CN1087063A - Process for combination producing of magnesium base - Google Patents
Process for combination producing of magnesium base Download PDFInfo
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- CN1087063A CN1087063A CN 93107143 CN93107143A CN1087063A CN 1087063 A CN1087063 A CN 1087063A CN 93107143 CN93107143 CN 93107143 CN 93107143 A CN93107143 A CN 93107143A CN 1087063 A CN1087063 A CN 1087063A
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- send
- ammonium
- ash
- magnesium
- magnesium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
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Abstract
The present invention is a raw material with carbon ammonium and crude salt, carries out replacement(metathesis)reaction and makes soda ash; With the dolomite ash is that raw material and alkali-making mother solution (contain NH
4Cl) reaction is to reclaim ammonia (NH
3), and obtain rich magnesium filter cake for system magnesium salts series product; Being obtained rich magnesium filter cake with system alkali is that raw material carries out carbonization with system magnesium salts series product.The present invention has improved steaming ammonium technology, has reduced the generation of steaming waste liquor of ammonium; Improve the technology of rhombspar carbonization legal system magnesium salts simultaneously, adopted high dense magnesium material, the output height, plant factor is big, and productive expense is low.
Description
The invention belongs to a kind of chemical technology method, specially refer to the technology of magnesium alkali combination producing soda ash combined producting calcium chloride and magnesium basic carbonate.
At present, soda ash production both at home and abroad is still basically and continues to use ammonia alkali technology or integrated soda production.Ammonia alkali technology for recycling of ammonia, is provided with and steams the ammonium process unit, produces a large amount of waste liquids behind the steaming ammonium, and producer enters marine more, causes Marine Environmental Pollution.Though the factory that has has therefrom reclaimed part calcium chloride, the amount that produces waste liquid because of ton alkali is too much, and it is excessive to consume energy when concentrating, so difficulty can all be utilized.Though and integrated soda production does not steam the waste liquor of ammonium generation, but the chloride yield that produces only can reach the farming fertilizer rank, early the field is more soil, the north is reluctant to use, so market is not very wide, often is unsalable gesture, moreover, no matter traditional alkali-making process, or magnesium salts technology all respectively are single product, the market coverage rate is little, and production cost is also than being height.
The objective of the invention is to keep the technologic ripe part of soda ash and magnesium salts, and then again both graftings, so that productive expense reduces greatly and obtains the great number benefit, for exploitation magnesium barium Mineral resources rhombspar, barite etc. are sought new technology, for seeking outlet in the existence and the market of little ammonium carbonate fertilizer containing factory.
Technical scheme of the present invention is achieved in that process for combination producing of magnesium base, it is characterized in that it comprises prepared in saline system, soda ash manufacturing system, Distallation systm, calcium chloride preparation system, magnesium salts preparation system, carbon ammonium system and grey kiln system:
A. prepared in saline system: crude salt is removed magnesium, calcium ion, makes refined brine, send " soda ash manufacturing system ";
B. soda ash manufacturing system: refined brine adds the carbon ammonium, and reaction is finished and filtered, filter cake calcining system soda ash, and pan gas send " magnesium salts preparation system ", and the alkali liquor of filtration send " distillation system ";
C. Distallation systm: by the alkali liquor that " soda ash manufacturing system " comes, dolomite ash breast reaction with being come by " grey kiln system " makes dense ammonium water for " carbon ammonium system ", and the emulsion of reaction is sent " calcium chloride preparation system ";
D. calcium chloride preparation system: the emulsion of emitting by " Distallation systm " reaction, " magnesium salts preparation system " sent in press filtration, filter cake, concentrating filter liquor, filtered and recycled regenerant salt, send " prepared in saline system ", the liquid that filters the back send the finished product of enduring calcium device system two water calcium oxide, Calcium Chloride Powder Anhydrous again;
E. magnesium salts preparation system: the rich magnesium filter cake that is come by " calcium chloride preparation system " adds water furnishing emulsion, send into the magnesium salts carbonating tower, the pan gas that feeding is come by " soda ash manufacturing system ", reaction back press filtration, filtrate pyrolysis after-filtration, filter cake leads to warm air drying, roasting system light magnesium oxide, and hot filtrate send " grey kiln system ";
F. carbon ammonium system: the dense ammonium water that will be come by " Distallation systm ", ash furnace kiln gas that " grey kiln system " comes be sent into carbon ammonium carbonating tower, generate the carbon crystalline ammonium at the bottom of the tower, separate brilliant liquid, and the crystalline carbon ammonium send " soda ash manufacturing system ", and carbon ammonium mother liquor send " Distallation systm ";
G. grey kiln system: rhombspar and coal are sent into ash furnace burn till dolomite ash, dolomite ash is used by " magnesium salts preparation system " next hot water digestion at digestive shelf and is the dolomite ash breast, the dolomite ash breast send " Distallation systm ", kiln gas is drawn on the kiln top, send " carbon ammonium system " after trifle in the world, compression, cooling are removed in water washing.
The present invention has following advantage:
1, improve the steaming ammonium operation of solvay soda process, utilized steaming ammonium device that soda ash and the grafting of magnesium salts technology are got up, employing dolomite ash breast [Ca(OH)
2Ng(OH)
2] react with mother liquor, reduce the generation of waste liquid, reduce and pollute.Steam outside ammonia obtains reclaiming in the ammonium, still can obtain containing rich magnesium [Ng(OH)
2] filter cake, as the cheap raw material of system magnesium salts.Also can from filtrate, reclaim refine salt simultaneously and obtain the calcium chloride product, reclaim salt and return reduction salt consumption in the system alkali system.
2, improved the technology of rhombspar carbonization legal system magnesium salts.The tradition method be adopt the dolomite ash breast [Ng(OH)
2Ca(OH)
2].The present invention adopt dolomite ash steam the rich magnesium filter cake of gained behind the ammonium [Ng(OH)
2], so from the device feed intake on, the present invention adopts high dense magnesium material, so the output height, plant factor is big, productive expense is low.And traditional dolomite ash steams ammonium, and the reaction back generates a large amount of CaCO
3Cause difficulty to filter operation.And make dolomite ash steam ammonium, filter cake is then because of most of Ca(OH)
2Become CaCl
2Go with filtrate, so after the carbonization, a large amount of magnesium compositions magnesium [Ng(HCO that becomes to attach most importance to
3)
2] entering solution, it is many that filter residue then relatively will lack, and therefore, technology is improved, and operation improves.Moreover CaCl
2The production marketing price will be far beyond CaCO
3Price is high, and its purposes is also wide.
3, traditional solvay soda process producing alkali with double decomposition reaction is gas-liquid-solid heterogeneous reaction, and technology of the present invention, metathesis is to adopt solid-liquid reaction, meets the best working district on the Fei Daoqi Prokofiev phase diagram theory on the system base reason more.The present invention is simple than conventional process flow, device is simple, and initial cost is little.
Below in conjunction with accompanying drawing the present invention is further described.
Accompanying drawing is technological process of production figure of the present invention.
With reference to accompanying drawing, the present invention includes prepared in saline system, soda ash manufacturing system, Distallation systm, calcium chloride preparation system, magnesium salts preparation system, carbon ammonium system and grey kiln system.
1, prepared in saline system: crude salt (NaCl, 90%) is dissolved as saturated brine with water under 60 ℃ in changing salt bath, proportion is about 1.21 under 15 ℃, squeeze into demagging groove (stirrer is arranged in the groove), Ng by analysis through pump
2+Content, adding milk of lime [Ca(OH)
2] carry out demagging:
And then squeeze into the deliming groove, analyze Ca
2+After add soda ash (Na again
2CO
3) deliming:
Squeeze into clarifying tank by pump again,, send " soda ash manufacturing system " through leaving standstill clarification for transparent refined brine (NaCl content is about 308 grams per liters).
2, soda ash system system: salt solution metering back (5.2M
3/ ton alkali) squeeze into metathesis alkali still, start stirrer, be warming up to ≯ 32 ℃, add powdery carbon ammonium (NH again
4HCO
3) (about 2.1 tons of/ton alkali).Reaction was carried out 30～40 minutes, discharging, and carry out centrifuging:
Filter cake alkali (the NaHCO that attaches most importance to
3) send calcining furnace, decompose at 180 ℃ down heavy alkali:
Na
2CO
3Through cooling, packing, be to be the soda ash product.Pan gas (NH
3+ CO
2+ H
2O) from calcining furnace, derive, wash with water, compressed again machine boil down to 6kgf/cm through washing tower
2Supply the usefulness of the carbonating tower of " magnesium salts preparation system " (to contain CO
285%).The alkali liquor of whizzer filtration is put and is stored in the alkali liquor groove, by the past Distallation systm of pumping.
