CN1151066C - Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation - Google Patents
Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation Download PDFInfo
- Publication number
- CN1151066C CN1151066C CNB021109389A CN02110938A CN1151066C CN 1151066 C CN1151066 C CN 1151066C CN B021109389 A CNB021109389 A CN B021109389A CN 02110938 A CN02110938 A CN 02110938A CN 1151066 C CN1151066 C CN 1151066C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- manganese
- cobalt
- type molecular
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- -1 ferrous manganese oxides Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 159000000003 magnesium salts Chemical class 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011707 mineral Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910001655 manganese mineral Inorganic materials 0.000 abstract 3
- 239000011148 porous material Substances 0.000 abstract 3
- 206010039509 Scab Diseases 0.000 abstract 2
- KZCNWEDSGMXJRR-UHFFFAOYSA-N [Mn].[Ca].[Ba] Chemical compound [Mn].[Ca].[Ba] KZCNWEDSGMXJRR-UHFFFAOYSA-N 0.000 abstract 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- YHANMXMDLYWOGX-UHFFFAOYSA-N [Mn].[Ca].[Ba].[Ca] Chemical compound [Mn].[Ca].[Ba].[Ca] YHANMXMDLYWOGX-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000584 environmental toxicity Toxicity 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a method for synthesizing barium-calcium-manganese mineral type molecular sieves by using manganese nodules and cobalt-rich crusts as raw materials, which is characterized in that fresh manganese nodules or cobalt-rich crusts react with an oxidizing agent to enhance the oxidation state of the manganese element in the raw materials, and then, magnesium ions are implanted into crystal lattices of manganese mineral to perform the functions of a template agent; various ferrous manganese oxides and hydroxides in the raw material are all converted into barium-calcium-manganese mineral type molecular sieves through thermal reaction in high-temperature water. The method has the advantages of simple technological process, low production cost and easy popularization and implementation. Due to the 3*3 canal pore structure of the molecular sieve prepared by the method, the sieve pore diameter is about 0.69 nanometer. Compared with the traditional molecular sieve synthesized by Al, Si, Fe and other elements, the molecular sieve has the advantages of large pore diameter, high catalytic activity, low toxicity, etc. and can be widely used in the fields of chemical engineering catalysis, environmental engineering, high performance batteries, etc. The method also opens up a new way for the reasonable development and utilization of marine metallic mineral resources.
Description
Technical field
The present invention relates to a kind of is the method for the synthetic todorokite type molecular sieve of raw material with manganese nodule, cobalt-bearing crust.
Background technology
Todorokite (todorokite) is a kind of manganese-base oxide molecular sieve.Its crystals has been full of hole, one dimension tunnel, its transverse section be 3 * 3 manganese oxygen octahedras surround square, its length of side is 0.69 nanometer.In similar manganese oxide molecular sieve, its tunnel bore dia maximum.Corresponding, the crystalline internal surface area is also maximum, thereby good adsorption catalysis activity and ion-exchange performance are arranged.It is in the wide attention that should have prospect to cause domestic and international academia in functional material field.Soluble ion and small molecules in the multi-cellular structure energy strong adsorption water body of Todorokite, can be used to adsorb heavy metal and radioelement, and the great surface-area of Todorokite makes it have very high chemically reactive, can be with the transition metal ion in the solution from being oxidized to high price at a low price, reducing its environmental toxicity and make it be easy to remove from water, is ideal water treatment scavenging agent.The ion-exchange performance that Todorokite is good makes it become lithium magnesium rechargeable cell potential electrode materials.Catalysis industry also is one of Todorokite most important applications field.The catalytic activity of manganese metal is much higher than by general catalyzer of element synthetic such as Al, Si, Fe.Therefore, Todorokite has that toxicity is low, the catalytic activity advantages of higher, in chemical catalysis field sizable application potential is arranged.
At present, this molecular sieve analog is mainly used the chemical reagent synthetic, and raw materials cost height, Production Flow Chart are long, are unfavorable for its practical application.
Ocean manganese nodule is common in the submarine surface of 4,000 to six kms, and total reserves is no less than 3,000,000,000,000 tons according to estimates.Cobalt-bearing crust generally is grown in the top layer of seamount rock.China units concerned have made a large amount of investigation in early stage and Mining Test to Eastern Pacific's submarine manganese nodule under National Bureau of Oceanography and Chinese ocean association tissue, and have obtained the mineral right in 150,000 square kilometres of marine sites.To the present well afoot of reconnoitring of cobalt-bearing crust.These two classes Mineral resources all have huge reserves, compare to the chemical reagent of synthetic todorokite, relative low price.
The essential mineral of ocean manganese nodule is the birnessite (bimessite) with sheet structure, secondly is todorokite, in addition amorphousness iron and manganese oxides, the oxyhydroxide that also has quantity not wait.Wherein birnessite is the intermediates in synthetic calcium barium calcium manganese ore deposit, and amorphousness is equivalent to the raw material of synthetic, and original calcium barium calcium manganese ore deposit plays a part structure cell, embryo in the manganese nodule in reaction.The mineral of cobalt-bearing crust and Chemical Composition and manganese nodule are very similar.Their main thing all can be transformed into todorokite mutually under proper condition.This is to be raw material with manganese nodule, cobalt-bearing crust, the basis of preparation BaCaMn ore type molecular sieve.
Owing to be rich in Mn, Ni, Cu, Co and Fe, it is the ore of extracting metals that ocean manganese nodule and cobalt-bearing crust are being seen always.Till settled the present, its economic worth is all gone to estimate in countries in the world from the mineral metal products resource view.The major obstacle of oceanic multi-metal nodule and cobalt-bearing crust commercial production is an economic factors at present, and promptly the deep-sea mining cost is much higher than the mine of land.If still treat oceanic multi-metal nodule and cobalt-bearing crust resource with traditional eye, their actual development and use can only lie on the table after the similar mineral products in land are exhausted substantially so.With manganese nodule, cobalt-bearing crust is raw material, and preparation todorokite type molecular sieve will be opened new approaches for these two classes reasonable resources development and use, and the commercial-scale operation of ocean mineral metal products resource is arrived in advance.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for the synthetic todorokite type molecular sieve of raw material with manganese nodule, cobalt-bearing crust.
Preparation method's step is as follows:
1), under moisture state, is ground to granularity less than 60 orders without ocean manganese nodule that dehydrates or cobalt-bearing crust;
2) add the hydrogen peroxide be equivalent to 10～15 times of raw material volumes, or concentration is the saline oxidizing agent solution of 0.1～0.3M, violent stirring 15～30 minutes;
3) behind the centrifugal or filter dehydration, clean 2～3 times, and dehydration again;
4) the gained solid phase moves into new container, adds to be equivalent to raw material volume 8-12 doubly, and concentration is the magnesium salt solution of 0.5～1.5M, stirs, react 10～12 hours, during keep concussion or slowly stirring;
5) behind the centrifugal or filter dehydration, select for use distilled water or magnesium salt solution, the gained solid phase is mixed with the ore pulp of concentration about 5～15% as dispersion medium;
6) above-mentioned ore pulp is poured autoclave into, makes ore pulp be full of autoclave, after the sealing with autoclave at 120～200 ℃ of constant temperature more than 24 hours;
7) open autoclave after being cooled to room temperature, the centrifugal or filter dehydration with reaction product cleans 3～5 times;
8) gains are cool naturally shines dryly, or dries being lower than under 90 ℃ of temperature, promptly obtains todorokite type molecular sieve.
Said saline oxidizing agent solution is NaMnO
4, KMnO
4, K
28
2O
8In one or more.Oxidizing agent solution all should be now with the current.
Said magnesium salts is one or more in magnesium chloride, magnesium nitrate, the sal epsom.
Said autoclave inwall is added with polytetrafluoroethylene bushing, the teflon seal lid is arranged at the top, and compressive strength is not less than 10MPa.
Advantage of the present invention is:
1) utilize natural matter to prepare the BaCaMn ore type molecular sieve, production cost is low;
2) opened up new way for the rational exploitation and utilization of ocean manganese nodule, cobalt-bearing crust;
3) manganese element in the raw material, transition metal have higher catalytic activity, and product performance will be better than the molecular sieve of other type, and use chemical reagent synthetic congeneric elements sieve;
4) the BaCaMn ore type molecular sieve with price advantage has broad application prospects at industrial circles such as environmental protection, chemical industry catalysis, heavy-duty batteries.
Embodiment
The raw material that the present invention uses is the manganese nodule that picks up from oceanic deposit thing top layer, or is grown in the cobalt-bearing crust of seamount rock surface.Two kinds of raw materials all should avoid dry before use, and original thing might take place to decompose or phase transformation behind drying and dehydrating in the raw material.
The grinding of raw material and stirring technique are well-known, can select conventional mining equiment for use.
Be applicable to that oxidizing agent solution requirement of the present invention is not very strict.The oxygenant of recommending use is one or more in hydrogen peroxide, sodium permanganate, potassium permanganate, the potassium persulfate solution, also can be with oxygen by the pure water of suitable flow importing with volume.The purpose that adds oxygenant is the oxidation state that improves manganese element in the raw material, and the Mn that draws up
3O
4Generation, make amorphousness Mn oxide, oxyhydroxide in the raw material be transformed into birnessite.
