CN103172089A - Method for preparing sodium bicarbonate - Google Patents
Method for preparing sodium bicarbonate Download PDFInfo
- Publication number
- CN103172089A CN103172089A CN2012105856762A CN201210585676A CN103172089A CN 103172089 A CN103172089 A CN 103172089A CN 2012105856762 A CN2012105856762 A CN 2012105856762A CN 201210585676 A CN201210585676 A CN 201210585676A CN 103172089 A CN103172089 A CN 103172089A
- Authority
- CN
- China
- Prior art keywords
- sodium
- crystal
- stream
- sodium carbonate
- impurity
- 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
Images
Classifications
-
- 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
- C01D7/10—Preparation of bicarbonates from carbonates
-
- 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
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
-
- 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
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
- C01D7/126—Multi-step processes, e.g. from trona to soda ash
-
- 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
- C01D7/22—Purification
- C01D7/24—Crystallisation
Abstract
Provided is a method for preparing sodium bicarbonate out of a flow (A) containing sodium carbonate. The flow (A) containing sodium carbonate includes sodium carbonate and at least one impurity with concentration Ci and composed of alkali metal soluble salt. The method includes the steps of: a) mixing the flow (A) containing sodium carbonate and at least part of a flow (B) to generate a flow (C); b) bicarbonating a flow (C) by a gas (D) including CO2 to generate an aqueous suspension liquid (E), the aqueous suspension liquid (E) including crystals (F) which include sodium bicarbonate crystals; c) separating the aqueous suspension liquid (E) to obtain a crystal (F) including sodium bicarbonate crystals on one hand and obtain an aqueous mother liquid (G) on the other hand; d) removing bicarbonate out of at least part of the aqueous mother liquid (G) and moving part of water out of at least part of the aqueous mother liquid (G) to obtain at least one impurity flow (B) of alkali metal soluble salt with the concentration of Cf (B) and optional gas (H); e) circulating at least part of the flow (B) to the step a) to make a concentration rate Cf (B)/Ci (A) of at least one impurity of alkali metal soluble salt be at least 1.4, advantageously being at least 2 and more advantageously being 4 and better advantageously being 7; and f) removing a residuum (1) of the flow (B) or a residuum (J) of the mother liquid (G) to perform further processing.
Description
Technical field
The application requires the right of priority of the U.S. Provisional Application submitted on December 20th, 2011 number 61/578162, for all purposes are combined in this by reference with the full content of this application.
The present invention relates to a kind of for produce the method for sodium bicarbonate from the stream that contains sodium carbonate, this stream that contains sodium carbonate comprises sodium carbonate and at least a impurity that is comprised of the basic metal water-soluble salt, the method can reduce to produce the required final flushing dose of sodium bicarbonate simultaneously, and has reduced and the loss of cleaning relevant soda.
Background technology
Sodium bicarbonate (NaHCO
3) being a kind of soft basic cpd with widespread use, application comprises for human food prods, animal-feed, flue gas treatment and chemical industry.The global output of sodium bicarbonate in 2008 is counted roughly 2,800,000 tons.Its most of product source is from natural and carbonate synthesis sodium (Na
2CO
3).The sodium bicarbonate product is mainly by aqueous sodium carbonate and gas CO
2Carbonation make.This aqueous sodium carbonate can come from pure sodium carbonate soluble in water, perhaps come from the slurries from the part decarbonation of the thick sodium bicarbonate of Su Wei (Solvay) method, perhaps come from the sodium carbonate solution that obtains from the crystallize sodium carbonate device, wherein this crystallize sodium carbonate device is supplied with the solution that comes from urao or nahcolite ore.
When sodium bicarbonate was made by solid prepared calcium carbonate sodium, the content of sodium carbonate impurity such as basic metal water-soluble salt was very low, thereby this sodium bicarbonate method can be extracted those impurity effectively certainly, obtains the sodium bicarbonate of final production.Therefore, in the sodium bicarbonate method of correspondence, do not need the specific cleaning to those impurity.
Yet, when sodium bicarbonate is made by the sodium carbonate stream of synthetic SODA ASH LIGHT 99.2 (Su Wei or derivative Hou's process for soda production) or natural soda ash (urao or nahcolite methods involving), these sodium carbonate streams comprise high-caliber soluble impurity, thereby in this sodium bicarbonate method, need to clean to control the level of impurity.In the sodium carbonate method of correspondence, this scavenging solution is usually more and be returned or be sent to large capacity sedimentation basin, the method described in US7507388 or US2009/0291038 or US2011/112298.
Except sodium bicarbonate, sodium carbonate also referred to as SODA ASH LIGHT 99.2, is a kind of a large amount of bases commodity, and whole world ultimate production was 4,800 ten thousand tons in 2008, and sodium carbonate is mainly used in glass, chemical preparations, detergent industry and sodium bicarbonate manufacture.The main method of sodium carbonate production is the Su Wei ammonia synthesis, be derived from the ammonium chloride method of Su Weifa (Hou's process for soda production) and based on the method for urao.
Trona ore is to comprise approximately 99% concentrated crystal soda (Na
2CO
3.NaHCO
3.2H
2O) a kind of mineral.By descending traditionally production technique, exploit or lake water is processed by solution, obtain the SODA ASH LIGHT 99.2 based on urao from the trona ore mineral deposit of green river (Wyoming State), Turkey, China and Kenya.The sodium carbonate based on urao from the Wyoming State has comprised about 90% of whole U.S. SODA ASH LIGHT 99.2 output.
As follows to the canonical analysis in the trona ore of green river exploitation:
Table 1
Native soda deposit comprises multiple highly soluble impurity, as alkali metal halide (sodium-chlor, Repone K, Sodium Fluoride, ...), alkali metal sulfates (sodium sulfate, vitriolate of tartar, ...), base metal nitrate (SODIUMNITRATE, saltpetre ...), alkali metal borate, alkali metal phosphate etc.According to the geographical position in mineral deposit, these highly soluble impurity ratios are different.Especially, according to the geographical position, sodium-chlor and sodium sulfate can account for percentum or tens percent of urao.
Native soda deposit also comprises microsolubility mineral or organic impurity.The example of microsolubility mineral is: alkali and alkaline earth metal ions silicate, aluminate, titanate, vanadate, metallic compound and salt.Organic impurity comes from organic sediments, and wherein this organic sediments is being hunted down during the formation in mineral deposit and often forms resinous shale between the geology aging time.When process urao in mine during or surface operates, also can partly produce mineral and organic soluble impurity.Especially, thermal treatment is as calcining common amount of amplifying the part soluble impurity, as water glass, and the sodium salt of the organic compound by hot saponification.
In urao or near other " insoluble " of finding native soda deposit or the atomic water-soluble dirt mixture that is generally different minerals, modal is calcite, rhombspar, pirssonite, zeolite, feldspar, clay mineral, ferric metasilicate/pure aluminium silicate and calcium sulfate.
In the art, known two kinds of major techniques are used for reclaiming trona ore from the trona ore mineral deposit.The first technology is machine instruction statement mining, also referred to as the tradition exploitation, as room and pillar mining (room and pillar panel operation) or broadwall.The second technology is that the solution exploitation is reclaimed, and wherein uses water dissolution urao and is recovered as solution.
In the variety of way that reclaims sodium carbonate from the trona ore that comprises other salt and impurity, widespread use be so-called " monohydrate sodium carbonate method ".In the method, the trona ore of exploitation is pulverized, then the trona ore of pulverizing is sintered into black ash, then make the water leaching, with the purifying aqueous solutions of generation and for to crystallizer, in this crystallizer, pure crystal carbonate crystal structure.These monohydrate crystals are isolated from its mother liquor and subsequent drying becomes anhydrous sodium carbonate.Most of mother liquors are circulated in crystallizer.Yet the soluble impurity that comprises in trona ore tends to gather in crystallizer.For fear of the accumulation of impurity, mother liquor must be cleaned.This scavenging solution is sent in evaporation tank (also referred to as tailing pond) usually, and wherein this scavenging solution quantity is great for industrial monohydrate factory.Therefore, a large amount of alkali that comprises in this scavenging solution is lost.In addition, a large amount of scavenging solutions are stored in and have caused environmental problem in evaporation tank, and reason is the utilization ratio deficiency that new zone is used for storage.