3, Distallation systm: by " soda ash manufacturing system " alkali liquor that comes and dolomite ash breast that comes by " grey kiln system " [Ca(OH)
2Mg(OH)
2], in distillation tower, in 95-105 ℃ of following reacting by heating of tower temperature:
Gas (the NH that decomposites
3+ CO
2+ steam) import condenser by cat head, the liquid that contains ammonia of condensation is put into the ammonium tank, uses for the dense ammonium water of system.Condensed gas is made dense ammonium water through dense ammonium water preparation apparatus, removes to prepare carbon ammonium (recovery ammonia) for " carbon ammonium system ", or send monoammonium phosphate device.
4, calcium chloride preparation system by the emulsion that distillation column reaction is emitted, is that rich magnesium material send " magnesium salts preparation system " through press filtration, filter cake, for making the magnesium salts series product.Filtrate send the calcium liquid bath to stock, and squeezes into thickening equipment through pump, and the crystallization that will avale when reaching 140 ℃ gets reclaiming salt (NaCl) after filtration and send " prepared in saline system " for salt manufacturing water.The liquid that filters the back contains CaCl
2Nearly 40%, send again and endure the calcium device, greatly about 160 ℃ of its CaCl of following water evaporates
2Content will reach 〉=and 70%.Take out cooling, make Calcium dichloride dihydrate (CaCl
22H
2O) finished product.
5, magnesium salts preparation system: the rich magnesium filter cake that is come by " calcium chloride preparation system " adds water furnishing emulsion, sends into the magnesium salts carbonating tower, [is containing CO by feeding the pan gas that is come by " soda ash manufacturing system " under the tower under 25 ℃
2〉=85%(pressure is 6kgf/cm
2)], react about 30 minutes blowings.Through press filtration, filter cake is slag mud (lightweight CaCO
3) go to handle, abandon or other products of one-tenth to be processed; Filtrate is sent into the pyrolysis groove, is blown into steam, and temperature is controlled at 〉=carry out pyrolytic reaction under 90 ℃:
Magnesium basic carbonate avales after the pyrolysis, gets the filter cake of water content 70%-80% after filtration, and logical warm air drying in ℃ drying plant of temperature ≯ 230 gets the Magnesium Carbonate Light 41-45 finished product again.As further roasting again, controlled temperature gets light magnesium oxide (MgO) finished product at 850 ℃:
Hot filtrate mainly is a water, send " grey kiln system " to digest with system dolomite ash breast or milk of lime for dolomite ash or lime (CaO).
6, carbon ammonium system: the dense ammonium water that will be come by " Distallation systm " (contains ammonia 〉=180tt) squeeze into carbon ammonium carbonating tower through pump, will (contain CO by the grey kiln gas that " grey kiln system " comes again
235%) to be compressed to 8kgf/cm
2Send into carbon ammonium carbonating tower, generate the carbon crystalline ammonium at the bottom of the tower.Emit the brilliant liquid of part, separate brilliant liquid through whizzer.The crystalline carbon ammonium send " soda ash manufacturing system " for system soda ash, and carbon ammonium mother liquor send " Distallation systm " for the dense ammonium water of system.
7, grey kiln system: rhombspar (granularity φ 75-200n/m) and coal (hard coal granularity 25-50n/m) are sent into vertical ash furnace through elevating hopper, burn till dolomite ash for 1000 ℃ in the kiln temperature:
CaCO
3MgCO
3(rhombspar contains MgO about 21%) → CaOMgO(dolomite ash)+CO
2↑ dolomite ash is used in digestive shelf by " magnesium salts preparation system " next hot water (pyrolysis filtrate) digestion and is the dolomite ash breast:
The dolomite ash breast send " Distallation systm ".Kiln gas (CO is constantly drawn on the kiln top
235%), remove trifle in the world through water washing, compressed again machine is compressed to 8kgf/cm
2Pressure, be cooled to 30 ℃ of ∠ after, send " carbon ammonium system " to send into system carbon ammonium by carbon ammonium carbonating tower bottom.During calcined dolomite, also can use the anthracite calcining.
Claims (4)
1, a kind of process for combination producing of magnesium base is characterized in that it comprises prepared in saline system, soda ash manufacturing system, Distallation systm, calcium chloride preparation system, magnesium salts preparation system, carbon ammonium system and grey kiln system:
A. prepared in saline system: crude salt is removed magnesium, calcium ion: make refined brine, send " soda ash manufacturing system ";
B. soda ash manufacturing system: refined brine adds the carbon ammonium, and reaction is finished and filtered: filter cake calcining system soda ash, and pan gas send " magnesium salts preparation system ", and the alkali liquor of filtration send " Distallation systm ";
C. Distallation systm: by the alkali liquor that " soda ash manufacturing system " comes, dolomite ash breast reaction with being come by " grey kiln system " makes dense ammonium water for " carbon ammonium system ", and the emulsion of reaction is sent " calcium chloride preparation system ";
D. calcium chloride preparation system: the emulsion of emitting by " Distallation systm " reaction, " magnesium salts preparation system " sent in press filtration, filter cake, concentrating filter liquor, filtered and recycled regenerant salt, send " prepared in saline system ", the liquid that filters the back send the finished product of enduring calcium device system two water calcium oxide, Calcium Chloride Powder Anhydrous again;
E. magnesium salts preparation system: the rich magnesium filter cake that is come by " calcium chloride preparation system " adds water furnishing emulsion, send into the magnesium salts carbonating tower, the pan gas that feeding is come by " soda ash manufacturing system ", reaction back press filtration, filtrate pyrolysis after-filtration, filter cake leads to warm air drying, roasting system light magnesium oxide, and hot filtrate send " grey kiln system ";
F. carbon ammonium system: the dense ammonium water that will be come by " Distallation systm ", ash furnace kiln gas that " grey kiln system " comes be sent into carbon ammonium carbonating tower, generate the carbon crystalline ammonium at the bottom of the tower, separate brilliant liquid, and the crystalline carbon ammonium send " soda ash manufacturing system ", and carbon ammonium mother liquor send " Distallation systm ";
G. grey kiln system: rhombspar and coal are sent into ash furnace burn till dolomite ash, dolomite ash is used in digestive shelf by " magnesium salts preparation system " next hot water digestion and is the dolomite ash breast, and the dolomite ash breast send " Distallation systm ", and kiln gas (CO is drawn on the kiln top
2), remove trifle in the world through water washing, send " carbon ammonium system " after compression, the cooling.
2, production technique according to claim 1, its spy is that the pan gas that produces in " soda ash manufacturing system " is derived from calcining furnace, washes compressed again machine boil down to 6Kgf/cm with water through washing tower
2For " magnesium salts preparation system ".
3, production technique according to claim 1 and 2 is characterized in that the ash furnace kiln gas of sending into carbon ammonium carbonating tower will be compressed to 8kgf/cm in " carbon ammonium system "
2
4, production technique according to claim 1 and 2 is characterized in that when grey kiln system calcined dolomite, can use the anthracite calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93107143 CN1087063A (en) | 1993-06-23 | 1993-06-23 | Process for combination producing of magnesium base |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93107143 CN1087063A (en) | 1993-06-23 | 1993-06-23 | Process for combination producing of magnesium base |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1087063A true CN1087063A (en) | 1994-05-25 |
Family
ID=4986587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93107143 Pending CN1087063A (en) | 1993-06-23 | 1993-06-23 | Process for combination producing of magnesium base |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1087063A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011199A (en) * | 2012-12-27 | 2013-04-03 | 衡阳市海联盐卤化工有限公司 | Process for deamination and degasification of filtrated stock generated during alkali making |
| CN104229836A (en) * | 2014-09-12 | 2014-12-24 | 中国科学院过程工程研究所 | Acid-base co-production process and aid-base co-production system for preparing sodium carbonate and hydrochloric acid by utilizing sodium chloride |
| CN109279630A (en) * | 2018-11-28 | 2019-01-29 | 南京浦世环境科技发展有限公司 | The device and method of light magnesium carbonate is refined in a kind of magnesium carbonate product from carbon sequestration |
-
1993
- 1993-06-23 CN CN 93107143 patent/CN1087063A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011199A (en) * | 2012-12-27 | 2013-04-03 | 衡阳市海联盐卤化工有限公司 | Process for deamination and degasification of filtrated stock generated during alkali making |
| CN104229836A (en) * | 2014-09-12 | 2014-12-24 | 中国科学院过程工程研究所 | Acid-base co-production process and aid-base co-production system for preparing sodium carbonate and hydrochloric acid by utilizing sodium chloride |
| CN109279630A (en) * | 2018-11-28 | 2019-01-29 | 南京浦世环境科技发展有限公司 | The device and method of light magnesium carbonate is refined in a kind of magnesium carbonate product from carbon sequestration |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |