CN102417195A - Improvement of production process for producing magnesium oxide by carbonization method - Google Patents
Improvement of production process for producing magnesium oxide by carbonization method Download PDFInfo
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- CN102417195A CN102417195A CN2010102945407A CN201010294540A CN102417195A CN 102417195 A CN102417195 A CN 102417195A CN 2010102945407 A CN2010102945407 A CN 2010102945407A CN 201010294540 A CN201010294540 A CN 201010294540A CN 102417195 A CN102417195 A CN 102417195A
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- carbonization
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Abstract
The invention relates to a production process of an inorganic compound and particularly relates to improvement of a production process for producing magnesium oxide by a carbonization method. The carbonization method is a main method for producing magnesium oxide, however, the carbonization method has two defects: 1, the content of a calcium impurity in a product is overhigh; and 2, raw material utilization rate is not high, wherein the main reason of low raw material utilization rate is as follows: a large amount of inert magnesium carbonate is produced in the carbonization, and inert magnesium carbonate dose not participate in carbonization reaction and enters into waste slag. In the patent of the invention, aiming at the defects in the carbonization production process, inert magnesium carbonate is converted; dolomitic lime or lime slaking product namely calcium hydroxide are utilized to react with magnesium carbonate in the presence of a catalyst, and magnesium carbonate is converted to magnesium hydroxide so that magnesium hydroxide can be subjected to carbonization reaction again, thus magnesium is extracted, and the utilization rate of magnesium is greatly improved; and in the conversion reaction, calcium hydroxide can be simultaneously converted to calcium carbonate, calcium carbonate is inert to carbonization and can not be carbonized, thereby reducing the content of the calcium impurity in the product. Practice shows that by using the improved production process, the content of the calcium impurity (CaO) in the product is reduced to 0.1%, the purity of magnesium oxide can reach more than 98%; and a high-quality magnesium oxide product can be produced by the processes such as carbonization, filtration, filtrate pyrolysis, re-filtration, filter cake drying, calcination, smashing and the like from the carbonized waste slag after conversion according to the existing process.
Description
Technical field
The present invention relates to the magnesian production technique of mineral compound, specifically is the improvement of carborization being produced the Natural manganese dioxide production technique.
Background technology:
Carborization is to produce Natural manganese dioxide and intermediates thereof.The main working method of Magnesium Carbonate Light 41-45; But carborization is produced the magnesium compound method two big deficiencies are arranged: calcium oxide impurity too high levels in the first product Natural manganese dioxide; Natural manganese dioxide national standard (HG/T2573-2000) premium grads requires≤1.0% to the CaO foreign matter content, this standard, carborization be do not allow readily accessible; Especially the rhombspar carborization is difficult to reach this standard.It two is that raw material availability is low, and carborization is produced Natural manganese dioxide, and the raw material of actual consumption is much higher than theoretical value, produces a large amount of carbonization waste residues in the production, and not only contaminate environment has also caused the waste of resource.
No matter carborization is produced Natural manganese dioxide and use what raw material, last direct carbonization all be Mg (OH)
2, Mg (OH)
2Can carry out carburizing reagent smoothly:
Mg(OH)
2+2CO
2＝Mg(HCO
3)
2
Mg (HCO
3)
2Be soluble, magnesium entering solution and other impurity are separated, obtain magnesium oxide product at last through the post-order process process.But part Mg (OH) is also arranged simultaneously
2Following reaction takes place during carbonization:
Mg(OH)
2+CO
2＝MgCO
3+H
2O
MgCO
3In carbonization, be inertia, no longer participate in carburizing reagent, get in the carbonization waste residue.This is the low major cause of raw material availability.