The present invention uses the purpose of magnesium salt solution, is to make magnesium ion partly replace sodium ion between the birnessite lattice layer, generates the Mg-birnessite.If use Co2
+, Ni
2-, Cu
2+Salt substitutes magnesium salts, can synthesize todorokite equally, but product thermostability and electrochemical activity reduction, and environmental toxicity and production cost rise.Therefore the present invention recommends to use magnesium salts.Change in the reaction of todorokite at birnessite, interlayer cation plays a part template.
The used autoclave of hydro-thermal reaction can use non-brittle metallic substance such as red copper, stainless steel to make, and kettle and sealing material need can tolerate in the 10Mpa and press and 250 ℃ of high temperature.The reactor domestic demand adds the tetrafluoroethylene lining, and the teflon seal lid is arranged at the top, corrodes kettle to prevent solution.
In making processes of the present invention, it is not very strict that the water yield that relevant step is added requires.For reaction is carried out thoroughly, pulp density preferably is no more than 10%.Use the ore pulp of higher concentration as need, can corresponding raising oxygenant, the concentration of magnesium salts or sodium salt solution.
Embodiment 1: be feedstock production todorokite type molecular sieve with the manganese nodule
Originate from Eastern Pacific's submarine manganese nodule 1.1 take 5 grams (weight in wet base), appropriateness is ground in mortar;
1.2 0.15M K with 50 milliliters of existing preparations
2S
2O
8Solution is gone into beaker with sample wash, continues stir about 30 minutes;
1.3 product filters, and cleans 3 times with distilled water;
1.4 product is moved into 50 milliliters of 1M MgCl
2In the solution, stirring is spent the night;
1.5 product filters, and is moved into volume and is in 50 milliliters the autoclave;
1.6 add 1M MgCl
2About 45 milliliters of solution, appropriateness stirs, lid tightening seal, autoclave constant temperature 24 hours in 160 ℃ of baking ovens;
1.7 take out product after being cooled to room temperature, clean 3 times with distilled water;
1.8 product is dried about 90 ℃, promptly gets todorokite type molecular sieve.
Embodiment 2: be feedstock production todorokite type molecular sieve with the cobalt-bearing crust
2.1 take the cobalt-bearing crust that 5 grams (weight in wet base) originate from Pacific Ocean seamount, appropriateness is ground in mortar;
2.2 0.1M NaMnO with 50 milliliters of existing preparations
4Solution is gone into beaker with sample wash, continues stir about 30 minutes;
2.3 product filters, and cleans 3 times with distilled water;
2.4 product is moved into 50 milliliters of 1M Mg (NO
3)
2In the solution, stirring is spent the night;
2.5 product filters, and is moved into volume and is in 50 milliliters the autoclave;
2.6 add 1M Mg (NO
3)
2About 45 milliliters of solution, appropriateness stirs, lid tightening seal, reactor constant temperature 24 hours in 160 ℃ of baking ovens;
2.7 take out product after being cooled to room temperature, clean 3 times with distilled water;
2.8 product is dried about 90 ℃, promptly gets todorokite type molecular sieve.
The invention discloses a kind of is raw material with ocean manganese nodule, cobalt-bearing crust, prepares the method for todorokite type molecular sieve.The raw material that this invention relates to is from the natural resources that spreads all over seabed, ocean and seamount, and it is extremely extensive to originate, and preparation method's technical process is simple, and low production cost is easy to promotion and implementation.Molecular sieve based on the present invention makes can be widely used in industries such as chemical industry catalysis, environmental engineering, heavy-duty battery.This invention has also been opened up new way for rational exploitation and utilization ocean mineral metal products resource.
Claims (4)
1. one kind is the method for the synthetic todorokite type molecular sieve of raw material with manganese nodule, cobalt-bearing crust, it is characterized in that its step is as follows:
1), under moisture state, is ground to granularity less than 60 orders without ocean manganese nodule that dehydrates or cobalt-bearing crust;
2) add the hydrogen peroxide be equivalent to 10～15 times of raw material volumes, or concentration is the saline oxidizing agent solution of 0.1～0.3M, violent stirring 15～30 minutes;
3) behind the centrifugal or filter dehydration, clean 2～3 times, and dehydration again;
4) the gained solid phase moves into new container, adds to be equivalent to raw material volume 8-12 doubly, and concentration is the magnesium salt solution of 0.5～1.5M, stirs, react 10～12 hours, during keep concussion or slowly stirring;
5) behind the centrifugal or filter dehydration, select for use distilled water or magnesium salt solution, the gained solid phase is mixed with the ore pulp of concentration about 5～15% as dispersion medium;
6) above-mentioned ore pulp is poured autoclave into, makes ore pulp be full of autoclave, after the sealing with autoclave 120～200 ℃ of constant temperature 24 hours;
7) open autoclave after being cooled to room temperature, the centrifugal or filter dehydration with reaction product cleans 3～5 times;
8) gains are cool naturally shines dryly, or dries being lower than under 90 ℃ of temperature, promptly obtains todorokite type molecular sieve.
2. according to claim 1 a kind of be the method for the synthetic BaCaMn ore type molecular sieve of raw material with manganese nodule, cobalt-bearing crust, it is characterized in that said saline oxidizing agent solution is NaMnO
4, KMnO
4, K
2S
2O
8In one or more.
3. according to claim 1 a kind of be the method for the synthetic BaCaMn ore type molecular sieve of raw material with manganese nodule, cobalt-bearing crust, it is characterized in that said magnesium salts is one or more in magnesium chloride, magnesium nitrate, the sal epsom.
4. according to claim 1 a kind of be the method for the synthetic todorokite type molecular sieve of raw material with manganese nodule, cobalt-bearing crust, it is characterized in that said autoclave inwall is added with polytetrafluoroethylene bushing, the teflon seal lid is arranged at the top, compressive strength is not less than 10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021109389A CN1151066C (en) | 2002-02-28 | 2002-02-28 | Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021109389A CN1151066C (en) | 2002-02-28 | 2002-02-28 | Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1382630A CN1382630A (en) | 2002-12-04 |
| CN1151066C true CN1151066C (en) | 2004-05-26 |
Family
ID=4741329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021109389A Expired - Fee Related CN1151066C (en) | 2002-02-28 | 2002-02-28 | Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1151066C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348310C (en) * | 2003-12-03 | 2007-11-14 | 中国地质大学（北京） | Ocean polymetallic nodule-crust leaching slag adsorbent and preparation method thereof |
| CN101559988B (en) * | 2009-05-27 | 2013-08-07 | 北京矿冶研究总院 | Treatment method of ammonia nitrogen wastewater |
| CN101775495B (en) * | 2010-01-15 | 2011-05-18 | 浙江大学 | Preparation method of active cryptomelane |
-
2002
- 2002-02-28 CN CNB021109389A patent/CN1151066C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1382630A (en) | 2002-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Lithium extraction from high Mg/Li brine via electrochemical intercalation/de-intercalation system using LiMn2O4 materials | |
| CN1810353A (en) | Method for preparing lithium ion sieve adsorbent | |
| CN109317100B (en) | Normal-temperature pretreatment-hydrothermal carbonization method for preparing magnetic algae-based biochar | |
| Li et al. | Highly selective separation of lithium with hierarchical porous lithium-ion sieve microsphere derived from MXene | |
| CN108101043B (en) | Preparation method and application of coal-derived artificial graphite material | |
| CN109485036B (en) | Method for recovering and treating waste cathode carbon blocks of aluminum electrolytic cell | |
| CN107324454B (en) | Copper ion-loaded graphene aerogel electrode material and preparation method thereof | |
| CN103072980A (en) | Method for quickly preparing graphene sheets | |
| CN1803273A (en) | Preparation method of lithium adsorbent | |
| CN113151855A (en) | Copper nano electrode rich in twin crystal boundary and preparation and application thereof | |
| CN110394154B (en) | Preparation method and application of moso bamboo charcoal/FeMn-LDH composite material | |
| CN113184926A (en) | Method for preparing Ni-Cu LDH material by using electroplating sludge and application | |
| CN111977651A (en) | Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon | |
| CN1151066C (en) | Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation | |
| CN109671937B (en) | In-situ synthesis method of transition metal oxide/graphene composite material | |
| CN103086437B (en) | Method for preparing chemical manganese dioxide under ultrasonic-wave action | |
| CN108393067B (en) | Method for in-situ synthesis of manganous-manganic oxide/graphene composite adsorbent, product and application thereof | |
| CN105110300B (en) | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur | |
| CN107732209B (en) | Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste | |
| CN111302326A (en) | Nitrogen-doped hierarchical porous carbon material for lead-carbon battery and preparation method thereof | |
| CN106475052B (en) | A kind of application seaweed biomass prepares nano-sized magnesium hydroxide/N doping porous carbon composite material and preparation method thereof | |
| CN112537960B (en) | Method for preparing graphitized cathode by using aluminum electrolysis waste cathode carbon block | |
| CN110699552B (en) | Method for selectively extracting high-purity metal titanium from SCR catalyst | |
| CN111115623B (en) | Preparation method of natural microcrystalline graphite negative electrode material, negative electrode material and application | |
| Patnaik et al. | Synthesis and characterization of fibrous nickel hydroxide obtained from spent nickel catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |