CN1382630A - 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
- CN1382630A CN1382630A CN 02110938 CN02110938A CN1382630A CN 1382630 A CN1382630 A CN 1382630A CN 02110938 CN02110938 CN 02110938 CN 02110938 A CN02110938 A CN 02110938A CN 1382630 A CN1382630 A CN 1382630A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- bacamn
- type molecular
- raw material
- cobalt
- 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.)
- Granted
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation includes the reaction of fresh halobolite or Co-enriched incrustation on oxidant, transplanting Mg ions in the crystal lattice of Mn ore to make it play template agent role, and high-temp hydrothermal reaction. Its advantages are simple process and low cost. The result molecular sieve features 3X3 tunnel pore structure, big pore diameter (0.69nm), high activity and low toxicity.
Description
Technical field
The present invention relates to a kind of is the method for the synthetic BaCaMn ore type molecular sieve of raw material with manganese nodule, cobalt-bearing crust.
Background technology
Calcium barium calcium manganese ore deposit (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 sodium manganite (birnessite) with sheet structure, secondly is the calcium barium calcium manganese ore deposit, in addition amorphousness iron and manganese oxides, the oxyhydroxide that also has quantity not wait.Wherein the sodium manganite 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 the calcium barium calcium manganese ore deposit 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 BaCaMn ore 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 BaCaMn ore 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 oxidizing agent solution that is equivalent to 10～15 times of raw material volumes, 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 magnesium salt solution doubly, 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 reactor, after the sealing with autoclave about 24 hours of 120～200 ℃ of constant temperature;
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 the BaCaMn ore type molecular sieve.
Said oxidizing agent solution can be 3～5% H
2O
2, 0.1～0.3M NaMnO
4, 0.1～0.3M KMnO
4, 0.1～0.3M K
2S
2O
8In one or more.Oxidizing agent solution all should be now with the current.
Said magnesium salts is magnesium chloride, magnesium nitrate, sal epsom, and the concentration of solution is 0.5～1.5M.
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 the sodium manganite.
The present invention uses the purpose of magnesium salt solution, is to make magnesium ion partly replace sodium ion between sodium manganite lattice layer, generates Mg-sodium manganite.If use Co
2+, Ni
2+, Cu
2+Salt substitutes magnesium salts, can synthesize the calcium barium calcium manganese ore deposit 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 in calcium barium calcium manganese ore deposit at the sodium manganite, 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 BaCaMn ore 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 reactor;
1.6 add 1M MgCl
2About 45 milliliters of solution, appropriateness stirs, lid tightening seal, reactor 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 the BaCaMn ore type molecular sieve.
Embodiment 2: be feedstock production BaCaMn ore 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 reactor;
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 the BaCaMn ore type molecular sieve.
The invention discloses a kind of is raw material with ocean manganese nodule, cobalt-bearing crust, prepares the method for BaCaMn ore 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 BaCaMn ore 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 oxidizing agent solution that is equivalent to 10～15 times of raw material volumes, 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 magnesium salt solution doubly, 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 reactor, after the sealing with autoclave about 24 hours of 120～200 ℃ of constant temperature;
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 the BaCaMn ore 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 oxidizing agent solution is 3～5% H
2O
2, 0.1～0.3M NaMnO
4, 0.1～0.3M KMnO
4, 0.1～0.3M 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 magnesium chloride, magnesium nitrate, sal epsom, the concentration of solution is 0.5～1.5M.
4. 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 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 true CN1382630A (en) | 2002-12-04 |
| CN1151066C 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) |
Cited By (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 |
| CN101775495B (en) * | 2010-01-15 | 2011-05-18 | 浙江大学 | Preparation method of active cryptomelane |
| CN101559988B (en) * | 2009-05-27 | 2013-08-07 | 北京矿冶研究总院 | Treatment method of ammonia nitrogen wastewater |
-
2002
- 2002-02-28 CN CNB021109389A patent/CN1151066C/en not_active Expired - Fee Related
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1151066C (en) | 2004-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109317100B (en) | Normal-temperature pretreatment-hydrothermal carbonization method for preparing magnetic algae-based biochar | |
| CN1810353A (en) | Method for preparing lithium ion sieve adsorbent | |
| Li et al. | Highly selective separation of lithium with hierarchical porous lithium-ion sieve microsphere derived from MXene | |
| CN111584804B (en) | Preparation method of lithium-sulfur battery diaphragm barrier layer based on two-dimensional nano clay | |
| CN106082313A (en) | The preparation method of bar-shaped tin ash/two-dimensional nano titanium carbide composite | |
| CN103072980A (en) | Method for quickly preparing graphene sheets | |
| CN1803273A (en) | Preparation method of lithium adsorbent | |
| CN107739031B (en) | Method for preparing lithium ion carbon negative electrode material from mushroom residue waste | |
| CN107324454B (en) | Copper ion-loaded graphene aerogel electrode material and preparation method thereof | |
| CN111977651A (en) | Preparation method of potassium carbonate chemically activated low-order carbon source based porous carbon | |
| CN113501511A (en) | Method for adjusting nitrogen-doped carbon structure based on phytic acid and application of method | |
| 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 | |
| CN1151066C (en) | Process for synthesizing BaCaMn ore type molecular sieve from halobolite and Co-enriched incrustation | |
| CN113201759B (en) | Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof | |
| CN107732209B (en) | Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste | |
| CN113041991A (en) | Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent | |
| 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 | |
| CN114613967A (en) | FeS @ C composite material prepared rapidly by microwave method, and method and application thereof | |
| CN111115623B (en) | Preparation method of natural microcrystalline graphite negative electrode material, negative electrode material and application | |
| CN110699552B (en) | Method for selectively extracting high-purity metal titanium from SCR catalyst | |
| CN107681137B (en) | Sodium ion battery C/C70/CaS composite negative electrode material and preparation method thereof | |
| CN114134534B (en) | Oxygen evolution catalyst based on artificial diamond catalyst and preparation method and application thereof | |
| CN115911308B (en) | Composite sulfur positive electrode material and preparation method thereof, and composite sulfur positive electrode and preparation method thereof |
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 |