The present invention utilizes Ca (OH)
2With the MgCO in the carbonization waste residue
3Reaction can be with MgCO
3Be converted into Mg (OH)
2:
MgCO
3+Ca(OH)
2＝Mg(OH)
2+CaCO
3
Carbonization waste residue through conversion processing just can the secondary carbonization extract magnesium like this, improves the utilization ratio of magnesium greatly.But this conversion process must could be carried out in the presence of catalyzer-soluble calcium salt or magnesium salts smoothly, and principle is following:
Suppose that the catalyzer that adds is MgCl
2, MgCl so
2Will dissociate Mg
2+Ion, Mg
2+With Ca (OH)
2Reaction:
Mg
2++Ca(OH)
2＝Mg(OH)
2+Ca
2+
Because Mg (OH)
2Solubleness is than Ca (OH)
2Solubleness little, reaction can be carried out, free Ca
2+Again with MgCO
3Reaction:
Ca
2++MgCO
3＝CaCO
3+Mg
2+
CaCO
3Lysate compares MgCO
3Solubleness little, reaction can be carried out Ca
2+With Mg
2+Free, Mg
2+Ion again can with Ca (OH)
2Reaction, circulation is got off, and the total reaction equation is exactly:
MgCO
3+Ca(OH)
2＝Mg(OH)
2+CaCO
3
Add catalyzer and make solid-solid reaction,,, react smooth through IX Gu become solid-liquid-reaction.Can be included into the phase-transfer catalysis category by catalytic mechanism, be the application extension of phase-transfer catalysis theory in inorganic synthesizing of organic synthesis.
In the rhombspar carborization, contain a large amount of CaO in the raw material dolomite ash, aquation becomes Ca (OH) before the carbonization
2, other raw material all has the impurity CaO or the Ca (OH) of different amounts
2, in the production CaO also aquation become Ca (OH)
2, Ca (OH)
2Principal reaction when carbonization:
Ca(OH)
2+CO
2＝CaCO
3+H
2O
CaCO
3No longer participating in carburizing reagent is inertia and gets into the carbonization waste residue.But also have part that following reaction takes place:
Ca(OH)
2+2CO
2＝Ca(HCO
3)
2
Ca (HCO
3)
2With Mg (HCO
3)
2Get into filtrating together, after pyrolysis, filtration, drying, calcining, become CaO, reaction equation:
Ca(HCO
3)
2＝CaCO
3+CO
2+H
2O
CaCO
3＝CaO+CO
2
The CaO that generates becomes the impurity in the product, and this is the main source of products C aO impurity.
According to above argumentation, the present invention is with Ca (OH)
2Be converted into CaCO through conversion reaction
3, the CaCO that in carbonization, generates
3Carburizing reagent no longer takes place, thereby has reduced the content of CaO impurity in the product.
Can produce Natural manganese dioxide with the rhombspar carborization, how simple declaration improves the utilization ratio of magnesium and the content that reduces CaO impurity in the product with aforesaid method.
Rhombspar is CaCO
3And MgCO
3Composite minerals, calcining back generates CaO and MgO, aquation becomes Ca (OH)
2And Mg (OH)
2, last Mg (OH)
2Except that part becomes the product MgO, also have a large amount of Mg (OH)
2Become MgCO
3And the entering waste residue, a large amount of Ca (OH)
2Become CaCO after the carbonization
3, also get into waste residue, so the production of rhombspar carborization produces a large amount of carbonization waste residues.The 1t product approximately produces 5～7t waste residue.Through the above, can utilize conversion reaction, with MgCO wherein
3Be converted into Mg (OH)
2Carry out carbonization again, propose magnesium, improve the utilization ratio of magnesium in the raw material.The concrete practice is carbonization waste residue and dolomite ash to be added water break into slurry, adds little amount of catalyst again, carries out conversion processing by the previous reaction condition.The amount of carbonization waste residue and dolomite ash should be by MgCO in the waste residue
3With the ratio of CaO molar mass in the dolomite ash is to calculate at 1: 1.Conversion processing can be carried out carbonization, filtration by existing technology later fully ... Etc. the post-order process process.This process modification will improve the utilization ratio of magnesium greatly.The circular treatment utilization of carbonization waste residue, active MgCO
3Almost can all extract.CaO impurity also will reduce greatly in the product, and CaO content can reduce to 01%, and purity can reach more than 98%, has improved the class of product greatly.In addition because a large amount of MgCO
3Be extracted out, reduced and contain MgCO in the magnesium lime carbonate
3Content, also improved product specification.(aquation becomes Ca (OH) to a large amount of CaO in the dolomite ash
2) with waste residue in MgCO
3Reaction generates CaCO
3, make raw material in carbonization, no longer consume CO
2, reduced carbonization time, energy-saving and cost-reducing.
Except dolomite ash, other raw material also contains a certain amount of CaO and (is digested to Ca (OH)
2), or Ca (OH)
2Impurity like the light burnt powder of magnesite, generally has 1～3% CaO impurity.These CaO, Ca (OH)
2Impurity brings products C aO impurity.These raw materials can be through conversion processing with Ca (OH)
2Be converted into CaCO
3, make it not participate in carburizing reagent, thereby reduce CaO foreign matter content in the product.The MgCO that needs in the conversion
3Can take from the carbonization waste residue.Method is very simple, as making raw material of light burnt powder (MgO) when digesting, as long as press MgCO in impurity CaO and the waste residue
3Molar mass added the carbonization waste residue and gets final product than 1: 1, by former technology digest, carbonization ... Obtain the high quality magnesium oxide product at last.
With following instance production is described in detail as follows:
1, takes by weighing the carbonization waste residue of 240kg rhombspar carborization, add the 55kg dolomite ash, add 200g halogen sheet again, add pyrolysis water (85 ℃) 0.5 cubic meter; Keep 85 ℃, stirring reaction 1.5 hours, reaction finishes, after the cooling; Add 3.5 cubic meter cold water attemperation and concentration, under 20 ℃ of temperature, feed 0.3MPa, CO
2Volumetric concentration is 38% kiln gas reaction 1 hour, and controlled temperature is below 30 ℃.Reaction finishes after filtrations, the filtrating clarification, feeds 1.3MPa steam, is heated to 101 ℃, produces the light magnesium carbonate precipitation, after filtration, after the washing, in 140 ℃ dry down, dry back gets MgO product 32.1kg 900 ℃ of calcinings down.The Natural manganese dioxide quality reaches HG/T2573-2000 premium grads standard, impurity CaO content 0.12%.
2, in 5 cubic meter retort, add 240kg carbonization waste residue, add dolomite ash 55kg again, add 200g halogen sheet again; Add pyrolysis water (85 ℃) 0.5 cubic meter, keep 85～90 ℃ of temperature, stirring reaction 2 hours; Reaction finishes, and squeezes into 3.5 cubic meter cold water (15 ℃), attemperation and concentration; Under 22 ℃ of temperature, feed 0.5MPa, CO
2The kiln gas reaction of volumetric concentration 36% 1.5 hours, controlled temperature is below 32 ℃.Reaction finishes, and after the clarification of filtering, filtrate, feeds 1.2MPa steam; Be heated to 100 ℃, produce deposition, deposition is through filtration, washing; Be dried to moisture 4-5% in 130 ℃, again 850 ℃ of calcinings down, MgO31.5kg; The Natural manganese dioxide quality reaches HG/T2573-2000 premium grads standard, and purity reaches 98.2%, CaO content 0.10%.
3, get dolomite ash 115kg, add carbonization waste residue (butt) 23kg, add hot water 0.2 cubic meter, with halogen sheet 100g; Making beating keeps 80～90 ℃, stirring reaction 2 hours, and reaction finishes; Add 4 cubic meter cold water (15 ℃) attemperation and concentration, the feeding volumetric concentration is 42% kiln gas under 20 ℃, and control reaction temperature was reacted 1.5 hours below 25 ℃; Filter, filtrating feeds 1.3MPa and is steam heated to 100 ℃ after clarification, calcining under 900 ℃ again behind the preliminarily dried; Get Natural manganese dioxide 35kg, purity reaches 98.2%, CaO foreign matter content 0.09%.
MgCO among the present invention
3Can be the MgCO in the carbonization waste residue
3, also can be the MgCO in other waste liquid in producing, the waste residue
3, or underproof product MgCO
3, convert it into Mg (OH)
2Carbonization extracts magnesium once more, makes the best use of everything.
Ca in the conversion reaction of the present invention (OH)
2Can be the hydrated product of raw material dolomite ash or lime, also can be impurity Ca (OH) in the raw material
2Or CaO, the CaO aquation becomes Ca (OH)
2, make Ca (OH) through conversion reaction
2Change into CaCO
3Make it not participate in carburizing reagent, reduce the content of CaO impurity in the product.
Unspecified solid matter ratio in this specification sheets and claims is the mass ratio of common sense.
Claims (5)
1. carborization is produced the improvement of Natural manganese dioxide production technique, and its characteristics are carbonization waste residue that produces in the carbonization and Ca (OH)
2Break into slurry, add solubility magnesium salts or calcium salt and make catalyzer, under 80～90 ℃ of temperature, stirring reaction 0.5-2.0 hour, at this moment Ca (OH) takes place
2Reaction with magnesiumcarbonate in the waste residue: Ca (OH)
2+ MgCO
3=CaCO
3+ Mg (OH)
2In this reaction, MgCO
3Be converted into Mg (OH)
2, Ca (OH)
2Be converted into CaCO
3, Mg (OH)
2Be easy to carbonization, the carbonization waste residue carbonization once more after the conversion extracts magnesium, improves the utilization ratio of magnesium, carburizing reagent equation: Mg (OH)
2+ 2CO
2=Mg (HCO
3)
2, Mg (HCO
3)
2Water soluble, magnesium change solution over to separates Mg (HCO with calcium
3)
2Through the postorder operation, become product Natural manganese dioxide at last, Ca in above-mentioned conversion reaction (OH)
2Be converted into CaCO simultaneously
3, CaCO
3Carbonization is inertia, can not changes solution over to through carbonization, calcium impurities content reduces greatly in the product Natural manganese dioxide thereby make; Slurry after the conversion is lowered the temperature through heat exchange, add cold water attemperation and concentration again after, through carbonization, filtration, filtrating pyrolysis; Refilter, operation such as filtration cakes torrefaction, calcining, pulverizing gets magnesium oxide product; Calcium oxide content can reduce to 0.1% in the product, and Natural manganese dioxide purity can reach more than 98%, and this process circulation is carried out; Active carbonic acid magnesium almost can all extract, and improves the utilization ratio of magnesium greatly.
In the claim 1 in the conversion reaction with carbonization waste residue and Ca (OH)
2Break into slurry, amount of water (quality) is 1.5～5 times of waste residue amount (quality), 80～90 ℃ of temperature of reaction, and in 0.5～2.0 hour reaction times, magnesiumcarbonate is 1: 1 with calcium hydroxide molar mass ratio.
3. solubility magnesium salts of catalyzer described in the claim 1 or calcium salt refer to the muriate of calcium magnesium, nitrate salt, acetate etc., and acting in fact is calcium ion and mg ion, so can appoint wherein one or more, can dissociate calcium ions and magnesium ions and get final product.
4. MgCO in the claim 1
3Can be the MgCO in the carbonization waste residue
3, also can be the MgCO in other waste liquid in producing, the waste residue
3, or underproof product MgCO
3, convert it into Mg (OH)
2Carbonization extracts magnesium once more, makes the best use of everything.
5. the Ca in the conversion reaction (OH) in the claim 1
2Can be the hydrated product of raw material dolomite ash or lime, also can be impurity Ca (OH) in the raw material
2Or CaO, the CaO aquation becomes Ca (OH)
2, make Ca (OH) through conversion reaction
2Change into CaCO
3Make it not participate in carburizing reagent, reduce the content of CaO impurity in the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010294540.7A CN102417195B (en) | 2010-09-28 | 2010-09-28 | Improvement of production process for producing magnesium oxide by carbonization method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010294540.7A CN102417195B (en) | 2010-09-28 | 2010-09-28 | Improvement of production process for producing magnesium oxide by carbonization method |
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|---|---|
| CN102417195A true CN102417195A (en) | 2012-04-18 |
| CN102417195B CN102417195B (en) | 2014-02-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811448A (en) * | 2021-01-18 | 2021-05-18 | 朱广东 | Recovery process of magnesium oxide reducing slag |
| CN112844494A (en) * | 2020-12-25 | 2021-05-28 | 河北工程大学 | Method for recycling magnesium alkylation reaction catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100384A (en) * | 1993-09-13 | 1995-03-22 | 高佳令 | Method for extracting light magnesium carbonate from boron mud |
| CN1944259A (en) * | 2006-11-03 | 2007-04-11 | 高佳令 | Process for producing industrial magnesium oxide using dolomite ash and boron mud |
-
2010
- 2010-09-28 CN CN201010294540.7A patent/CN102417195B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100384A (en) * | 1993-09-13 | 1995-03-22 | 高佳令 | Method for extracting light magnesium carbonate from boron mud |
| CN1944259A (en) * | 2006-11-03 | 2007-04-11 | 高佳令 | Process for producing industrial magnesium oxide using dolomite ash and boron mud |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844494A (en) * | 2020-12-25 | 2021-05-28 | 河北工程大学 | Method for recycling magnesium alkylation reaction catalyst |
| CN112811448A (en) * | 2021-01-18 | 2021-05-18 | 朱广东 | Recovery process of magnesium oxide reducing slag |
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| Publication number | Publication date |
|---|---|
| CN102417195B (en) | 2014-02-26 |
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