The variant of producing sodium carbonate from trona ore is, when particularly using the solution exploitation:
After the water evaporation, then refining concentrated crystal soda crystallization is sintered into SODA ASH LIGHT 99.2 with concentrated crystal soda;
The sodium bicarbonate that perhaps thermolysis alternatively (use steam) or chemistry calcining (use caustic soda) are dissolved to be translated into the sodium carbonate of dissolving, is followed vaporize water, in order to the pure crystal carbonate of crystallization.
In these variants, the soluble impurity that comprises in trona ore also tends in sesquialter or hydrate crystallization device inner accumulated.For fear of the accumulation of impurity, also mother liquor must be cleaned, this has increased the environmental problem in the evaporation tank identical with the monohydrate sodium carbonate method.
Several alternate embodiments have been proposed to reduce the cleaning liquid measure of SODA ASH LIGHT 99.2 factory.
US2003/0143149 discloses a kind of for utilizing the sal soda crystallizer from sodium carbonate stream as scavenging solution and the waste streams recovery method based on the chemical of sodium, wherein, reclaim the decahydrate of purifying and it is circulated to the hydrate crystallization device, removing the scavenging solution that is rich in as impurity such as sodium sulfate.It is limited that but the scavenging solution of the method reduces coefficient, because when reaching high concentration impurities, sodium carbonate and sodium sulfate form ten hydration mixing salts.And if sodium sulfate is recycled a hydrated carbonate crystallizer in a large number, can produce burkeite crystal (Na
2CO
3.2Na
2SO
4), thereby unfavorable to the crystal carbonate quality.
US2004/0057892 discloses the production method of a kind of sodium carbonate and sodium bicarbonate, according to the method, to cause from the scavenging solution of crystal carbonate crystallizer in the sal soda crystallizer, and purified decahydrate crystal will be converted into sodium bicarbonate.Observe, when comprising high-caliber impurity, this method is invalid when this scavenging solution (depending on this urao raw material).In this scavenging solution, high-caliber sodium-chlor has stoped the steady crystallization of decahydrate.
US2926995 discloses a kind of method of producing sodium bicarbonate crystal from sodium carbonate solution, and wherein this sodium carbonate solution comprises the sodium-chlor that comes from caustic soda-chlorine electrolyzer.
US7507388 discloses a kind of method of producing sodium carbonate and sodium bicarbonate from the prepurification solution that comprises supercarbonate, at first carries out the part decarbonate and then is used for sodium bicarbonate production line and crystal carbonate production line.The purge flow of crystal carbonate crystallizer is delivered to sal soda and the concentrated crystal soda production line of mixing, wherein the last cleaning along with the method will abandon the filtrate that produces, perhaps after dilution, it is delivered to the Soda ash light production line, it comprises the carbonation step of the centre of sodium bicarbonate, supercarbonate is separated with filtrate, and this filtrate is also processed as final scavenging solution.The scavenging solution total amount that produces very large (dense soda ash per ton produces the 1.28t scavenging solution) and produce the sodium carbonate of the cleaning of 6 to 15 weight percents corresponding to resulting dense soda ash per ton.
US2009/0291038 (Su Wei) discloses the combine production method of a kind of sodium carbonate and sodium bicarbonate crystal, according to the method, the pressed powder that will stem from concentrated crystal soda is dissolved in water as the urao of calcining, obtained aqueous solution is caused in crystallizer, wherein produce crystals of sodium carbonate and mother liquor, partial mother liquid is taken out (cleaning of crystallize sodium carbonate device) and carbonization (carbonatization) to generate valuable sodium bicarbonate crystal and the second mother liquor from crystallizer, this randomly decarburization of the second mother liquor (decarbonate hydrogen salt) is also then delivered to storage pool with it.In this patent, taught the sodium-chlor that the mother liquor that is used for the sodium bicarbonate crystallization should comprise preferred 175g/kg sodium carbonate at least and be no more than 60g/kg, and the sodium sulfate that is no more than 20g/kg.Therefore, process with respect to the decahydrate of scavenging solution, reduced the scavenging solution level of the soda (carbonate or supercarbonate) of delivering to the pond, but it is still great and account for and deliver to the relatively large of pond.In addition, the final scavenging solution that is rich in sodium bicarbonate forms solid in evaporation tank, this solid is hard and be not easy to collect and be circulated to SODA ASH LIGHT 99.2 factory, because this solid comprises the less sal soda crystal that is easy to melt and more nonfused hard concentrated crystal soda and sodium bicarbonate crystal.
US2011/112298 discloses a kind of for the prolonging tailing method in pond life-span, this tailing pond is produced by the purge flow that comprises sodium carbonate, wherein similar with the US2009/0291038 method, before being introduced into this pond, use gaseous carbon dioxide to process purge flow, in order to produce sodium bicarbonate or concentrated crystal soda.Before handled purge flow was introduced into tailing pond, the recyclable sodium bicarbonate that produces perhaps reclaimed after it is deposited in this pond.The not mentioned gained rinse water of further rising in value when reclaiming sodium bicarbonate of this document.In addition, as the method for describing in US2009/0291038, the final scavenging solution that is rich in sodium bicarbonate forms solid in this evaporation tank, this solid is hard and be not easy to collect and be circulated to SODA ASH LIGHT 99.2 factory, because this solid comprises the less sal soda crystal that is easy to melt and more nonfused hard concentrated crystal soda and sodium bicarbonate crystal.
Therefore, consider Sustainable development, still need sodium bicarbonate and sodium carbonate industry can further reduce flushing dose, and reduce alkali loss in the mode of the working conditions that simply and not hinders methods involving.
Summary of the invention
Therefore, the present invention relates to a kind ofly for produce the method for sodium bicarbonate from the stream (A) that contains sodium carbonate, this stream (A) that contains sodium carbonate comprises sodium carbonate and at least a concentration is C
i(A), by the impurity that the basic metal water-soluble salt forms, the method includes the steps of:
The stream (A) that a) will contain sodium carbonate mixes to produce a stream (C) with at least a portion of stream (B),
B) use comprises CO
2Gas (D) come this stream of hydrogen-carbonate salinization (C), in order to produce waterborne suspension (E), this waterborne suspension (E) comprises crystal (F), this crystal (F) comprises sodium bicarbonate crystal,
C) separate this waterborne suspension (E), obtain comprising the crystal (F) of sodium bicarbonate crystal in order to one side, and obtain on the other hand aqueous mother liquor (G),
D) with at least a portion of aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water at least a portion of mother liquor (G), obtaining having concentration is C
fThe stream (B) of at least a impurity of basic metal water-soluble salt (B) and optional gas (H),
At least a portion that e) will flow (B) is circulated to step a), makes the ratio C of concentration of at least a impurity of basic metal water-soluble salt
f(B)/C
i(A) at least: 1.4, preferably at least 2, more preferably at least 4, and also more preferably 7, and
F) remove the residuum (J) of the residuum (I) of this stream (B) or this mother liquor (G) to be further processed.
First advantage of the present invention is that the present invention has greatly reduced the alkali loss amount in the scavenging solution of sodium bicarbonate process or sodium carbonate process with steady and cheap way, this is due to carbonatization step b) and part decarbonate hydrogen salt step b) and circulation step c) synergy, especially under a large amount of sodium-chlor or sodium sulfate exist.
Second advantage of the present invention be its for soluble impurity on a large scale and on a large scale impurity concentration be effective.
In conjunction with second advantage, the 3rd advantage of method of the present invention is that it can use from carbonate synthesis sodium method or from the sodium carbonate of natron method stream.
The 4th advantage of the present invention is that water-soluble impurity that resulting technical grade sodium bicarbonate comprises is less than the water-soluble impurity concentration that the sodium carbonate that produces will have under condition of equivalent.
In conjunction with second advantage, the 5th advantage of the present invention is that it can exploit one or more native soda deposits with soluble impurity of different levels, can process the SODA ASH LIGHT 99.2 of different levels or the scavenging solution of sodium bicarbonate factory with same procedure of the present invention simultaneously.
The 6th advantage of the present invention is that it can deliver to the tailing pond that sodium bicarbonate content reduces with final scavenging solution (I), and be easy to reclaim and fusing, because it forms more soft ten crystallines and less hard sodium sesquicarbonate crystals, and if need, be easy to circulate in SODA ASH LIGHT 99.2 factory.
The 7th advantage of the present invention is that it can make purge flow minimum, prepares for dry blowing scavenging solution or very little evaporation tank or with the scavenging solution method of adopting cavity of reinjecting.
The 8th advantage of the present invention is that it can remove final scavenging solution from SODA ASH LIGHT 99.2 process or sodium bicarbonate process, soda content reduces and is rich in mineral salt such as sodium-chlor or sodium sulfate, and this mineral salt can derive from the ocean and capable of circulation go back to ocean after dilution at first.
The 9th advantage of the present invention is that it has reduced equipment size and corresponding investment, and reduced and be intended to remove or the processing cost of the further processing of the concentrated stream (I) (or stream (L) or stream (J)) of the concentrated impurity of increment or treating part.
The of the present invention ten advantage is that it can reduce the water loss that SODA ASH LIGHT 99.2 production and/or sodium bicarbonate are produced, and mode be that it is reclaimed water of condensation as vaporizer, exploits for the urao leaching that it is circulated to calcining or to trona solution.
The 11 advantage of the present invention is that it can increase the output of valuable technical grade sodium bicarbonate from the soda stream that comprises impurity.
The 12 advantage of the present invention is that resulting technical grade sodium bicarbonate is very suitable for the specific end use that reduces discharging as (even high impurity concentration) flue gas.
Description of drawings
Fig. 1: be the schema of exemplary illustration the inventive method.
Fig. 2: be the schema according to the method for the embodiment of the present invention.
The reference number of below quoting refers to appended figure.
Definition
With regard to purpose of the present invention, some term is intended to have following implication.
Term " cleaning " refers to the stream of extracting out from the part of method, in order to limit the impurity concentration in the method.
Term " impurity " refers to the compound different from the sodium carbonate that is about to produce and/or sodium bicarbonate.
Term " solvability " refers to the water-soluble of a kind of compound in a kind of aqueous solution or liquid.
Term " carbonatization " refers to the effect of total carbonate (carbonate and the supercarbonate) amount that increases stream.
Term " decarburization hydrochlorate " refers to the effect of total carbonate (carbonate and the supercarbonate) amount that reduces to flow.
Term " hydrogen-carbonate salinization " refers to the effect of the supercarbonate amount that increases stream.
Term " decarbonate hydrogen salt " refers to the effect of the supercarbonate amount that reduces to flow.
Embodiment
The present invention relates to a kind ofly for produce the method for sodium bicarbonate from the stream (A) that contains sodium carbonate, this stream (A) that contains sodium carbonate comprises sodium carbonate and at least a concentration is C
i(A) the impurity that is formed by the basic metal water-soluble salt, the method includes the steps of:
The stream (A) that a) will contain sodium carbonate mixes to produce a stream (C) with at least a portion of stream (B),
B) use comprises CO
2Gas (D) come this stream of hydrogen-carbonate salinization (C), in order to produce waterborne suspension (E), this waterborne suspension (E) comprises crystal (F), this crystal (F) comprises sodium bicarbonate crystal,
C) separate this waterborne suspension (E), obtain comprising the crystal (F) of sodium bicarbonate crystal in order to one side, and obtain on the other hand aqueous mother liquor (G),
D) with at least a portion of aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water at least a portion of mother liquor (G), obtaining having concentration is C
fThe stream (B) of at least a impurity of basic metal water-soluble salt (B) and optional gas (H),
At least a portion that e) will flow (B) is circulated to step a), makes the concentration ratio C of at least a impurity of basic metal water-soluble salt
f(B)/C
i(A) at least: 1.4, preferably at least 2, more preferably at least 4, and also more preferably 7, and
F) remove the residuum (J) of the residuum (I) of this stream (B) or this mother liquor (G) to be further processed.
In the present invention, at least a impurity that is comprised of the basic metal water-soluble salt is generally inorganic water-soluble salt, the group that it selects free Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, Repone K, S-WAT, sodium sulfate, vitriolate of tartar, sodium selenate, Sodium Nitrite, SODIUMNITRATE, clorox, Textone, sodium phosphate, sodium aluminate, Sodium Tetraborate, water glass, sodium titanate, vanadic acid sodium and combination thereof to form.Especially, at least a impurity of the basic metal water-soluble salt composition of the group of preferred free Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, Repone K, sodium sulfate, vitriolate of tartar, Sodium Nitrite, sodium phosphate, vanadic acid sodium and combination composition thereof.In fact, this type of impurity is preferably stayed in mother liquor (G) and by method of the present invention and is controlled its concentration.This basic metal water-soluble salt is preferably sodium or potassium water-soluble salt, more preferably sodium water-soluble salt.
In an embodiment of the invention, at least a impurity that is comprised of the basic metal water-soluble salt is sodium-chlor (NaCl).Especially, even use the high density chlorination sodium of tens gram NaCl in every kilogram of stream (B), it is effective that the method has also turned out to be.Preferably, the concentration C of sodium-chlor
f(B) be preferably 130g/kg at least, more preferably 150g/kg at least, also more preferably 170g/kg at least.The concentration C of sodium-chlor (NaCl)
f(B) usually mostly be most 300g/kg, preferred 260g/kg at most, more preferably 220g/kg at most, also more preferably 180g/kg at most.
In yet another embodiment of the present invention, at least a impurity that is comprised of the basic metal water-soluble salt is sodium sulfate (Na
2SO
4).In this case, the concentration C of sodium sulfate
f(B) be generally 20g/kg at least, preferred 40g/kg at least, more preferably 80g/kg at least, also more preferably 120g/kg at least.The concentration C of sodium sulfate
f(B) usually mostly be most 200g/kg, preferred 180g/kg at most, more preferably maximum 160g/kg.
This stream (A) also can comprise at least a other impurity, and this other impurity is selected from the group of the part water-soluble salt of aluminium (Al), silver (Ag), arsenic (As), bismuth (Bi), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), molybdenum (Mo), manganese (Mn), nickel (Ni), plumbous (Pb), antimony (Sb), tin (Sn), titanium (Ti), thallium (Tl), zinc (Zn), vanadium (V) and combination thereof.Advantageously, at least a other impurity is selected from the group of the part water-soluble salt of arsenic (As), molybdenum (Mo) and combination thereof.In fact, this type of impurity is preferably stayed in mother liquor (G) and by method of the present invention and is controlled its concentration.Above-mentioned corresponding element the concentration (by weight) of stream in (A) usually this element with respect to the 1ppb (part per billion part) of the weight of stream (A) to the scope of 1000ppm (1,000,000/portion).And this concentration is more common between 0.1 to 100ppm.The part water-soluble salt impurity of above-mentioned element is generally: the carbonate of respective element, or supercarbonate, or oxyhydroxide, or muriate, or vitriol, or nitrate, or phosphoric acid salt, or aluminate, or silicate.
When at least a other impurity was selected from the group of part water-soluble salt of aluminium (Al), boron (B), cobalt (Co), iron (Fe), manganese (Mn), zinc (Zn) and combination thereof, the crystal (F) of the main involved sodium bicarbonate crystal of this type of impurity was caught.In stream (A), the concentration level of this type of impurity is usually less than 200ppm.Therefore, the invention still further relates to a kind of method, wherein at step b) in remove this type of impurity and crystal (F) from stream (A), wherein this crystal (F) is at step c) in separate with aqueous mother liquor (G).
And the present invention's method required for protection also demonstrates, and the alkali-soluble salt that uses organic compound is also effectively, particularly uses the alkali-soluble salt of oil bearing rock organic (organic matter in resinous shale is also referred to as kerabitumen).When the oil bearing rock organic matter comprises single or two or during poly carboxylic acid, this organic solvability increases and can be from tens ppm (by weight) to several thousand ppm.Therefore, in an embodiment of present method, at least a impurity that is comprised of alkali-soluble salt is the organo-metallic soluble salt.Alcohol, ketone and aldehyde radical are conducive to form corresponding organic high resolution in the sodium carbonate current.
The stream (A) that contains sodium carbonate can be and anyly comprises sodium carbonate by the suspension of solid in solid, the aqueous solution or the stream that the aqueous solution forms, and is suitable for entering the sodium bicarbonate crystallizer.
In first variant of present method, the stream (A) that contains sodium carbonate partly or entirely is derived from the thick sodium bicarbonate that obtains from synthesizing SODA ASH LIGHT 99.2 method such as Su Wei ammonia process or Hou Shi ammonium chloride method.Advantageously, the stream (A) that contains sodium carbonate is the aqueous solution, and this aqueous solution partly or entirely is derived from the slurry of the part decarburization hydrochlorate of the thick sodium bicarbonate that obtains from synthetic SODA ASH LIGHT 99.2 method such as Su Wei ammonia process or Hou Shi ammonium chloride method.
In the second variant of the present invention, the stream (A) that contains sodium carbonate partly or entirely is derived from urao or nahcolite.Preferably, the stream (A) that contains sodium carbonate partly or entirely is derived from urao.In the present invention, usually exploit processing urao by tradition.Advantageously, also can exploit this urao of processing by solution.In fact, when exploiting processing urao by solution, can increase the basic metal water-soluble salt, because water infiltrates into the contiguous ore bed that may comprise water-soluble mineral.Usually, these water-soluble mineral comprise, especially, and alkali metal halide (fluorochemical, muriate, bromide, iodide), vitriol, borate, phosphoric acid salt, aluminate, silicate, titanate, vanadate water-soluble salt.This makes the present invention be specially adapted to manufacture level sodium bicarbonate from exploit the urao of processing by solution.
The stream (A) that contains sodium carbonate also can partly or entirely be derived from the tailing pond solid that comprises sodium carbonate.If the tailing pond solid of considering is rich in silicate and organic matter, this will be advantageous particularly, because at step b) in the sodium bicarbonate crystal that forms will capture most of silica and the part organic matter that exists in this stream (C), thereby improved the mobility of crystal (F).
In the preferred embodiment of first or second variant of present method, the stream (A) that contains sodium carbonate is the aqueous solution that comprises sodium carbonate (A ').
Of the present invention first or the embodiment of the second variant in, should flow (A) and shift out from the crystallize sodium carbonate device.In the present invention, this crystallize sodium carbonate device refers to a kind of in wherein generating the crystallizer of the crystal that comprises sodium carbonate.This crystallize sodium carbonate device selects free crystallize anhydrous device, crystal carbonate crystallizer, seven hydrated sodium carbonate crystallizers, sal soda crystallizer, concentrated crystal soda crystallizer, wegscheiderite (Na
2CO
3.3NaHCO
3, also referred to as decemite) and the group that forms of crystallizer and combination thereof.Advantageously, this stream (A) is the aqueous solution that shifts out (A ') from the crystallize sodium carbonate device.More advantageously, this aqueous solution (A ') is the scavenging solution from the crystal carbonate crystallizer.
therefore, the invention still further relates to the method for the combination producing of a kind of sodium carbonate and sodium bicarbonate crystal, the method comprises: in first step, the sodium carbonate solution of at least a impurity that will comprise sodium carbonate and be comprised of the basic metal water-soluble salt is introduced in the crystallize sodium carbonate device, thereby produce the first waterborne suspension that comprises crystals of sodium carbonate, this first waterborne suspension is separated, in order to obtain on the one hand the value-added crystal that comprises sodium carbonate, and obtain on the other hand mother liquor, partial mother liquid is shifted out this crystallize sodium carbonate device contain the stream (A) of sodium carbonate with formation, this stream will be further processed according to the method for the production of the sodium bicarbonate of present method.
In above-mentioned embodiment of the present invention, this crystallize sodium carbonate device advantageously is supplied with and comprises sodium carbonate and concentration is C
0The sodium carbonate solution of at least a impurity that is formed by the basic metal water-soluble salt, and the concentration ratio C of this at least a impurity
f(B)/C
0Be at least 14, preferably at least 30, more preferably at least 60, and also more preferably at least 120.
In the present invention, this crystallize sodium carbonate device also can be container or evaporation tank, in wherein forming the crystal that comprises the sodium carbonate compound.
In the embodiment of second variant of present method, the aqueous solution (A ') is scavenging solution and the combination that is derived from the tailing pond solid of crystallize sodium carbonate device scavenging solution from the crystal carbonate crystallizer.
In another embodiment of second variant of present method, method of the present invention is combined with the method described in WO2011/138005A1 (Su Wei), incorporate into by reference at this.In this case, method of the present invention further comprises:
The residuum (I) that k) will flow (B) is deposited in tailing pond, and be wherein the solid material that comprises sal soda with the residue of the part in tailing pond crystallize sodium carbonate, and wherein form concentrated solution (Q), this concentrated solution (Q) comprises and selects free silicate, sodium-chlor, sodium sulfate, organism and the impurity of the group that forms of both or many persons' combination wherein
L) alternatively described solid material is contacted with leaching vat, in order to will optionally being dissolved in leaching vat from least a portion of the first impurity in the material of contact, to form leaching vat and leaching residue, collect the leaching residue, at least a portion of leaching residue is dissolved in aqueous medium to form liquid; Carry out alternatively second impurity and remove step, this step comprises carries out magnesium and processes to form treatment solution, described pack processing is contained in the leaching residue and adds magnesium compound between breaking-in period or add magnesium compound after leaching residue dissolving that extremely described liquid or its part have the water-fast material of at least a portion the second impurity with formation, then with described treatment solution by at least one separating unit removing water-fast material, thereby obtain the solution of purifying;
M) provide the raw material of the method for the solution of described solid material or described liquid or described purifying comprises sodium carbonate, sodium bicarbonate, sodium sulfate or other derivatives as production crystalline product.
The residuum (I) of stream (B) or part (L) (such as in the embodiment of Fig. 2 definition) or the part (J) of this mother liquor (G) be rich in soluble salt, and other impurity is present in the stream (A) that contains sodium carbonate.Therefore, in another variant of the present invention, the method further comprises following steps:
N) dispose solution exploitation chamber adopt cavity or deep well injection in residuum (I) or the part (J) of mother liquor (G) or the part (L) of liquid (K) of stream (B), perhaps
O) circulate soln exploitation chamber or residuum (I) or the part (J) of mother liquor (G) or the part (L) of liquid (K) of adopting the stream (B) in cavity, and exploit the chamber or reclaim aqueous sodium carbonate from adopt cavity from solution, the aqueous sodium carbonate that wherein reclaims comprises sodium-chlor and/or sodium sulfate, and the concentration of its sodium-chlor and/or sodium sulfate is less than the sodium chloride concentration in residuum (I) or part (J) or part (L) and/or the concentration of sodium sulfate.
When the stream that contains sodium carbonate (A) partly or entirely is derived from urao or nahcolite, step n) or o) especially favourable, because it makes the soluble salt circulation in the ore that is present at first in chamber, ore deposit, ore deposit or deep-well.In addition, according to sodium bicarbonate content, can control the pH of final scavenging solution, because sodium bicarbonate is natural pH buffer reagent.Therefore, with respect to the amount of the raw ore that extracts from the chamber or from the ore deposit or from deep-well, the amount that circulates in this chamber or ore deposit or deep-well is greatly reduced.
Usually, the stream (A) that contains sodium carbonate comprises the sodium carbonate (representing with dried soluble salt) of at least 15% (weight).Advantageously, stream (A) comprises at least: 20% (weight), the more preferably sodium carbonate of 24% (weight) (representing with dried soluble salt).
This stream (A) advantageously is selected from the group from the circulation of sodium carbonate or concentrated crystal soda crystallizer and purge flow, mine current, evaporation tank bittern stream, water and sal soda mineral deposit, other wastewater streams and combination thereof.
Stream (A) comprises 98% (weight) at the most usually, and preferred 95% (weight) more has the sodium carbonate (representing with dried soluble salt) that selects 85% (weight).When the stream that contains sodium carbonate (A) for solid the suspension in the aqueous solution the or during aqueous solution, it comprises at the most usually: 99% (weight), preferred 90% (weight) more has the water that selects 80% (weight).This can limit sodium bicarbonate cycle number of the present invention.
If this sodium carbonate stream is derived from efflux of solids or for waterborne suspension or for being rich in the aqueous solution of sodium carbonate, water (N) can be added into the stream (A) that contains sodium carbonate, thereby stream (B) and stream (A) are in conjunction with forming feedstream (C), and this feedstream (C) is suitable for forming the crystal (F) that comprises sodium bicarbonate crystal when the hydrogen-carbonate salinization.Especially, control the amount of water (N), thereby the suspension density of crystal (F) in waterborne suspension (E) is controlled at 60w% at the most usually, preferred 50w% at the most, preferably 40w% at the most, more select 35w% at the most.In waterborne suspension, the suspension density of solid is that solid-phase is for the weight ratio of waterborne suspension.
In the present invention, stream (A) comprises at least 2% (by weight) usually, and preferred at least 3% (by weight) more has sodium-chlor and/or the sodium sulfate of choosing at least 4% (by weight).
Stream (A) can comprise high-caliber sodium-chlor and/or sodium sulfate.Preferably, in stream (A), the concentration of sodium-chlor and/or sodium sulfate should be restricted to maximum value, make corresponding at step c) mother liquor of the supercarbonate crystallizer that separates, stream (G) has (260g/kg) (200g/kg) concentration of sodium sulfate of sodium-chlor or 20% (by weight) of maximum 26% (by weight), thereby avoids the dissolving restriction of sodium-chlor in stream (G) and/or sodium sulfate.
In stream (A) comprised the situation of sodium-chlor and sodium sulfate, in stream (G), these two kinds of impurity concentrations were expressed as respectively [NaCl] (G) and [Na
2SO
4] (G) and with g/kg represent, answer these two kinds of impurity concentrations in preferred streams (G) according to following equation;
[NaCl](G)/1.3+[Na
2SO
4](G)≤200g/kg
And, when other high resolution salt of large concentration has the co-ion of sodium ion or chlorion or sulfate ion, when the accumulation sodium-chlor of the stream of at least 5% (by weight) (A) and sodium sulfate amount increase in proportion gradually, these impurity salt concentration should be added to the summation of the concentration of sodium-chlor and sodium sulfate, and afterwards stream (G) in this summation should remain on 20% (by weight) at the most.
In the present invention, stream (I) or (J) (or (L)) be used for to control hydrogen-carbonate salinization step b) during the basic metal water-soluble salt concentration of aqueous mother liquor (G), as sodium-chlor or sodium sulfate concentration.When stream (I) or (J) flow of (or (L)) increases, the concentration C of basic metal water-soluble salt in this cycle for the treatment of
i(G) reduce, and vice versa.Can regulate these flows, thereby set aqueous mother liquor (G) or stream (I) or (J) concentration of basic metal water-soluble salt in (or (L)) according to purpose, when the flow of corresponding stream (I) or the basic metal water-soluble salt that (J) is cleaned in (or (L)) equals start method, the basic metal water-soluble salt enters flow (as by (A), (A '), (A ") and (A " ')) has the basic metal water-soluble salt of crystal (F) when deducting ending method flow.
Usually, when stream (A) when being the rinse water of a crystalline hydrate device, the NaCl concentration of scavenging solution is at the most 5% and the Na of scavenging solution
2SO
4Concentration is 7% (representing with aqueous solution weight) at the most.In fact, traditional MVR (function of mechanical steam recompression) crystallizer can not in the situation that non-crystallizable anhydrous sodium carbonate move under 2%-3% in the NaCl level, thereby cause operation difficulty.According to a plurality of factors, triple effect one hydration evaporative crystallizer can move at low temperatures, and acceptable high concentration NaCl, up to 4%-5%.According to mould temperature (between 40 ℃ to 100 ℃), Na
2SO
4Concentration can cause burkeite crystal (Na greater than 3% to 7%
2CO
3.2Na
2SO
4) form.
The urao that typical natural soda ash factory uses has in liquid 28% to 30% Na
2CO
3Input concentration, about 0.2% NaCl input concentration and/or about Na of 0.05% to 0.2%
2SO
4Input concentration this means in the conventional plant of the prior art that comprises the crystallize sodium carbonate device and can move between 10 to 20 concentration multiples.This concentration multiple approaches usually: the ultimate density of soluble impurity and the ratio of input concentration.This will finally cause in natural soda ash factory the product loss, clean liquid measure and pond size, and dispose thing, and do not reclaim valuable alkali.The present invention can increase to from 10 to 20 times of concentration multiples up to 75 times delicately, even in simple mode.In addition, when sodium carbonate stream (A) is the scavenging solution of crystallize sodium carbonate device, because this scavenging solution usually be equivalent to enter the crystallize sodium carbonate device the sodium carbonate flow 2% to 15%, present method can limit energy expenditure and the associated cost relevant with total carbonic acid sodium output.
In the present invention, by any any means known in this area, can carry out steps d) the middle part decarbonate hydrogen salt of aqueous mother liquor (G) and removing of part water.Can carry out removing of part decarbonate hydrogen salt and part water in a step or multistep.Usually, calcine by chemistry and utilize caustic soda that the part of the sodium bicarbonate of solution (G) is converted into sodium carbonate to carry out the decarbonate hydrogen salt, perhaps utilize steam by the effect of hot decarbonate hydrogen salt or utilize boiler that a part of thermolysis of sodium bicarbonate is sodium carbonate, water and CO
2And carry out the decarbonate hydrogen salt.Preferably utilize the hot decarbonate hydrogen salt effect of steam or boiler.Can carry out the removing of part water of solution (G) in falling-film evaporator known in the art or boiler or pump feed evaporator or forced circulation evaporation crystallizer.
Fig. 1 (accompanying drawing 1) has illustrated method of the present invention.The stream (A) that contains sodium carbonate mixes to form stream (C) with the part of stream (B).In carbonatization device 1, use to comprise CO
2Gas (D) come this stream of hydrogen-carbonate salinization (C), comprise the waterborne suspension (E) of crystal (F) in order to generation, described crystal (F) comprises sodium bicarbonate crystal.Use tripping device 2 that suspension (E) is divided into the crystal (F) that comprises sodium bicarbonate crystal and is divided on the other hand aqueous mother liquor (G) on the one hand.In decarbonate hydrogen salt device 3, with aqueous mother liquor (G) part decarbonate hydrogen salt and remove part water, thereby obtain stream (B) and comprise CO
2Optional gas (H).Therefore, stream (B) is higher than the water-soluble salt content of stream (G).To flow at least a portion circulation of (B) to flow (C) with stream (A) in conjunction with forming.Remove the residuum (I) of stream (B) or remove the part (J) of aqueous mother liquor (G) from circulation loop, in order to be further processed.
Fig. 2 is the schema according to the method for embodiment of the present invention.In this embodiment, the removing of the stream decarbonate hydrogen salt effect of (G) and part water was divided into for two steps carries out, and optional water and CO
2Gas (H) circulation is with dotted lines.In this embodiment, the stream (A) that contains sodium carbonate mixes the aqueous solution (A ') that comprises sodium carbonate with formation with optional water (N), and then this aqueous solution (A ') mixes with generation with stream (B) and flows (C).In carbonatization device 1, use to comprise CO
2Gas (D) come this stream of hydrogen-carbonate salinization (C), comprise the waterborne suspension (E) of crystal (F) in order to generation, described crystal (F) comprises sodium bicarbonate crystal.Use tripping device 2 that suspension (E) is divided into the crystal (F) that comprises sodium bicarbonate crystal and is divided on the other hand aqueous mother liquor (G) on the one hand.In decarbonate hydrogen salt device 3, with this aqueous mother liquor (G) part decarbonate hydrogen salt, exhaust or the mother liquor (K) of poor sodium bicarbonate and the steam (H) that comprises carbonic acid gas in order to generation, and in vaporizer 4, mother liquor (K) part is evaporated to remove the water of at least a portion, thereby obtain stream (B) and water vapour (P).Stream (B) can be clear liquid or slurry.Randomly, partly or entirely water vapour (P) is capable of circulation to decarbonate hydrogen salt device and by direct or injection after vapor recompression, and perhaps along with the indirect heating of boiler, this part or all of water vapour (P) is capable of circulation to decarbonate hydrogen salt device.At least a portion of concentrated stream (B) is recycled to flow (C) with stream (A) in conjunction with forming.Remove the residuum (I) of stream (B), and/or remove the part (J) of aqueous mother liquor (G) from circulation loop, and/or from circulation loop the part of mother liquor (K), in order to be further processed.In hydrogen-carbonate salinization device 1, at hydrogen-carbonate salinization step b) during, these streams (I), (J), (K) are for controlling in aqueous mother liquor useful really by at least a impurity that basic metal water-soluble salt enriched material forms.
In the variant of this embodiment, mother liquor (K) part evaporation is being removed part water with the stream (B) that obtains to concentrate before, the stream (A ") that contains sodium carbonate can be added into and exhaust or the mother liquor (K) of poor sodium bicarbonate, wherein this stream (A ") that contains sodium carbonate can be the water as pit water, tailing pond water or dilution.This solubility limit for sodium carbonate in the device that avoids evaporating and/or basic metal water-soluble salt is favourable.
In another variant of this embodiment, if the stream (A " ') that contains sodium carbonate has sodium bicarbonate content or water-content and the sodium bicarbonate content that need to reduce before in being circulated to hydrogen-carbonate salinization device; the suitable point of introducing in the method this stream is when being introduced in the decarbonate hydrogen salt device 3 with aqueous mother liquor G, wherein this stream (A " ') that contains sodium carbonate can be the water as pit water, tailing pond water or dilution.
Randomly, in the embodiment shown in Figure 2, gas (H) can be with gas (D) in conjunction with flowing (C) partly to be used for the hydrogen-carbonate salinization.
In fact, gas (H) comprises the CO of high-content
2And all the other are mainly steam (water vapour), gas (H) is being caused stream (D) before, this gas can be in the situation that step b) in remove and reuse being with or without water condensation and water, thereby remove and flow automatically (A), (A '), (A "), (A " ') total water input are controlled water balance of the present invention together with the water of gravity flow (F), (I), (L), (J), (P).
In the method, at step b) in, gas (D) is for comprising at least 20 volume %, preferred 30 volume %, more having and select 40 volume %, the more preferably CO of 80 volume % also
2The gas of (representing with dry gas).
This hydrogen-carbonate salinization step b) can carry out at any temperature compatible with the known range of sodium bicarbonate.Preferably, at least 20 ℃, preferred 38 ℃, more preferably 55 ℃ and also more preferably carry out this hydrogen-carbonate salinization step at the temperature of 70 ℃.
When operating under the pressure higher than barometric point, too high temperature is unfavorable for CO
2Absorb.Therefore, hydrogen-carbonate salinization step b) usually at 100 ℃ at the most, preferred 90 ℃, more preferably 80 ℃ and also more preferably carry out at the temperature of 75 ℃.
In the present invention, at step b) in the crystal (F) that obtains comprise sodium bicarbonate crystal.Preferably, should control working point (mother liquid concentration of sodium bicarbonate, the mother liquid concentration of sodium carbonate and basic metal water-soluble salt such as NaCl and Na in the carbonatization step
2SO
4Mother liquid concentration), make in its sodium bicarbonate zone that remains on solubility curve.By provide enough CO in hydrogen-carbonate salinization device
2, making under working temperature, in hydrogen-carbonate salinization device mother liquor (G), concentration of sodium carbonate (is expressed as [Na less than the concentration of sodium carbonate of concentrated crystal soda dissolving
2CO
3] (sesquialter)) limit, and then realize above-mentioned purpose.
If [X] (G) represents NaCl's or Na
2SO
4If soluble salt concentration or have two kinds of salt represent NaCl and Na
2SO
4Concentration and (representing with g/kg), its realization between 20 ℃ to 80 ℃ usually, the concentration of sodium carbonate of mother liquor (G) (is expressed as [Na
2CO
3] (G)) less than lower value (representing with g/kg):
170-0.66[X](G)(g/kg)
Should take safety range, this value subtracts 5g/kg to make concentration of sodium carbonate be preferably at the most, and more preferably this value subtracts 10g/kg at the most, and most preferably at the most this value subtract 20g/kg.
This makes main crystalline sodium bicarbonate.If with corresponding crystal from being rich in NaCl and/or Na
2SO
4Its mother liquor (G) in separate, and when removing high-caliber saturated mother liquor and soluble salt such as NaCl or Na
2SO
4The time, if wash alternatively the gained crystal, the content that comprises the crystal (F) of sodium bicarbonate crystal is generally 40w% at least, or 50w% at least, preferred 60w% at least, more preferably 80w% at least, and the sodium bicarbonate of 90w% most preferably.Crystal (F) comprises 50w% at the most usually, or 30w% at the most, or 20w% at the most, preferred 10w% at the most, more preferably 5w% at the most, and the sodium carbonate of 3w% at the most most preferably.
The content of crystal (F) is generally 10w.% at the most in soluble salt (as sodium-chlor and/or sodium sulfate), preferred 4w.% at the most, more preferably 1w.% at the most.
According to the resulting end-use that comprises the crystal (F) of sodium bicarbonate crystal, method of the present invention can further comprise:
G) randomly wash the crystal (F) that comprises sodium bicarbonate, the crystal that comprises sodium bicarbonate after randomly washing with generation,
(h) dry this comprises crystal after the optionally washing of sodium bicarbonate.
Mode as an alternative can partly or entirely be calcined sodium bicarbonate rather than dried crystals only.
In this case, the method according to this invention further comprises following steps:
G) randomly wash sodium bicarbonate crystal, the crystal that comprises sodium bicarbonate after randomly washing with generation,
I) will comprise the crystal (F) of sodium bicarbonate crystal or randomly the crystal calcining that comprises sodium bicarbonate after washing for comprising the crystal of sodium carbonate.
When in step I) in partly or entirely during the calcining sodium bicarbonate crystal, can produce the gas (O) that comprises carbonic acid gas.Can all or part of recovery carbonic acid gas and water and it is circulated to the step of hydrogen-carbonate salinization.
Therefore, method of the present invention can further comprise step:
J) reclaim at least a portion of the gas (O) comprise carbonic acid gas and it is circulated to step b).
Example
Following instance only is intended to illustration the present invention and is not intended to limit scope of invention required for protection.
Example 1
Table 1 illustration the mass flow meter of embodiment of the described method of the present invention of Fig. 2, wherein the main soluble salt impurity of sodium carbonate stream (A) is sodium-chlor.
This example has shown that sodium carbonate stream (A) is the situation from the scavenging solution of crystallize sodium carbonate device: due to the circulation loop relevant with vaporizer with the decarbonate hydrogen salt device of present method, the mass rate of final scavenging solution (I) is 226kg/h, it is worth less than 1/4th of the value 1000kg/h of initial scavenging solution (A), and the loss of the sodium carbonate of final scavenging solution (I) is 27kg/h, with respect to the initial value of the 242kg/h of sodium carbonate in initial scavenging solution (A), quality has reduced approximate 9 times.
By contrast US2009/0291038 (Su Wei) and prior art, soda loss in the final scavenging solution of example 1 minimizing 60% of demonstration respective file, compare with it, this example reduces about 90%, and the example 1 of respective file reduces the mass rate of 10% initial clean liquid, compare with it, this example approximately reduces 77%.
Example 2
In this example, but the mass flow meter of the embodiment of the identical data explanatory view 2 described methods of the present invention of table 1, and wherein the main soluble salt impurity of sodium carbonate stream (A) is sodium sulfate (Na
2SO
4).In this case, sodium-chlor (NaCl) mass rate and sodium-chlor (NaCl) concentration should be interpreted as respectively Na
2SO
4Mass rate and Na
2SO
4Concentration but not mass rate and the concentration of NaCl.
Example 3 to 7 (E0 is to E6)
In this example, use equipment and the working conditions similar to the example 1 of US2009/0291038 (Su Wei), except in 3 liters of stirred reactors, under 70 ℃, use 100%vol to do the CO of concentration
2, carry out the hydrogen-carbonate salinization in batches, and make water make it saturated, keep 1 hour residence time.
Filter the gained crystal, make water and washing with alcohol, drying is 24 hours under envrionment temperature.
Table 2 has provided the analytical results of initial and final mother liquor, the analytical results of resulting crystal, the size-grade distribution of suspension density (solid weight is with respect to suspension weight) and gained crystal.
If description and the afoul degree of this explanation in any patent, patent application and publication that is combined in by reference this may make a term unclear to it, this disclosure should be preferential.
The working conditions of table 2-example 3 to 7 and chemistry and the physical analysis (respectively referring to E0, E2, E3, E6) of gained crystal.
Claims (20)
1. one kind is used for from the method for stream (A) the production sodium bicarbonate that contains sodium carbonate, and this stream (A) that contains sodium carbonate comprises sodium carbonate and at least a concentration is C
i(A) the impurity that is formed by the basic metal water-soluble salt, the method includes the steps of:
A) stream (A) that this is contained sodium carbonate mixes to produce stream (C) with at least a portion of stream (B),
B) use comprises CO
2Gas (D) come this stream of hydrogen-carbonate salinization (C), in order to produce waterborne suspension (E), this waterborne suspension (E) comprises crystal (F), described crystal (F) comprises sodium bicarbonate crystal,
C) separate this waterborne suspension (E), obtain comprising the crystal (F) of sodium bicarbonate crystal in order to one side, and obtain on the other hand aqueous mother liquor (G),
D) with at least a portion of this aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water in described at least a portion of this mother liquor (G), obtaining having concentration is C
fThe stream (B) of at least a impurity of basic metal water-soluble salt (B) and optional gas (H),
E) at least a portion with described stream (B) is circulated to described step a), makes the ratio C of concentration of at least a impurity of described basic metal water-soluble salt
f(B)/C
i(A) be at least 1.4, advantageously be at least 2, more advantageously be at least 4, and be more advantageously also 7, and
F) remove the residuum (J) of the residuum (I) of this stream (B) or this mother liquor (G) to be further processed.
2. the method for claim 1, at least a impurity that wherein is comprised of the basic metal water-soluble salt is inorganic water-soluble salt, and it is selected from Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, Repone K, S-WAT, sodium sulfate, vitriolate of tartar, sodium selenate, Sodium Nitrite, SODIUMNITRATE, clorox, Textone, sodium phosphate, sodium aluminate, Sodium Tetraborate, water glass, sodium titanate, vanadic acid sodium and combination thereof.
3. method as claimed in claim 2, wherein this basic metal water-soluble salt water-soluble salt that is sodium or potassium, be advantageously the water-soluble salt of sodium.
4. the method according to any one of the preceding claims, wherein this stream (A) also comprises at least a other impurity, this other impurity is selected from aluminium (Al), silver (Ag), arsenic (As), bismuth (Bi), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), molybdenum (Mo), manganese (Mn), nickel (Ni), plumbous (Pb), antimony (Sb), tin (Sn) titanium (Ti), thallium (Tl), zinc (Zn), the part water-soluble salt of vanadium (V) and combination thereof.
5. the method according to any one of the preceding claims, one of at least a impurity that wherein is comprised of the basic metal water-soluble salt is the organic alkali metal water-soluble salt.
6. the method according to any one of the preceding claims, one of at least a impurity that wherein is comprised of the basic metal water-soluble salt is sodium-chlor (NaCl).
7. method as claimed in claim 6, the concentration C f (B) of wherein said sodium-chlor (NaCl) is 130g/kg at least.
8. the method according to any one of the preceding claims, one of at least a impurity that wherein is comprised of described basic metal water-soluble salt is sodium sulfate Na
2SO
4
9. method as claimed in claim 8, wherein said sodium sulfate (Na
2SO
4) concentration C
f(B) be 20g/kg at least, advantageously be 40g/kg at least, more advantageously be 80g/kg at least to be preferably 120g/kg at least.
10. the method according to any one of the preceding claims, wherein described stream (A) is shifted out the group that this crystallize sodium carbonate device selects free crystallize anhydrous device, crystal carbonate crystallizer, seven hydrated sodium carbonate crystallizers, sal soda crystallizer, concentrated crystal soda crystallizer, wegscheiderite crystallizer and combination thereof to form from the crystallize sodium carbonate device; Advantageously, described crystallize sodium carbonate device is the crystal carbonate crystallizer.
11. method as claimed in claim 10, wherein said crystallize sodium carbonate device are supplied with and comprise sodium carbonate and concentration is C
0The sodium carbonate solution of at least a impurity that is formed by the basic metal water-soluble salt, and the ratio C of the concentration of described at least a impurity
f(B)/C
0Be at least 14, advantageously be at least 30, more advantageously be at least 60, and also more advantageously be at least 120.
12. the method according to any one of the preceding claims, this sodium carbonate in wherein said stream (A) partly or entirely be derived from the urao that reclaims by the exploitation of machine instruction statement mining or solution.
13. the method according to any one of the preceding claims, wherein said stream (A) partly or entirely be derived from the tailing pond solid that comprises sodium carbonate.
14. the method according to any one of the preceding claims, wherein said stream (A) is for comprising the aqueous solution of sodium carbonate, and advantageously described stream (A) is the scavenging solution from the crystal carbonate crystallizer.
15. the method according to any one of the preceding claims, wherein in described steps d) in, this optional gas (H) for comprise take dry gas represent be at least 20 volume %, advantageously as 30 volume %, more advantageously as 40 volume %, also more advantageously as the CO of 80 volume %
2Gas.
16. the method according to any one of the preceding claims, wherein at least 20 ℃, advantageously at least 38 ℃, more advantageously at least 55 ℃ and also more advantageously for carrying out described step b at the temperature of at least 70 ℃).
17. the method according to any one of the preceding claims, it further comprises:
G) randomly wash these crystal that comprises sodium bicarbonate crystal (F), the crystal that comprises sodium bicarbonate after randomly washing with generation,
(h) dry these comprise the crystal (F) of sodium bicarbonate crystal or the crystal after these randomly washings that comprises sodium bicarbonate.
18. the method according to any one of the preceding claims, it further comprises:
G) randomly wash these crystal that comprises sodium bicarbonate crystal (F), with generation comprise sodium bicarbonate randomly the washing after crystal,
I) these are comprised crystal calcining after the randomly washing that the crystal (F) of sodium bicarbonate crystal or these the comprise sodium bicarbonate crystal after for the calcining that comprises sodium carbonate.
19. the method according to any one of the preceding claims, it further comprises:
N) dispose solution exploitation chamber adopt cavity or deep well injection in residuum (I) or the part (J) of this mother liquor (G) or the part (L) of this liquid (K) of this stream (B), perhaps
O) circulate soln exploitation chamber or residuum (I) or the part (J) of described mother liquor (G) or the part (L) of described liquid (K) of adopting the described stream (B) in cavity, and exploit the chamber or reclaim aqueous sodium carbonate from adopt cavity from solution, the aqueous sodium carbonate that wherein reclaims comprises sodium-chlor and/or sodium sulfate, and the concentration of its described sodium-chlor and/or sodium sulfate is less than the sodium-chlor in described residuum (I) or described part (J) or described part (L) and/or the concentration of sodium sulfate.
