CN101288821A - Preparation method of calcium zincate and calcium zincate reclaiming agent at normal temperature - Google Patents
Preparation method of calcium zincate and calcium zincate reclaiming agent at normal temperature Download PDFInfo
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- CN101288821A CN101288821A CN200710098515.XA CN200710098515A CN101288821A CN 101288821 A CN101288821 A CN 101288821A CN 200710098515 A CN200710098515 A CN 200710098515A CN 101288821 A CN101288821 A CN 101288821A
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Abstract
The invention provides a calcium zincate and a method for preparing normal-temperature desulfurizer of the calcium zincate. The calcium zincate preparation method provided by the invention requires no crystal seeds, is directly formed, has simple operation, high yield and low cost and can be used for large-scale industrialized production. The desulfurizer provided by the invention consists of calcium zincate structural promoter. The desulfurizer of the invention reduces the cost and improves the production safety; furthermore, the desulfurization effect of the desulfurizer is much better than that of traditional normal-temperature desulfurizer and the sulfur capacity can reach 35.2%.
Description
Technical field
The present invention relates to the preparation method of zincic acid calcium and calcium zincate reclaiming agent at normal temperature, particularly in petrochemical industry, essence under various gaseous states, the liquid material normal temperature is taken off H
2The zincic acid calcium of S and the preparation method of calcium zincate reclaiming agent at normal temperature.
Background technology
At present, the various unstripped gas of petrochemical industry, the widely used desulfurizing agent of the smart desulfurization of industrial gas are zinc oxide, are divided into high temperature desulfuration agent and ambient temperature desulfuration agent two big classes in the commercially available prod.High-temperature oxydation zinc desulfurizing agent has higher sulfur capacity when high temperature (350～400 ℃) desulfurization, but ambient temperature desulfuration agent is in the normal temperature desulfurization, and Sulfur capacity but reduces greatly, and its Sulfur capacity is all below 12%.European patent 279116,207645,230146 disclosed normal temp zinc oxide desulfuriging agents have certain low temperature active, at 20 ℃, 1500h
-1The time Sulfur capacity only 5.7%; Chinese patent CN1094331A discloses a kind of normal temp zinc oxide desulfuriging agent, and its activity is at 20 ℃, 1500h
-1The time Sulfur capacity also have only 8.2%.Because the price of non-ferrous metal Zn rises steadily, make the cost of ZnO desulfurizing agent soaring significantly again.，
In sum, currently used ambient temperature desulfuration agent is the production cost height not only, and Sulfur capacity is lower.
The present invention has found the application of zincic acid calcium as desulfurizing agent.
But for the preparation of zincic acid calcium, the industrial method that also do not provide a kind of weak point simple to operate, consuming time, productive rate height in the prior art, can be mass-produced.
The negative material that zincic acid calcium is used for alkaline secondary zinc electrode is a material newly developed in recent years, constantly maturation and industrialization.Its preparation method Chinese patent CN 1397498A and CN 1595688A disclose the synthetic zincic acid calcium of ball-milling method, and wherein disclosed among the Chinese patent CN 1397498A is with Ca (OH)
2Put into ball grinder with ZnO in the ratio in the zincic acid calcium chemical formula, add suitable quantity of water, ball milling is 8～18 hours under the argon atmospher protection, obtains product in baking under 30～80 ℃ after 10～15 hours then; Disclosed among the Chinese patent CN 1595688A is calcium hydroxide or calcium oxide by stoichiometric proportion; zinc hydroxide or zinc oxide are put into ball mill; add suitable quantity of water; the argon atmospher protection down; ratio of grinding media to material 3～20: ball milling is 5～25 hours under 1 the condition, obtains product in baking under 30～80 ℃ after 5～20 hours then.From as can be seen above-mentioned, this method exists shortcomings such as complicated operation, length consuming time, productive rate be low, can not large-scale production.
In addition, also have patent disclosure chemical precipitation method synthesize.United States Patent (USP) 5,460,899 disclose a kind of ZnO of using and Ca (OH)
2Reaction generates the method for zincic acid calcium in alkali lye; Disclosed among the Chinese patent CN 1753212A is to add 400 orders～800 order zincic acid calcium crystal of about 0.5～1.5% to do crystal seed in alkaline solution, 20～95 ℃ with soluble zinc salt and calcium salt with Zn: Ca=2: 1 mixed in molar ratio evenly after, join in the aforementioned solution, product is reclaimed in the back that reacts completely.The shortcoming of this method is to need NaOH or KOH that alkaline environment is provided, and this part alkali does not provide positive-effect to product, needs washing after product generates, and has just introduced new impurity again if washing is clean; This method also needs 400 orders～800 order zincic acid calcium crystal of 0.5～1.5% to do crystal seed.Method provided by the invention does not then need crystal seed.
Summary of the invention
The present invention has found that zincic acid calcium can be as desulfurizing agent, and the effect of zincic acid calcium normal temperature desulfurization is better than existing desulfurizing agent greatly.
The present invention provides the preparation method of zincic acid calcium simultaneously.The preparation method comprises the steps:
A, when product is soluble-salt except that zincic acid calcium:
(1) soluble zinc salt is prepared zinc solution; Preferred zinc solution concentration 〉=1%;
(2) with Ca (OH)
2Be made into emulsion; Preferably take by weighing Ca (OH) by stoichiometric proportion with zinc salt
2Consumption;
(3) with Ca (OH)
2Emulsion and zinc solution mix; Preferably under agitation with Ca (OH)
2Emulsion adds in the zinc solution, stirs 1 hour again;
(4) with the sedimentation and filtration, the washing that are generated; Preferred water is with the washing of precipitate that generated three times;
(5) filtration cakes torrefaction promptly gets the pure former powder of zincic acid calcium;
B, when product all is insoluble compound:
(1) with solid zinc salt and solid Ca (OH)
2Kneading and compacting; Preferably take by weighing Ca (OH) by stoichiometric proportion
2With zinc salt, add suitable quantity of water, fully mix the back straight forming.
(2) be drying to obtain the agent of zincic acid calcium desulfurizing.
Zinc salt among the present invention is preferably Zn (NO
3)
26H
2O, ZnCl
2, Zn (CH
3COO)
22H
2O, zinc sulfate ZnSO
47H
2O or basic zinc carbonate Zn
2(OH)
2CO
3
The present invention also provides a kind of ambient temperature desulfuration agent that contains zincic acid calcium and preparation method thereof.
The composition that contains the ambient temperature desulfuration agent of zincic acid calcium provided by the invention comprises zincic acid calcium CaZn
2(OH)
62H
2The structural promoter of O and desulfurizing agent.In the preferred sesbania gum of used structural promoter, kaolin, cement and the blanc fixe one or more.
In the calcium zincate reclaiming agent at normal temperature provided by the invention, the shared weight portion of each composition is preferably: CaZn
2(OH)
62H
2O 60-95 part, sesbania gum 0.5-10 part, kaolin 05-5 part, cement 0.5-5 part, blanc fixe 0.5-20 part.
The shared weight portion of each composition CaZn more preferably in the desulfurizing agent
2(OH)
62H
2O 80-90 part, sesbania gum 8-10 part, kaolin 2-3 part, cement 2-3 part, blanc fixe 8-10 part.
The preparation method of above-mentioned desulfurizing agent provided by the invention comprises the steps: the abundant mixing on kolleroang with zincic acid calcium and structural promoter, adds suitable quantity of water, grinds into mud shape material, adopts extrusion or the moulding of balling-up equipment, is drying to obtain.
The calcium zincate reclaiming agent at normal temperature that the present invention prepares, side pressure strength are 90-150N/cm, and bulk density is 0.70-1.0 gram/ml.
Because the particularity of zincic acid calcium structure is to belong to the polyhydroxy compounds, itself and H
2The reaction speed of S has substantially exceeded ZnO and H
2The reaction speed of S, and product is also different.Zincic acid calcium and H at normal temperatures
2S reaction back product is ZnSS
X(X is 0.6-0.7), ZnO and H
2S reaction back product is ZnS
X(X is 0.25); So the Sulfur capacity of zincic acid calcium is higher than ZnO far away.
The former powder of zincic acid calcium of the present invention is behind the compressing tablet broken (40～60 order), at 20 ℃, 3000h
-1, H
2S concentration is 4% standard gas evaluation Sulfur capacity, and the disposable Sulfur capacity that penetrates is up to 35.2%.
Zincic acid calcium of the present invention, can with different structural promoters, adopt different ratios, allotment obtains the desulfurizing agent of required different Sulfur capacity, different side pressure strength and different bulk densities.
Technical scheme provided by the invention compared with prior art has following outstanding effect:
(1), adopting zincic acid calcium is that the ambient temperature desulfuration agent of desulphurizing activated component is compared Sulfur capacity with traditional ambient temperature desulfuration agent and increased considerably.
(2), be that the desulfurizing agent cost of active component is significantly less than existing desulfurizing agent with zincic acid calcium.
(3), zincic acid calcium production method provided by the invention, do not need crystal seed, operate simple, convenient and swift, productive rate is high, can be used for large-scale industrial production.
(4), the normal temperature Fe-series desulfurizing agent generates FeS or Fe after because of desulfurization
2S
3, when unloading agent or running into air, can produce a large amount of heat or burning, and zincic acid calcium desulfurizing of the present invention agent is met air and is not produced heat release and burning after desulfurization, improved production security.
(5), existing forming method, it all is earlier synthetic former powder, add the structural promoter moulding again, in order to improve Sulfur capacity, even also will add peptizing agent and come pore-creating (Chinese patent CN 1094331), the method that provides among the present invention can straight forming, has reduced operation, improve speed of production, reduced cost.
Description of drawings
Fig. 1 is ZnNO
36H
2With the synthetic former powder of zincic acid calcium of solwution method, product detects with XRD at normal temperatures for O and calcium powder, and its thing is extremely pure CaZn mutually
2(OH)
62H
2O.
Fig. 2 is ZnSO
47H
2O and calcium powder be the agent of kneading method synthetic sweetening at normal temperatures, and product detects with XRD, and gained desulfurizing agent thing phase composition is CaZn
2(OH)
62H
2O and CaSO
42H
2O.
Fig. 3 is basic zinc carbonate Zn
2(OH)
2CO
3With calcium powder kneading method synthetic sweetening agent at normal temperatures, product detects with XRD, and gained desulfurizing agent thing phase composition is CaZn
2(OH)
62H
2O and CaCO
3
The specific embodiment
Substantive distinguishing features that the present invention gives prominence to and marked improvement can be embodied from following example, but they are not that the present invention is imposed any restrictions.
Embodiment 1
Take by weighing 151.5 gram Zn (NO
3)
26H
2O, the reactor that places the 1000ml band to stir adds 200ml water, at room temperature is stirred to zinc salt and dissolves fully.Take by weighing 58.2 gram Ca (OH) again
2Powder places the 400ml beaker, adds 200ml water and makes Ca (OH)
2Slurries.With Ca (OH)
2Slurries slowly add in the zinc solution, up to adding.Continue to stir one hour.
Filtering-depositing is with 600ml water washing precipitation three times (each 200ml); Filtration cakes torrefaction gets the former powder of zincic acid calcium, and its thing of XRD determining (Fig. 1) is extremely pure CaZn mutually
2(OH)
62H
2O.
With this zincic acid calcium raw material,, filter out 40～60 order samples, standard H with 4.02% through the compressing tablet granulation
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 35.2%.
Take by weighing embodiment 1 zincic acid calcium 18.0 gram, sesbania gum 2.0 grams, kaolin 0.5 gram, cement 0.5 gram, blanc fixe 2.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 120N/cm, and bulk density is 0.90 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 25.1%.
Take by weighing embodiment 1 zincic acid calcium 20.0 gram, sesbania gum 3.0 grams, kaolin 1.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.Gained desulfurizing agent, side pressure strength are 130N/cm, and bulk density is 0.82 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 28.6%.
Take by weighing embodiment 1 zincic acid calcium 18.0 gram, sesbania gum 3.0 grams, kaolin 1.5 grams, cement 1.5 grams, blanc fixe 6.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 148N/cm, and bulk density is 0.93 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 20.4%.
Embodiment 5
Take by weighing 70.0 gram ZnCl
2The reactor that places the 1000ml band to stir adds 200ml water, at room temperature is stirred to zinc salt and dissolves fully.Take by weighing 58.2 gram Ca (OH) again
2Powder places the 400ml beaker, adds 200ml water and makes Ca (OH)
2Slurries.With Ca (OH)
2Slurries slowly add in the zinc solution, up to adding.Continue to stir one hour.
Filtering-depositing is with 600ml water washing precipitation three times (each 200ml); Filtration cakes torrefaction gets the former powder of zincic acid calcium, and its thing of XRD determining is extremely pure CaZn mutually
2(OH)
62H
2O.
With this zincic acid calcium raw material,, sift out 40～60 order samples, standard H with 4.02% through the compressing tablet granulation
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 34.8%.
Embodiment 6
Take by weighing embodiment 5 zincic acid calcium 18.0 gram, sesbania gum 2.0 grams, kaolin 0.5 gram, cement 0.5 gram, blanc fixe 2.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 120N/cm, and bulk density is 0.90 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 24.8%.
Embodiment 7
Take by weighing embodiment 5 zincic acid calcium 20.0 gram, sesbania gum 1.0 grams, kaolin 0.5 gram, cement 0.5 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 103N/cm, and bulk density is 0.79 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 31.7%.
Embodiment 8
Take by weighing embodiment 5 zincic acid calcium 16.0 gram, sesbania gum 3.0 grams, kaolin 1.0 grams, cement 1.0 grams, blanc fixe 2.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 130N/cm, and bulk density is 0.90 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 22.6%.
Embodiment 9
Take by weighing 110.6 gram Zn (CH
3COO)
22H
2The reactor that O places the 1000ml band to stir adds 200ml water, at room temperature is stirred to zinc salt and dissolves fully.Take by weighing 58.2 gram Ca (OH) again
2Powder places the 400ml beaker, adds 200ml water and makes Ca (OH)
2Slurries.With Ca (OH)
2Slurries slowly add in the zinc solution, up to adding.Continue to stir one hour.
Filtering-depositing is with 600ml water washing precipitation three times (each 200ml); Filtration cakes torrefaction gets the former powder of zincic acid calcium, and its thing of XRD determining is extremely pure CaZn mutually
2(OH)
62H
2O.
With this zincic acid calcium raw material,, filter out 40～60 order samples, standard H with 4.02% through the compressing tablet granulation
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 34.2%.
Take by weighing embodiment 9 zincic acid calcium 24.0 gram, sesbania gum 4.0 grams, kaolin 2.0 grams, cement 2.0 grams, blanc fixe 8.0 gram and suitable quantity of water, the bar shaped desulfurizing agent of Ф 4 is extruded in moulding on the small capacity double screw extruder, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent, side pressure strength are 140N/cm, and bulk density is 0.93 gram/ml, powder to 40～60 orders, the standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 18.6%.
Embodiment 11
Take by weighing 232.8 gram Ca (OH)
2Powder and 598.0 gram ZnSO
47H
2O fully mixes on the small capacity double screw extruder, directly extrudes the bar shaped desulfurizing agent of Ф 4 then, does the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent thing phase composition is CaZn
2(OH)
62H
2O and CaSO
42H
2O (Fig. 2), side pressure strength 96N/cm, bulk density 0.74 gram/ml, powder to 40～60 orders, standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 16.2%.
Embodiment 12
Take by weighing 157.0 gram Ca (OH)
2Powder and 230.0 gram basic zinc carbonates add suitable quantity of water, fully mix on the small capacity double screw extruder, directly extrude the bar shaped desulfurizing agent of Ф 4 then, do the Sulfur capacity evaluation after the drying.
Gained desulfurizing agent thing phase composition is CaZn
2(OH)
62H
2O and CaCO
3(Fig. 3), side pressure strength 90N/cm, bulk density 0.72 gram/ml, powder to 40～60 orders, standard H with 4.02%
2(spirit is a high-purity N to S gas
2), air speed 3000h
-1, 20 ℃ of conditions of room temperature next time property to penetrate Sulfur capacity be 24.3%.
Embodiment 13
Take by weighing and be crushed to 20～40 embodiment, 3 desulfurizing agents, 5 grams, be seated at 3: 1 in the liquid material desulfurization evaluating apparatus by ratio of height to diameter, the micro pump charging goes out on advancing under the feeding manner.
Remove the H in the gasoline
2S is at liquid air speed 2h
-1Under the condition, can be with H
2S content is the H in the catalytic gasoline of 200PPm
2S removes, and takes off the H of back gasoline
2S does not separate out.
Embodiment 14
Take by weighing and be crushed to 20～40 embodiment, 11 desulfurizing agents, 5 grams, be seated at 3: 1 in the liquid material desulfurization evaluating apparatus by ratio of height to diameter, the micro pump charging goes out on advancing under the feeding manner.
Remove the H in the aviation kerosine
2S is at liquid air speed 4h
-1Under the condition, can be with H
2S content is greater than the H in the boat coal of 15PPm
2S removes, and takes off the H of back boat coal
2S does not separate out.
Claims (10)
1, zincic acid calcium CaZn
2(OH)
62H
2O is as the purposes of desulfurizing agent.
2, a kind of preparation method of zincic acid calcium comprises the step among following A or the B:
A, when product is soluble-salt except that zincic acid calcium:
(1) soluble zinc salt is prepared zinc solution;
(2) with Ca (OH)
2Be made into emulsion;
(3) with Ca (OH)
2Emulsion is mixed with zinc solution, stirs;
(4) with the sedimentation and filtration, the washing that are generated;
(5) filtration cakes torrefaction promptly gets the pure former powder of zincic acid calcium;
B, when product all is insoluble compound:
(1) with solid zinc salt and solid Ca (OH)
2Kneading and compacting;
(2) be drying to obtain the agent of zincic acid calcium desulfurizing.
3, method according to claim 2 is characterized in that described zinc salt is Zn (NO
3)
26H
2O, ZnCl
2, Zn (CH
3COO)
22H
2O, zinc sulfate ZnSO
47H
2O or basic zinc carbonate Zn
2(OH)
2CO
3
4, according to claim 2 or 3 described methods, it is characterized in that among the described A:
Step (1): zinc solution concentration 〉=1%;
Step (2): take by weighing Ca (OH) by stoichiometric proportion with zinc salt
2Consumption;
Step (3): under agitation with Ca (OH)
2Emulsion adds in the zinc solution, stirs 1 hour again;
Step (4): water is with the washing of precipitate that generated three times;
Among the described B:
Step (2): take by weighing Ca (OH) by stoichiometric proportion
2With zinc salt, add suitable quantity of water, fully mix, then straight forming.
5, a kind of desulfurizing agent is characterized in that its composition comprises zincic acid calcium CaZn
2(OH)
62H
2The structural promoter of O and desulfurizing agent.
6, desulfurizing agent according to claim 5 is characterized in that described structural promoter is selected from one or more in sesbania gum, kaolin, cement and the blanc fixe.
7, desulfurizing agent according to claim 6 is characterized in that the shared weight portion of each composition is:
CaZn
2(OH)
62H
2O 60-95 part, sesbania gum 0.5-10 part, kaolin 0.5-5 part, cement 0.5-5 part, blanc fixe 0.5-20 part.
8, desulfurizing agent according to claim 7 is characterized in that the shared weight portion of each composition is:
CaZn
2(OH)
62H
2O 80-90 part, sesbania gum 8-10 part, kaolin 2-3 part, cement 2-3 part, blanc fixe 8-10 part.
9, the described desulfurizing agent of each claim among the claim 5-8, it is characterized in that its preparation method comprises the steps: zincic acid calcium and structural promoter are weighed up in proportion, abundant mixing on kolleroang, add suitable quantity of water, grind into mud shape material, adopt extrusion or the moulding of balling-up equipment, drying both got.
10, according to the desulfurizing agent described in the claim 9, it is characterized in that the desulfurizing agent side pressure strength is 90-150N/cm, bulk density is 0.70-1.0 gram/ml.
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|---|---|---|---|
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|---|---|---|---|
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| CN101746810B (en) * | 2008-12-16 | 2012-05-02 | 天津蓝天高科电源股份有限公司 | Method for preparing battery cathode active substance calcium zincate |
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| CN105327597A (en) * | 2015-12-08 | 2016-02-17 | 徐伟鹏 | Solid desulfurizer |
| CN108939904A (en) * | 2018-07-04 | 2018-12-07 | 华润水泥技术研发有限公司 | A kind of desulfurizing agent composition and its application in clinker production |
| WO2020019823A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing calcium zincate |
| CN111603915A (en) * | 2020-05-13 | 2020-09-01 | 循天能源环境科技有限公司 | Flue gas purification process |
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| CN1046213C (en) * | 1993-04-26 | 1999-11-10 | 中国石化齐鲁石油化工公司 | Normal temperature zinc oxide desulfurizer and preparation method thereof |
| US6428761B1 (en) * | 2000-09-29 | 2002-08-06 | Engelhard Corporation | Process for reduction of gaseous sulfur compounds |
| US20030077512A1 (en) * | 2001-10-18 | 2003-04-24 | Allen Charkey | Electrolyte for alkaline rechargeable batteries |
| CN1397498A (en) * | 2002-09-03 | 2003-02-19 | 南开大学 | Process for preparing calcium zincate as negative electrode material of secondary ZnNi battery |
| CN1235303C (en) * | 2003-01-30 | 2006-01-04 | 江苏海四达集团有限公司 | Preparation method of alkaline secondary zinc battery negative electrode active material |
| CN1274042C (en) * | 2004-07-07 | 2006-09-06 | 南开大学 | Negative electrode material for alkaline secondary zinc electrode |
| EP1715536A3 (en) * | 2005-04-20 | 2007-10-10 | ReVolt Technology AS | Zinc electrode comprising an organic gelling agent and an organic binder. |
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| CN101746810B (en) * | 2008-12-16 | 2012-05-02 | 天津蓝天高科电源股份有限公司 | Method for preparing battery cathode active substance calcium zincate |
| CN104826392A (en) * | 2015-04-21 | 2015-08-12 | 蚌埠德美过滤技术有限公司 | High-temperature adsorption filtering agent capable of absorbing carbon dioxide and preparation method therefor |
| CN105327597A (en) * | 2015-12-08 | 2016-02-17 | 徐伟鹏 | Solid desulfurizer |
| CN105327597B (en) * | 2015-12-08 | 2017-12-05 | 东营国安化工有限公司 | A kind of solid desulfurating agent |
| CN108939904A (en) * | 2018-07-04 | 2018-12-07 | 华润水泥技术研发有限公司 | A kind of desulfurizing agent composition and its application in clinker production |
| WO2020019823A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing calcium zincate |
| US11247913B2 (en) | 2018-07-24 | 2022-02-15 | Chongqing Dongqun Technology Co., Ltd. | Method for producing calcium zincate |
| CN111603915A (en) * | 2020-05-13 | 2020-09-01 | 循天能源环境科技有限公司 | Flue gas purification process |
| CN111603915B (en) * | 2020-05-13 | 2022-03-08 | 循天能源环境科技有限公司 | Flue gas purification process |
| CN112546845A (en) * | 2020-11-20 | 2021-03-26 | 沈阳三聚凯特催化剂有限公司 | Hydrolysis absorption type desulfurizer and preparation method and application thereof |
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| CN101288821B (en) | 2012-09-05 |
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