacuum reaction still by step (2), precipitation can be made fully can to disperse mixing.Step of the present invention (1) ~ (3) just make zinc ion and copper ion co-precipitation form the sediment of each self-stabilization by two-step reaction, its reason is, fractional precipitation can play certain cushioning effect to zinc and copper ion on the time needed for formation precipitation, that is, under the prerequisite not reducing reaction solution concentration and prolongation reaction time, zinc and copper ion not only can be made to form precipitation with slower speed by the method for fractional precipitation, also help the precipitation completely of zinc and copper ion, therefore, the present invention causes equipment investment high by adopting the mode of fractional precipitation to overcome in prior art because reactant liquor volume is large, and the defect such as reaction time long and human cost that is that cause is high.
Compared with the preparation method of Zinc oxide desulfurizer of the prior art, preparation method's tool of zinc oxide ambient temperature desulfuration agent of the present invention has the following advantages:
The preparation method of zinc oxide ambient temperature desulfuration agent of the present invention, by controlling the first precipitating reagent and zinc salt, the mol ratio of mantoquita, part zinc ion and copper ion is first made to form zinc carbonate and the basic copper carbonate precipitation of relative less stable separately, then again in bipyramid rotary vacuum reaction still, make it front unprecipitated remaining zinc ion and copper ion, and zinc carbonate and basic copper carbonate precipitation be all converted into stable zinc hydroxide and Kocide SD precipitation, the present invention not only can make zinc ion and copper ion be fully formed stable sediment by the method for fractional precipitation, also can make zinc in this sediment, being evenly distributed of copper, compared with the sediment obtained with a step coprecipitation of the prior art, sediment of the present invention has good degree of crystallinity, and further the particle diameter of the composite granule of the zinc oxide obtained after this sediment roasting and cupric oxide is only had 20-40nm, reach desirable nano zine oxide and the quality requirements of nano cupric oxide.
In addition, the composite granule of zinc oxide of the present invention and cupric oxide is made Zinc oxide desulfurizer further, its active component is nano zine oxide and nano cupric oxide, as everyone knows, single zinc oxide Sulfur capacity is at low temperatures lower, and the heat resistance of single cupric oxide is poor, more than 200 DEG C easy-sinterings, desulfurizing agent of the present invention is by adopting double activated component, to combine with nano cupric oxide by nano zine oxide and reach performance complement, make full use of nano zine oxide fully to react with sulfide, nano cupric oxide particulate is dispersed in again the characteristic of the surrounding of zinc oxide fine particles, desulfurizing agent of the present invention inside is made to have good pore passage structure and specific area, effectively can improve the activity of metal oxide in desulfurizing agent, thus reach the object of high accuracy and high sulfur capacity desulfurization, desulfurizing agent of the present invention desulfurization precision is at normal temperatures 0.02ppm, and working sulfur capacity is up to more than 20.3wt%, this not only can reduce the consumption of desulfurizing agent, also significantly can reduce the input to equipment and the energy, greatly save cost and decreased pollution.
The preparation method of zinc oxide ambient temperature desulfuration agent of the present invention, its processing step is simple, too many requirement be there is no to the control of condition and the operation of equipment, and being evenly distributed of zinc in the composite granule of the zinc oxide prepared and cupric oxide, copper, the particle diameter of composite granule only has 20-40nm, therefore, preparation method of the present invention can be applicable to large-scale production, is of very high actual application value.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the zinc oxide of embodiment 1 and the composite granule of cupric oxide.
Detailed description of the invention
Below in conjunction with specific embodiment, the preparation method to zinc oxide ambient temperature desulfuration agent provided by the invention is described in detail.Wherein 1 weight portion is 1Kg, and 1 parts by volume is 1L.
Embodiment 1
Described in the present embodiment, the preparation method of zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc nitrate, add the aqueous solution of sodium carbonate, the mol ratio of described zinc nitrate and described sodium carbonate is 1: 0.5, stirs and carries out reaction 0.5 hour, obtain the first slurries at 60 DEG C;
(2) in the aqueous solution of copper nitrate, add the aqueous solution of sodium carbonate, stir at 60 DEG C and carry out reaction 0.5 hour, obtain the second slurries; Wherein, the mol ratio of described copper nitrate and described zinc nitrate is 1: 18, and the mol ratio of described copper nitrate and described sodium carbonate is 1: 0.5;
(3) in bipyramid rotary vacuum reaction still, described first slurries and described second slurries are mixed, and under the vacuum condition of-0.08MPa, add the aqueous solution of NaOH, stir at 60 DEG C and carry out reaction 1 hour, obtain presoma slurries, the mol ratio of wherein said NaOH and described zinc nitrate is 5.5: 1;
(4) centrifugal treating is carried out to described presoma slurries, filter, collecting precipitation thing, by deionized water, described sediment is washed 3 times, 120 DEG C of dryings after 3 hours, then 350 DEG C of roastings 4 hours, obtain the composite granule of zinc oxide and cupric oxide, the pattern carrying out composite granule described in scanning discovery under ESEM is nano-powder, and its particle diameter is 20nm; The XRD collection of illustrative plates of the composite granule of described zinc oxide and cupric oxide, as shown in Figure 1;
(5) first the cellulose powder of 5 weight portions is added in the water of 5 parts by volume, is mixed with translucent pore creating material slurries, stand-by; Again the described zinc oxide of 95 weight portions and the composite granule of cupric oxide, the attapulgite of 3 weight portions are stirred, add the described pore creating material slurries prepared, after stirring, form mixture; This mixture is put into kneader fully to mediate evenly, then insert in banded extruder, material is extruded into
strip article shaped; At then this article shaped being placed in 120 DEG C after dry 4 hours, then roasting 4 hours at 400 DEG C, namely obtain described zinc oxide ambient temperature desulfuration agent.
Embodiment 2
Described in the present embodiment, the preparation method of zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc chloride, add potash, the mol ratio of described zinc chloride and described potash is 1: 0.8, stirs and carries out reaction 40min, obtain the first slurries at 55 DEG C;
(2) in the aqueous solution of copper chloride, add potash, stir at 60 DEG C and carry out reaction 40min, obtain the second slurries; Wherein, the mol ratio of described copper chloride and described zinc chloride is 1: 16, and the mol ratio of described copper chloride and described potash is 1: 0.6;
(3) in bipyramid rotary vacuum reaction still, described first slurries and described second slurries are mixed, and under the vacuum condition of-0.07MPa, add the aqueous solution of potassium hydroxide, stir at 70 DEG C and carry out reaction 1 hour, obtain presoma slurries, the mol ratio of wherein said potassium hydroxide and described zinc chloride is 5: 1;
(4) centrifugal treating is carried out to described presoma slurries, filter, collecting precipitation thing, by deionized water, described sediment is washed 3 times, 100 DEG C of dryings after 4 hours, then 380 DEG C of roastings 3 hours, obtain the composite granule of zinc oxide and cupric oxide, its particle diameter is 40nm;
(5) first the sesbania powder of 3 weight portions is added in the water of 4 parts by volume, is mixed with translucent pore creating material slurries, stand-by; Again that the alumino-silicate cement mixing of the composite granule of the described zinc oxide of 80 weight portions and cupric oxide, 0.5 weight portion is even, add the described pore creating material slurries prepared, after stirring, form mixture; This mixture is put into kneader fully to mediate evenly, then insert in banded extruder, material is extruded into
strip article shaped; At then this article shaped being placed in 120 DEG C after dry 4 hours, then roasting 4 hours at 400 DEG C, namely obtain described zinc oxide ambient temperature desulfuration agent.
Embodiment 3
Described in the present embodiment, the preparation method of zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc sulfate, add the aqueous solution of sodium carbonate, the mol ratio of described zinc sulfate and described sodium carbonate is 1: 0.65, stirs and carries out reaction 20min, obtain the first slurries at 55 DEG C;
(2) in the aqueous solution of copper sulphate, add the aqueous solution of sodium carbonate, stir at 55 DEG C and carry out reaction 20min, obtain the second slurries; Wherein, the mol ratio of described copper sulphate and described zinc sulfate is 1: 16, and the mol ratio of described copper sulphate and described sodium carbonate is 1: 0.8;
(3) in bipyramid rotary vacuum reaction still, described first slurries and described second slurries are mixed, and NaOH is added under the vacuum condition of-0.09MPa, stir at 65 DEG C and carry out reaction 1 hour, obtain presoma slurries, the mol ratio of wherein said NaOH and described zinc sulfate is 5.2: 1;
(4) centrifugal treating is carried out to described presoma slurries, filter, collecting precipitation thing, by deionized water, described sediment is washed 3 times, 110 DEG C of dryings after 4 hours, then 360 DEG C of roastings 4 hours, obtain the composite granule of zinc oxide and cupric oxide, its particle diameter is 30nm;
(5) joined in the water of 5 parts by volume by the carbonic hydroammonium of the described zinc oxide of 90 weight portions and the composite granule of cupric oxide, the sheep liver soil of 5 weight portions and 0.5 weight portion, stir formation mixture; This mixture is put into kneader fully to mediate evenly, then insert in banded extruder, material is extruded into
strip article shaped; At then this article shaped being placed in 120 DEG C after dry 4 hours, then roasting 4 hours at 400 DEG C, namely obtain described zinc oxide ambient temperature desulfuration agent.
Comparative example 1
In this comparative example, the preparation method of zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc nitrate and copper nitrate, add the aqueous solution of NaOH, the mol ratio of described copper nitrate, zinc nitrate and NaOH is 1: 18: 99, stirs and carries out reaction 0.5 hour, obtain presoma slurries at 60 DEG C;
(2) carry out centrifugal treating to described presoma slurries, filter, collecting precipitation thing, washs 3 times by deionized water by described sediment, 120 DEG C of dryings after 3 hours, then 350 DEG C of roastings 4 hours, obtains the composite granule of zinc oxide and cupric oxide;
(3) first the cellulose powder of 5 weight portions is added in the water of 5 parts by volume, is mixed with translucent pore creating material slurries, stand-by; Again the described zinc oxide of 95 weight portions and the composite granule of cupric oxide, the attapulgite of 3 weight portions are stirred, add the described pore creating material slurries prepared, after stirring, form mixture; This mixture is put into kneader fully to mediate evenly, then insert in banded extruder, material is extruded into
strip article shaped; At then this article shaped being placed in 120 DEG C after dry 4 hours, then roasting 4 hours at 400 DEG C, namely obtain described zinc oxide ambient temperature desulfuration agent.
Comparative example 2
In this comparative example, the preparation method of zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc nitrate, add the aqueous solution of NaOH, the mol ratio of described zinc nitrate and described NaOH is 1: 0.5, stirs and carries out reaction 0.5 hour, obtain the first slurries at 60 DEG C;
(2) in the aqueous solution of copper nitrate, add the aqueous solution of NaOH, stir at 60 DEG C and carry out reaction 0.5 hour, obtain the second slurries; Wherein, the mol ratio of described copper nitrate and described zinc nitrate is 1: 18, and the mol ratio of described copper nitrate and described NaOH is 1: 0.5;
(3) in bipyramid rotary vacuum reaction still, described first slurries and described second slurries are mixed, and under the vacuum condition of-0.08MPa, add the aqueous solution of NaOH, stir at 60 DEG C and carry out reaction 1 hour, obtain presoma slurries, the mol ratio of wherein said NaOH and described zinc nitrate is 5.5: 1;
(4) carry out centrifugal treating to described presoma slurries, filter, collecting precipitation thing, washs 3 times by deionized water by described sediment, 120 DEG C of dryings after 3 hours, then 350 DEG C of roastings 4 hours, obtains the composite granule of zinc oxide and cupric oxide;
(5) first the cellulose powder of 5 weight portions is added in the water of 5 parts by volume, is mixed with translucent pore creating material slurries, stand-by; Again the described zinc oxide of 95 weight portions and the composite granule of cupric oxide, the attapulgite of 3 weight portions are stirred, add the described pore creating material slurries prepared, after stirring, form mixture; This mixture is put into kneader fully to mediate evenly, then insert in banded extruder, material is extruded into
strip article shaped; At then this article shaped being placed in 120 DEG C after dry 4 hours, then roasting 4 hours at 400 DEG C, namely obtain described zinc oxide ambient temperature desulfuration agent.
Experimental example
By embodiment of the present invention 1-3, the zinc oxide ambient temperature desulfuration agent that comparative example 1-2 prepares carries out Sulfur capacity mensuration, condition determination is: in desulfurizer, the loadings of desulfurizing agent is 2mL, sulfide hydrogen 5000ppm in the unstripped gas in desulfurizer is entered by gas feed, carrier gas in unstripped gas is hydrogen nitrogen mixed gas, wherein the volume ratio of hydrogen and nitrogen is 3: 1, be normal temperature in desulfurizer, normal pressure, the Hydrogen Sulfide Tail Gas content of desulfurizer gas vent controls at 0.02ppm, in gas, the content of hydrogen sulfide is analyzed by gas-chromatography, and by chemical analysis to embodiment 1-3, the zinc oxide ambient temperature desulfuration agent working sulfur capacity at normal temperatures that comparative example 1-2 prepares measures, result is as shown in table 1.
The Sulfur capacity (%, 25 DEG C) of the zinc oxide ambient temperature desulfuration agent that table 1 embodiment 1-3, comparative example 1-2 prepare
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Sulfur capacity (%) | 21.1 | 20.5 | 20.3 | 2.6 | 5.3 |
As can be seen from Table 1, the zinc oxide ambient temperature desulfuration agent obtained according to the preparation method of zinc oxide ambient temperature desulfuration agent of the present invention Sulfur capacity is at normal temperatures up to more than 20.3%, far above the Sulfur capacity of the zinc oxide ambient temperature desulfuration agent in comparative example 1-2, this illustrates zinc in the composite granule of zinc oxide and the cupric oxide obtained by step-by-step precipitation method of the present invention, copper is uniformly dispersed, thus make the zinc oxide ambient temperature desulfuration agent prepared further by the composite granule of described zinc oxide and cupric oxide have good pore passage structure and specific area, effectively can improve the activity of metal oxide in desulfurizing agent, thus reach the object of high accuracy and high sulfur capacity desulfurization.
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 the protection domain of the invention.
Claims (10)
1. a preparation method for zinc oxide ambient temperature desulfuration agent, comprises the steps:
(1) in the aqueous solution of zinc salt, add the first precipitating reagent, the mol ratio of described zinc salt and described first precipitating reagent is 1: (0.5-0.8), stirs and reacts, obtain the first slurries at 55-60 DEG C;
(2) in the aqueous solution of mantoquita, add the first precipitating reagent, stir at 55-60 DEG C and react, obtain the second slurries; Wherein, the mol ratio of described mantoquita and described zinc salt is 1: (15-18), and the mol ratio of described mantoquita and described first precipitating reagent is 1: (0.5-0.8);
Described in above-mentioned steps (1) and (2), the first precipitating reagent is respectively any one in solid sodium carbonate, solid carbonic acid potassium, aqueous sodium carbonate, wet chemical;
(3) described first slurries and described second slurries are mixed, and add the second precipitating reagent under vacuum, stir at 60-70 DEG C and react, obtain presoma slurries, the mol ratio of wherein said second precipitating reagent and described zinc salt is (5-5.5): 1, and described second precipitating reagent is any one in solid sodium hydroxide, solid potassium hydroxide, sodium hydrate aqueous solution, potassium hydroxide aqueous solution;
(4) centrifugal treating is carried out to described presoma slurries, collecting precipitation thing, described sediment is washed successively, dry, roasting, obtain the composite granule of zinc oxide and cupric oxide;
(5) composite granule of described zinc oxide and cupric oxide, binding agent, pore creating material and water are carried out being mixed to form mixture, described mixture are mediated successively, shaping, dry, calcination process, obtain described zinc oxide ambient temperature desulfuration agent.
2. preparation method according to claim 1, is characterized in that, in step (1), described zinc salt is one or more in zinc nitrate, zinc chloride, zinc sulfate, zinc acetate.
3. preparation method according to claim 1 and 2, is characterized in that, in step (2), described mantoquita is one or more in copper nitrate, copper chloride, copper sulphate, Schweinfurt green.
4., according to the arbitrary described preparation method of claim 1-3, it is characterized in that, the reaction time of step (1) is 20-40min, and the reaction time of step (2) is 20-40min.
5., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, step (3) mixes described first slurries and described second slurries in bipyramid rotary vacuum reaction still.
6., according to the arbitrary described preparation method of claim 1-5, it is characterized in that, the vacuum of step (3) is-(0.07-0.09) Mpa, and the reaction time is 1h.
7., according to the arbitrary described preparation method of claim 1-6, it is characterized in that, in step (4), the temperature of described drying is 100-120 DEG C; The temperature of described roasting is 350-380 DEG C, and the time of described roasting is 3-4h.
8., according to the arbitrary described preparation method of claim 1-7, it is characterized in that, in step (4), the average grain diameter of the composite granule of described zinc oxide and cupric oxide is 20-40nm.
9., according to the arbitrary described preparation method of claim 1-8, it is characterized in that, in step (5), the composite granule of described zinc oxide and cupric oxide is 80-95 weight portion; Described binding agent is 0.5-5 weight portion; Described pore creating material is 0.5-5 weight portion; Described water is 0.5-5 weight portion.
10. preparation method according to claim 9, is characterized in that, described binding agent is one or more in kaolin, attapulgite, sheep liver soil, alumino-silicate cement, molecular screen primary powder; Described pore creating material is one or more in cellulose powder, sesbania powder, activated carbon powder, carbonic hydroammonium.
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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 |
| CN105842184A (en) * | 2016-05-26 | 2016-08-10 | 天邦膜技术国家工程研究中心有限责任公司 | Special water-soluble helium evaluation system |
| CN107335445A (en) * | 2017-08-17 | 2017-11-10 | 江苏天东新材料科技有限公司 | A kind of preparation method and application of double-function fine desulfurizing agent |
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| CN112552969A (en) * | 2020-11-20 | 2021-03-26 | 沈阳三聚凯特催化剂有限公司 | Desulfurizing agent and preparation method and application thereof |
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| CN105842184A (en) * | 2016-05-26 | 2016-08-10 | 天邦膜技术国家工程研究中心有限责任公司 | Special water-soluble helium evaluation system |
| CN105842184B (en) * | 2016-05-26 | 2019-04-26 | 天邦膜技术国家工程研究中心有限责任公司 | A kind of exclusive evaluation system of water-soluble helium |
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| CN108554137A (en) * | 2018-04-10 | 2018-09-21 | 湖北华特尔净化科技股份有限公司 | A kind of superhigh precision compound oxidizing zinc desulfurizing agent and preparation method thereof |
| CN110813292A (en) * | 2019-10-24 | 2020-02-21 | 湖北浚然新材料有限公司 | Dearsenic agent and preparation method thereof |
| CN111905735A (en) * | 2020-08-24 | 2020-11-10 | 清华大学深圳国际研究生院 | Preparation method and application of waxberry-shaped catalytic material |
| CN111905735B (en) * | 2020-08-24 | 2023-02-24 | 清华大学深圳国际研究生院 | Preparation method and application of waxberry-shaped catalytic material |
| CN112552969A (en) * | 2020-11-20 | 2021-03-26 | 沈阳三聚凯特催化剂有限公司 | Desulfurizing agent and preparation method and application thereof |
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