20. the combine production method of a sodium carbonate and sodium bicarbonate crystal, the method comprises: in first step, the sodium carbonate solution of at least a impurity that will comprise sodium carbonate and be comprised of the basic metal water-soluble salt is introduced in the crystallize sodium carbonate device, thereby produce the first waterborne suspension that comprises crystals of sodium carbonate, this the first waterborne suspension is separated, to obtain on the one hand the value-added crystal that comprises sodium carbonate, and obtain on the other hand mother liquor, partial mother liquid is shifted out this crystallize sodium carbonate device to consist of the described stream (A) that contains sodium carbonate, the method of production sodium bicarbonate described according to any one in the claims is further processed described stream (A).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161578162P | 2011-12-20 | 2011-12-20 | |
| US61/578,162 | 2011-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172089A true CN103172089A (en) | 2013-06-26 |
| CN103172089B CN103172089B (en) | 2016-09-14 |
Family
ID=46319491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210585676.2A Expired - Fee Related CN103172089B (en) | 2011-12-20 | 2012-12-20 | For the method producing sodium bicarbonate |
Country Status (9)
| Country | Link |
|---|---|
| CN (1) | CN103172089B (en) |
| BE (1) | BE1021662B1 (en) |
| DE (1) | DE102012003485B3 (en) |
| ES (1) | ES2409083B2 (en) |
| FR (1) | FR2984299A1 (en) |
| IT (1) | ITMI20120352A1 (en) |
| NL (1) | NL2008354C2 (en) |
| PT (1) | PT106208B (en) |
| TR (1) | TR201202945A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698483A (en) * | 2017-01-19 | 2017-05-24 | 青海盐湖工业股份有限公司 | Method for producing molten salt-grade sodium nitrate |
| CN107758699A (en) * | 2017-10-23 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of sodium acid carbonate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647365A (en) * | 1970-01-06 | 1972-03-07 | Olin Corp | Coarse light sodium bicarbonate |
| CN1047839A (en) * | 1989-04-24 | 1990-12-19 | 索尔维公司 | sodium bicarbonate and crystallization method thereof |
| CN1270925A (en) * | 1999-04-19 | 2000-10-25 | 内蒙古伊克昭化工研究设计院 | Cold separation and carbonization process for preparing sodium carbonate from natural soda |
| US20030049192A1 (en) * | 2001-09-12 | 2003-03-13 | Braman Victor Eugene | Method for producing enhanced sodium carbonate crystals for making sodium bicarbonate |
| CN1849263A (en) * | 2004-08-24 | 2006-10-18 | 旭硝子株式会社 | Method for producing alkali metal hydrogencarbonate |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR7903330A (en) * | 1978-05-30 | 1979-12-11 | Stauffer Chemical Co | CARBONATING PROCESS FOR SODIUM BIOCARBONATE MANUFACTURE |
| JPS5560021A (en) * | 1978-10-27 | 1980-05-06 | Toyo Soda Mfg Co Ltd | Production of sodium bicarbonate |
| US5989505A (en) * | 1996-03-18 | 1999-11-23 | Solvay Minerals, Inc. | Method for recovery of alkali values from trona using air stripping |
| US7255841B2 (en) * | 2001-07-20 | 2007-08-14 | Church & Dwight Co., Inc. | Sodium bicarbonate production method |
| US20030017099A1 (en) * | 2001-07-20 | 2003-01-23 | Church & Dwight Co., Inc. | Sodium bicarbonate production method |
| US7611208B2 (en) * | 2004-08-17 | 2009-11-03 | Sesqui Mining, Llc | Methods for constructing underground borehole configurations and related solution mining methods |
| TR200403060A2 (en) * | 2004-11-11 | 2006-06-21 | Eti Soda Üretim Pazarlama Nakliyat ve Elektrik Üretim Sanayi ve Ticaret A. Ş. | Production of heavy soda, sodium bicarbonate, light soda and sodium silicate from bicarbonate containing solutions |
| EP2078697A1 (en) * | 2008-01-08 | 2009-07-15 | SOLVAY (Société Anonyme) | Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate |
| MX337503B (en) * | 2008-05-13 | 2016-03-03 | Solvay | Process for the joint production of sodium carbonate and sodium bicarbonate. |
| US20090291038A1 (en) * | 2008-05-23 | 2009-11-26 | Solvay (Societe Anonyme) | Process For The Joint Production of Sodium Carbonate and Sodium Bicarbonate |
| ES2503571T3 (en) * | 2010-05-04 | 2014-10-07 | Solvay Chemicals, Inc. | Removal of impurities from waste solids in the production of soda ash, sodium bicarbonate and / or other derivatives |
-
2012
- 2012-02-21 DE DE102012003485A patent/DE102012003485B3/en not_active Expired - Fee Related
- 2012-02-21 FR FR1251556A patent/FR2984299A1/en active Pending
- 2012-02-27 NL NL2008354A patent/NL2008354C2/en not_active IP Right Cessation
- 2012-03-05 ES ES201230331A patent/ES2409083B2/en not_active Expired - Fee Related
- 2012-03-07 IT IT000352A patent/ITMI20120352A1/en unknown
- 2012-03-14 PT PT106208A patent/PT106208B/en active IP Right Grant
- 2012-03-15 TR TR2012/02945A patent/TR201202945A1/en unknown
- 2012-05-31 BE BE2012/0368A patent/BE1021662B1/en not_active IP Right Cessation
- 2012-12-20 CN CN201210585676.2A patent/CN103172089B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647365A (en) * | 1970-01-06 | 1972-03-07 | Olin Corp | Coarse light sodium bicarbonate |
| CN1047839A (en) * | 1989-04-24 | 1990-12-19 | 索尔维公司 | sodium bicarbonate and crystallization method thereof |
| CN1270925A (en) * | 1999-04-19 | 2000-10-25 | 内蒙古伊克昭化工研究设计院 | Cold separation and carbonization process for preparing sodium carbonate from natural soda |
| US20030049192A1 (en) * | 2001-09-12 | 2003-03-13 | Braman Victor Eugene | Method for producing enhanced sodium carbonate crystals for making sodium bicarbonate |
| CN1849263A (en) * | 2004-08-24 | 2006-10-18 | 旭硝子株式会社 | Method for producing alkali metal hydrogencarbonate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698483A (en) * | 2017-01-19 | 2017-05-24 | 青海盐湖工业股份有限公司 | Method for producing molten salt-grade sodium nitrate |
| CN107758699A (en) * | 2017-10-23 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of sodium acid carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102012003485B3 (en) | 2013-06-20 |
| NL2008354C2 (en) | 2014-02-18 |
| PT106208A (en) | 2013-06-20 |
| ES2409083B2 (en) | 2013-12-26 |
| ES2409083A1 (en) | 2013-06-24 |
| FR2984299A1 (en) | 2013-06-21 |
| CN103172089B (en) | 2016-09-14 |
| TR201202945A1 (en) | 2013-08-22 |
| NL2008354A (en) | 2013-06-24 |
| ITMI20120352A1 (en) | 2013-06-21 |
| BE1021662B1 (en) | 2015-12-23 |
| PT106208B (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11396452B2 (en) | Method for preparing lithium concentrate from lithium-bearing natural brines and processing thereof into lithium chloride or lithium carbonate | |
| US9255011B2 (en) | Method for producing lithium carbonate | |
| CN1315730C (en) | Getting alkali from salt solution and calcining sesquicarbonate of soda | |
| US8865095B2 (en) | Process for producing sodium bicarbonate | |
| US11465907B2 (en) | Process for producing a concentrated aqueous sodium hydroxide solution | |
| CN109207716A (en) | A kind of bone coal adds calcium sodium roasting vanadium-extracting method | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN108101077A (en) | Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer | |
| CN103172090A (en) | Process for producing sodium bicarbonate | |
| CN107140660B (en) | A kind of preparation method of potassium carbonate | |
| CN103172089A (en) | Method for preparing sodium bicarbonate | |
| JP2020175344A (en) | Method for fixing carbon dioxide | |
| RU2780216C2 (en) | Method for producing bromide salts during comprehensive processing of polycomponent commercial bromide brines of petroleum and gas producing facilities (variants) | |
| Ulashevich et al. | PROBLEMS OF UTILIZATION OF DISTILLED SUSPENSION OF SODA PLANTS AND WAYS TO SOLVE THEM | |
| WO2023038541A1 (en) | Method of obtaining bromide salts | |
| CN105102759B (en) | Method for reclaiming soda value from the soda mineral deposit of underground | |
| ES2409084B2 (en) | PROCEDURE TO PRODUCE SODIUM BICARBONATE. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160914 Termination date: 20171220 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |