CN103172090A - Process for producing sodium bicarbonate - Google Patents
Process for producing sodium bicarbonate Download PDFInfo
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- CN103172090A CN103172090A CN2012105857021A CN201210585702A CN103172090A CN 103172090 A CN103172090 A CN 103172090A CN 2012105857021 A CN2012105857021 A CN 2012105857021A CN 201210585702 A CN201210585702 A CN 201210585702A CN 103172090 A CN103172090 A CN 103172090A
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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
- C01D7/10—Preparation of bicarbonates from carbonates
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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
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
- C01D7/126—Multi-step processes, e.g. from trona to soda ash
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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
- C01D7/22—Purification
- C01D7/24—Crystallisation
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Abstract
A process for producing sodium bicarbonate from a sodium carbonate bearing stream (A) of which a part is generated by a sodium carbonate crystallizer and comprises at least 2% parts of sodium chloride and/or sodium sulfate by weight, comprises the steps of: a) mixing the sodium carbonate bearing stream (A) with at least part of a stream (B) to produce a stream (C); b)bicarbonating the stream (C) with a gas (D) comprising CO2 to produce an aqueous suspension (E) comprising crystals (F), said crystals (F) comprising sodium bicarbonate crystals; c) separating the aqueous suspension (E) in order to obtain crystals (F) comprising sodium bicarbonate crystals on the one hand and an aqueous mother liquor (G) on the other hand; d) partly debicarbonating the aqueous mother liquor (G) and removing at least part of the water to obtain the stream (B) and an optional gas (H); e) recycling part of the stream (B) to step a); and f) removing the remainder of the stream (B) or a part of the liquor (G) to be further processed.
Description
Technical field
The application requires the right of priority of the U.S. Provisional Application submitted in 20.12.11 number 61/578160, for all purposes are combined in this by reference with the full content of this application.
The present invention relates to a kind of method is used for producing sodium bicarbonate from the stream that contains sodium carbonate, the final removing liquid measure that simultaneous minimization needs when producing sodium carbonate, and minimize the loss of the sodium carbonate relevant to such cleaning, the part of this stream produces by the crystallize sodium carbonate device, and such stream that contains sodium carbonate comprises sodium carbonate and a kind of water-soluble impurity.
Background technology
Sodium carbonate (Na
2CO
3) or SODA ASH LIGHT 99.2, be one of maximum alkalescence commodity of world wide manufacturing, it is 4,800 ten thousand tons the ultimate production of 2008.The main application of sodium carbonate is in glass, chemical, detergent industry, and in the sodium bicarbonate manufacture.The main method that is used for sodium carbonate production is Suo Weier (Solvay) ammonia synthesis, the ammonium chloride method, 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
| Component | Weight percent |
| Na 2CO 3 | 43.4 |
| NaHCO 3 | 34.4 |
| H 2O (crystallization and free moisture) | 15.4 |
| NaCl | 0.01 |
| Na 2SO 4 | 0.01 |
| Fe 2O 3 | 0.14 |
| Insolubles | 6.3 |
| Organism | 0.3 |
Native soda deposit comprises multiple high dissolubility 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 (roomand 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 removing liquid is sent in evaporation tank (also referred to as tailing pond) usually, wherein should remove liquid quantity for industrial monohydrate factory great.Therefore, a large amount of alkali that comprises in this removing liquid is lost.In addition, sweep off liquid and be stored in and caused environmental problem in evaporation tank, it is not enough that reason is that new zone is used for the utilization ratio that stores.
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.
Except sodium carbonate, sodium bicarbonate (NaHCO
3) be the basic prod that another kind has widespread adoption, these application comprise human food prods, animal-feed, flue gas treatment and chemical industry.Solid or the aqueous solution and the gaseous state CO of sodium carbonate are almost completely passed through in the production of sodium bicarbonate at present
2The carbonating manufacturing, these CO
2In SODA ASH LIGHT 99.2 factory produced in situ also or independent the purchase.
Several alternate embodiments have been proposed to reduce the removing liquid measure of SODA ASH LIGHT 99.2 factory.
US2003/0143149 has disclosed a kind of for reclaim the method for sodium base chemical from sodium carbonate stream (recirculation, cleaning and the waste streams that for example precipitate from crystallize sodium carbonate device, pit water, evaporation tank water and sal soda).Come partial destruction from the sodium bicarbonate of those streams by decarbonate, and the monohydrated sodium carbonate crystallizer is got back in the mainly charging of stream that generates, and the residuum of the stream of the decarburization that generates is fed to the Sodium carbonate decahydrate crystallizer, therefrom reclaim the decahydrate of purifying, and be recycled to the hydrate crystallization device, and dispose the removing liquid that is rich in impurity (for example sodium sulfate).It is limited that but the removing liquid 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 in the sal soda crystallizer from the removing liquid of crystal carbonate crystallizer, and purified decahydrate crystal is converted into sodium bicarbonate.Observe, when comprising high-caliber impurity, this method is invalid when this removing liquid (depending on this urao raw material).In this removing liquid, 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 the final liquid of removing.The removing liquid total amount that produces very large (dense soda ash per ton produces 1.28t and removes liquid) 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 that cleans, reduced the removing liquid 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.
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.
Yet, consider Sustainable development, still need sodium carbonate and sodium bicarbonate industry can further reduce flushing dose, and reduce alkali loss in the mode of the operational condition that simply and not hinders methods involving.
Summary of the invention
Therefore, the present invention relates to a kind of method of producing sodium bicarbonate from the stream (A) that contains sodium carbonate, the part of this stream is produced by the crystallize sodium carbonate device, the described stream (A) that contains sodium carbonate comprises sodium carbonate and by weight at least 2%, advantageously at least 3%, more advantageously at least 4% sodium-chlor and/or sodium sulfate, the method comprises the following steps:
The stream (A) that a) will contain 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), 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 with one side, and obtain on the other hand a kind of aqueous mother liquor (G),
D) with aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water, obtaining this stream (B) and optional gas (H),
At least a portion that e) will flow (B) is recycled to step a), and
F) remove the part (J) of the residuum (I) of this stream (B) or this aqueous mother liquor (G) to be further processed.
First advantage of the present invention is that it has greatly reduced alkali loss amount in evaporation tank (or tailing pond) 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 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 cleaning of sodium bicarbonate factory with same procedure of the present invention simultaneously.
The 4th advantage of the present invention is that it can reduce purge flow, for dry blowing clear liquid or the very little evaporation tank method of adopting cavity of maybe cleaning being reinjected is prepared.
The 5th advantage of the present invention is that it can reduce the water loss that SODA ASH LIGHT 99.2 production and/or sodium bicarbonate are produced, and it is reclaimed water of condensation as vaporizer, is used for it is circulated to the urao leaching of calcining or exploits to trona solution.
The 6th 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 7th 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.
The 8th advantage of the present invention is that resulting technical grade sodium bicarbonate is very suitable for the specific end use as the flue gas reduction of discharging of high impurity concentration.
Description of drawings
Fig. 1 is the schema of exemplary illustration the inventive method.
Fig. 2 is 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 regaining 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 obtain 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 of method of producing sodium bicarbonate from the stream (A) that contains sodium carbonate, the part of this stream is produced by the crystallize sodium carbonate device, the described stream (A) that contains sodium carbonate comprises sodium carbonate and by weight at least 2%, advantageously at least 3%, more advantageously at least 4% sodium-chlor and/or sodium sulfate, the method comprises the following steps:
The stream (A) that a) will contain 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), 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 with one side, and obtain on the other hand a kind of aqueous mother liquor (G),
D) with aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water, obtaining this stream (B) and optional gas (H),
At least a portion that e) will flow (B) is recycled to step a), and
F) remove the part (J) of the residuum (I) of this stream (B) or this aqueous mother liquor (G) to be further processed.
the invention still further relates to the method for the combination producing of a kind of sodium carbonate and sodium bicarbonate crystal, comprise: in first step, the sodium carbonate solution of at least a impurity that will comprise sodium carbonate and be comprised of sodium-chlor and/or sodium sulfate is introduced in a crystallize sodium carbonate device, thereby produce first waterborne suspension that comprises crystals of sodium carbonate, this the first waterborne suspension experience 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 contain the stream (A) of sodium carbonate with formation, the method according to this invention is further processed as with it crystal (F) that comprises sodium bicarbonate crystal.
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.The crystallize sodium carbonate device is selected from lower group, and this group is comprised of the following: crystallize anhydrous device, crystal carbonate crystallizer, seven hydrated sodium carbonate crystallizers, sal soda crystallizer, concentrated crystal soda crystallizer, (wegscheiderite is Na to the wegscheiderite crystallizer
2CO
3.3NaHCO
3And be called decemite) and their any combination.In the present invention, this crystallize sodium carbonate device also can be evaporation tank or tailing pond, in wherein forming the crystal that comprises the sodium carbonate compound.
Advantageously, the crystallize sodium carbonate device is monohydrated sodium carbonate crystallizer or concentrated crystal soda crystallizer.More advantageously, the crystallize sodium carbonate device is the monohydrated sodium carbonate crystallizer.
The stream (A) that contains sodium carbonate can be the suspension in the aqueous solution or comprise any stream that the aqueous solution of sodium carbonate is made by solid, solid, and is fit to be fed to the sodium bicarbonate crystallizer.
The stream (A) that contains sodium carbonate can be partially or even wholly derived from urao or nahcolite.Preferably, contain the stream (A) of sodium carbonate partially or even wholly derived from urao.In the present invention, general mining by routine processed urao.Advantageously, can also process urao by solution exploitation.
The stream (A) that contains sodium carbonate can also be partly or entirely derived from the tailing pond solid that comprises sodium carbonate.If the tailing pond solid of considering is rich in silicate, this can have special advantage so, because at step b) sodium bicarbonate crystal that forms will be caught most silicas of existence in stream (C), and this can improve the flowable of crystal (F).
In a preferred embodiment, the stream (A) that contains sodium carbonate is a kind of aqueous solution of comprising sodium carbonate (A ').In a preferred embodiment, and the aqueous solution (A ') be a kind of removing liquid from the crystallize sodium carbonate device.And in a most preferred embodiment, and the aqueous solution (A ') be a kind of removing liquid from the monohydrated sodium carbonate crystallizer.In a variant of this most preferred embodiment, and the aqueous solution (A ') be a kind of removing liquid from the monohydrated sodium carbonate crystallizer that is combined with the tailing pond solid, these tailing pond solids are removed liquid derived from the crystallize sodium carbonate device.
In another variant of this most preferred embodiment, method of the present invention is combined with the method described in WO2011/138005A1 (Su Wei chemistry), be combined in by reference this 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, be wherein the solid 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 the impurity of the group of selecting free silicate, sodium-chlor, sodium sulfate, organism and two or more combination compositions
L) described solid is contacted alternatively with leaching vat, in order to will optionally being dissolved in leaching vat from least a portion of the first impurity of contact substance, form leaching vat and leaching residue, collect the leaching residue, at least a portion of leaching residue is dissolved in water medium to form liquid; Carry out alternatively the 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; And
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, S-WAT or other derivatives as production crystalline product.
There are under water-soluble salt and other impurity condition the residuum (I) of concentrated this stream (B) or the part (J) of mother liquor (G) in containing the stream of sodium carbonate (A).Therefore, in another variant of the present invention, at least one during the method is further comprising the steps:
N) dispose solution exploitation chamber adopt cavity or deep well injection in the residuum (I) of stream (B) or the part (J) of mother liquor (G), 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 its sodium-chlor and/or sodium sulfate concentration are less than sodium chloride concentration and/or sodium sulfate concentration in residuum (I) or part (J) or part (L).
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 water-soluble salt recirculation in the ore that is present at first in chamber, ore deposit, ore deposit or deep-well.In addition, by sodium bicarbonate content, can control the pH of final removing liquid, 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 15% (weight).Represent with dried soluble salt, advantageously, stream (A) comprises at least 20, the sodium carbonate of more favourable at least 24 weight percents.
This stream (A) advantageously is selected from lower group, and this group is comprised of the following: 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 their any combination.
Represent with dried soluble salt, stream (A) generally includes at the most 98, and advantageously at the most 95, the sodium carbonate of 85 weight percents at the most more advantageously.When the stream that contains sodium carbonate (A) during for the suspension of solid in the aqueous solution or the aqueous solution, it generally includes at the most 99, and advantageously at the most 90, the water of 80 weight percents at the most more advantageously.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), 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) (200g/kg) concentration of sodium sulfate of sodium-chlor or 20% (by weight) of maximum 26% (by weight), thereby avoids reaching the water-soluble restriction of the middle sodium-chlor of 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 highly water-soluble 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 preferably remain on 20% (200g/kg) (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)) increased, in this cycle for the treatment of, the concentration C i of basic metal water-soluble salt (G) reduced, and vice versa.Can regulate these flows, thereby aqueous mother liquor (G) or stream (I) or (J) aimed concn of basic metal water-soluble salt in (or (L)), the beginning flow of basic metal water-soluble salt when the flow of corresponding stream (I) or the basic metal water-soluble salt that (J) is cleaned in (or (L)) equals start method (as by (A), (A '), (A ") and (A " ')) has the flow of the basic metal water-soluble salt of crystal (F) when deducting ending method.
Usually, when stream (A) when being the rinse water of a crystalline hydrate device, the NaCl concentration of cleaning be at the most 5% and the Na of cleaning
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%.At 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 the grey factory of typical natural soda uses has 28% to 30% Na by weight
2CO
3Liquid feeding 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.The cycle number of this concentration is usually near the ratio of ultimate density and the input concentration of water-soluble impurity.This will finally cause in natural soda ash factory the product loss, remove liquid measure and pond size, and dispose thing, and do not reclaim valuable alkali.The present invention can increase to from 10 to 20 circulations of concentration circulating number up to 75 circulations delicately in simple mode, and is even more.In addition, when sodium carbonate stream (A) is the removing liquid of crystallize sodium carbonate device, because this removing liquid usually be equivalent to enter the crystallize sodium carbonate device the sodium carbonate flow from 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 in steps d) use the method for the present invention of hot decarbonate hydrogen salt device.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).At least a portion recirculation of stream (B), with box lunch its with stream (A) in conjunction with the time form stream (C).Remove the residuum (I) of stream (B) or remove the part (J) of aqueous mother liquor (G) from loop (comprising device 1,2,3), 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 part of the stream decarbonate hydrogen salt effect of (G) and 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 can mix with optional water (N) aqueous solution (A ') that comprises sodium carbonate with formation, 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, that exhaust in order to generation or the mother liquor (K) of poor sodium bicarbonate and the steam (H) that comprises carbonic acid gas, in vaporizer 4, mother liquor (K) part is evaporated to remove part water, thereby obtain stream (B) and water vapour (P).Stream (B) can be clear liquid or slurry.Randomly, part or all water vapour (P) can be recycled to decarbonate hydrogen salt device 3 and directly or after vapor recompression be injected, and along with the indirect heating of boiler, this part or all of water vapour (P) can be recycled to decarbonate hydrogen salt device 3.When it, will flow at least a portion recirculation of (B) and flow (C) to form when (A) in conjunction with stream.From the residuum (I) of loop sucking-off stream (B), and/or from the loop part (J) of sucking-off aqueous mother liquor (G), and/or from the loop part (L) of sucking-off mother liquor (K), in order to be further processed.In hydrogen-carbonate salinization device 1, at hydrogen-carbonate salinization step b) during, useful really these streams (I), (J), (K) water-soluble salt concentration (for example sodium-chlor or sodium sulfate concentration) in controlling aqueous mother liquor.
In the variant of this embodiment,, the stream (A ") (for example water of one or more pit waters, tailing pond water or dilution) that contains sodium carbonate can be added into and exhaust or the mother liquor (K) of poor sodium bicarbonate obtaining stream (B) before in a part of its part being evaporated remove water.This allows advantageously to be avoided sodium carbonate and/or sodium-chlor or the water miscible solubility limits of sodium sulfate in vaporizer 4.
In another variant of this embodiment, if the stream (A " ') (for example one or more pit waters, tailing pond water or dilution water) that contains sodium carbonate has sodium bicarbonate content or water-content and sodium bicarbonate content before in being recycled to hydrogen-carbonate salinization device 1, introduce in the method this stream A " ' suitable point be when being introduced in the decarbonate hydrogen salt device 3 with aqueous mother liquor G.
Randomly, in the present invention, in steps d), produce optional gas (H), and the described gas of at least a portion (H) uses with gas (D) together with, be used for the hydrogen-carbonate salinization and be somebody's turn to do and flow (C).In the embodiment of showing in Fig. 2, at least a portion gas (H) is used to this stream of hydrogen-carbonate salinization (C) together with gas (D).In fact, gas (H) comprises the CO of high-content
2And the residuum of content is mainly steam (water vapour), causing stream (D) before, these steam can be in the situation that step b) in remove and reuse being with or without water condensation and water, thereby together with via remove to control the water balance of present method from this circulation sucking-off stream (I), (L), (J) and water (P).
In the method, at step b), gas (D) comprises the CO of at least 20, advantageously at least 30, more advantageously at least 40, even more advantageously at least 80 volume % for to represent with dry gas
2Gas.
This hydrogen-carbonate salinization step b) can carry out at any temperature compatible with the known range of sodium bicarbonate.Preferably, at least 20 ℃, advantageously 38 ℃, more advantageously at least 55 ℃, and this hydrogen-carbonate salinization step of operation b at the temperature of at least 70 ℃ even more advantageously).
When operating under the pressure higher than barometric point, too high temperature is unfavorable for CO
2Absorb.Therefore, generally at 100 ℃ at the most, advantageously at the most 90 ℃, more advantageously at the most 80 ℃, and this hydrogen-carbonate salinization step of operation b at the temperature of 75 ℃ at the most even more advantageously).
In the present invention, at step b) in the crystal (F) that obtains comprise sodium bicarbonate crystal.Advantageously, (mother liquid concentration of sodium bicarbonate, the mother liquid concentration of sodium carbonate and water-soluble salt are (for example as NaCl and Na should to control working point in the carbonatization step
2SO
4) mother liquid concentration), make in its sodium bicarbonate zone that remains on water-soluble figure.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 soluble salt concentration (representing with g/kg), as the concentration of NaCl, perhaps Na
2SO
4If concentration or have two kinds of salt represent NaCl and Na
2SO
4Concentration and, it realizes 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 thereby concentration of sodium carbonate is 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 allows mainly crystalline sodium bicarbonate.If then corresponding crystal (F) is rich in NaCl and/or Na from it
2SO
4Mother liquor (G) in separate, and when removing high-caliber saturated mother liquor and water-soluble salt (for example NaCl or Na
2SO
4) time, if randomly wash the gained crystal, comprise that the content of 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) generally includes 50w% at the most, 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 water-soluble salt (for example sodium-chlor and/or sodium sulfate), preferred 4w.% at the most, and more preferably 1w.% at the most,
Relate to the resulting end-use that comprises the crystal (F) of sodium bicarbonate, 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 crystal that comprises sodium bicarbonate after randomly washing.
Alternately, may partly or entirely calcine sodium bicarbonate rather than drying step h only) in crystal.
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, and
I) the crystal calcining that comprises sodium bicarbonate after randomly washing is the crystal that comprises 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 hydrogen-carbonate salinization step.
Therefore, method of the present invention can be further comprising the steps:
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 water-soluble salt impurity of sodium carbonate stream (A) is sodium-chlor.
This example is illustrated in the important meaning in following situation: wherein sodium carbonate stream (A) is the removing liquid from the crystallize sodium carbonate device; The final mass rate of removing liquid (I) is 226kg/h, such value representation is less than 1/4th of the value 1000kg/h that initially removes liquid (A), and the loss that comes the sodium carbonate of self-cleaning liquid (I) is 27kg/h, due to the recirculation loop relevant with vaporizer with the decarbonate hydrogen salt device of present method, compare with the initial value of the 242kg/h of sodium carbonate in initial removing liquid (A), such quality has reduced the factor of approximate 9 times.
By comparing, US2009/0291038 (Su Wei) shows in the example 1 and reduces soda loss in 60% final removing liquid, compare with it, this example reduces approximately 90%, and the example 1 of documents reduces the mass rate of 10% initial removing 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 water-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
4Those of concentration but not NaCl.
Example 3 to 7 (E0 is to E6)
In these examples, those similar equipment and working conditions of using in the example 1 of use and 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, and under room temperature dry 24 hours.
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. method of producing sodium bicarbonate from the stream (A) that contains sodium carbonate, the part of this stream is produced by the crystallize sodium carbonate device, the described stream (A) that contains sodium carbonate comprises sodium carbonate and by weight at least 2%, advantageously at least 3%, more advantageously at least 4% sodium-chlor and/or sodium sulfate, the method comprises the following steps:
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), 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 with one side, and obtain on the other hand aqueous mother liquor (G),
D) with this aqueous mother liquor (G) decarbonate hydrogen salt partly, and remove part water, obtaining this stream (B) and optional gas (H),
At least a portion that e) will flow (B) is recycled to step a), and
F) remove the part (J) of the residuum (I) of this stream (B) or this aqueous mother liquor (G) to be further processed.
2. the method for claim 1, wherein this crystallize sodium carbonate device is selected from lower group, and this group is comprised of the following: crystallize anhydrous device, crystal carbonate crystallizer, seven hydrated sodium carbonate crystallizers, sal soda crystallizer, concentrated crystal soda crystallizer, wegscheiderite crystallizer and their any combination; Advantageously, this crystallize sodium carbonate device is the crystal carbonate crystallizer.
3. according to the described method of any one in above claim, wherein from this sodium carbonate of stream (A) that contains sodium carbonate partially or even wholly derived from urao.
4. method as claimed in claim 3, wherein from this sodium carbonate of stream (A) that contains sodium carbonate partially or even wholly derived from the urao of processing by routine exploitation.
5. method according to claim 3, wherein from this sodium carbonate of stream (A) that contains sodium carbonate partially or even wholly derived from the urao of processing by solution exploitation.
6. according to the described method of any one in above claim, wherein this stream (A) that contains sodium carbonate partly or entirely is derived from the tailing pond solid that comprises sodium carbonate.
7. according to the described method of any one in above claim, wherein this stream (A) that contains sodium carbonate is the aqueous solution that comprises sodium carbonate (A ').
8. method as claimed in claim 7, wherein this aqueous solution (A ') is the removing liquid from the crystal carbonate crystallizer.
9. the method according to any one of the preceding claims, wherein in steps d) in, optional gas (H) for comprise at least 20 volume % that represent take dry gas, advantageously as 30 volume %, more advantageously as 40 volume %, also more advantageously be the CO of 80 volume %
2Gas.
10. according to the described method of any one in above claim, wherein in steps d) produce this optional gas (H), and at least a portion of wherein said gas (H) is used together with gas (D), and being used for the hydrogen-carbonate salinization should stream (C).
11. the method according to any one of the preceding claims, wherein at least 20 ℃, advantageously be at least 38 ℃, more advantageously be at least 55 ℃ and also more advantageously be at least at the temperature of 70 ℃ carry out step b).
12. the method according to any one of the preceding claims, described method further comprises:
G) randomly wash these crystal that comprises sodium bicarbonate (F), producing the randomly washed crystal that comprises sodium bicarbonate, and
H) dry these washed sodium bicarbonate crystals randomly.
13. the method according to any one of the preceding claims, described method further comprises:
G) randomly wash these crystal that comprises sodium bicarbonate crystal (F), producing the randomly washed crystal that comprises sodium bicarbonate, and
I) with these randomly the washed crystal calcining that comprises sodium bicarbonate for comprising the crystal of sodium carbonate.
14. method according to claim 13 is wherein at described calcining step i) in produce the gas (O) comprise carbonic acid gas, and wherein the method further comprises:
J) reclaim at least a portion of this gas that comprises carbonic acid gas (O), and be recirculated to step b).
15. according to the described method of any one in above claim, wherein in described steps d) in, make this aqueous mother liquor (G) decarbonate hydrogen salt in decarbonate hydrogen salt device, exhaust or the mother liquor (K) of poor sodium bicarbonate and comprise the steam (H) of carbonic acid gas with generation, and part is evaporated this and is exhausted or the mother liquor (K) of poor sodium bicarbonate therein, with remove portion water, thereby obtain this stream (B), randomly at described step b) in, this comprises at least a portion of the steam (H) of carbonic acid gas further to comprise recirculation.
16. method according to claim 15, it further is included in and this is exhausted or the evaporation of the mother liquor (K) of poor sodium bicarbonate part obtains with remove portion water before this stream (B), adds the stream that contains sodium carbonate (A ") to this mother liquor.
17. the method according to any one of the preceding claims, it further comprises:
K) residuum (I) of this stream of precipitation (B) in a tailing pond, wherein a part of crystallization of residue sodium carbonate is the solid material that comprises Sodium carbonate decahydrate in this tailing pond, and the concentrated solution (Q) that wherein forms comprises the impurity that selects in the group that free silicate, sodium-chlor, sodium sulfate, organic substance and two or more the combination in them form
L) randomly 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 described leaching residue is dissolved in aqueous medium to form liquid; Randomly carry out the step that removes of the second impurity, this step comprises carries out magnesium and processes to form treatment solution, described pack processing is contained in the leaching residue between breaking-in period, add magnesium compound or add this magnesium compound to described liquid or in the part of described liquid after the dissolving of leaching residue, the water-fast material that has at least a portion the second impurity with formation, then with described treatment solution by at least one separating unit to remove water-fast material, thereby obtain the solution of purifying, and
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, S-WAT or other derivatives as production crystalline product.
18. the described method of any one according to claim 1 to 17, 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).
19. the described method of any one according to claim 1 to 17, it further comprises:
O) circulate soln exploitation chamber or residuum (I) or the part (J) of this mother liquor (G) or the part (L) of this liquid (K) of adopting this 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 wherein the concentration of this sodium-chlor and/or sodium sulfate is less than sodium chloride concentration and/or sodium sulfate concentration in residuum (I) or part (J) or part (L).
20. the combine production method of a sodium carbonate and sodium bicarbonate crystal, the method comprises: in first step, the sodium carbonate solution that will comprise sodium carbonate and at least a impurity that is comprised of sodium-chlor and/or sodium sulfate 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, the part of this mother liquor is shifted out described crystallize sodium carbonate device contain the stream (A) of sodium carbonate with formation, the method of production sodium bicarbonate described according to any one in the claims is further processed this stream (A).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161578160P | 2011-12-20 | 2011-12-20 | |
| US61/578,160 | 2011-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103172090A true CN103172090A (en) | 2013-06-26 |
Family
ID=46319490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105857021A Pending CN103172090A (en) | 2011-12-20 | 2012-12-20 | Process for producing sodium bicarbonate |
Country Status (8)
| Country | Link |
|---|---|
| CN (1) | CN103172090A (en) |
| BE (1) | BE1023372B1 (en) |
| DE (1) | DE102012003487B3 (en) |
| FR (1) | FR2984298A1 (en) |
| IT (1) | ITMI20120351A1 (en) |
| NL (1) | NL2008357C2 (en) |
| PT (1) | PT106209B (en) |
| TR (1) | TR201202944A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108996526A (en) * | 2017-06-07 | 2018-12-14 | 中国科学院过程工程研究所 | A kind of preparation method of bulky grain heavy sodium bicarbonate |
| CN109790042A (en) * | 2016-09-30 | 2019-05-21 | 威立雅水务技术支持公司 | The method of silica is removed from sodium bicarbonate production waste water |
| CN111201199A (en) * | 2017-08-29 | 2020-05-26 | 赛德环境公司 | Method for value-added utilization of gaseous effluent produced by alcoholic fermentation |
| CN111908489A (en) * | 2020-08-25 | 2020-11-10 | 湖南省银桥科技有限公司 | Feed additive sodium bicarbonate system and process thereof |
| CN116199243A (en) * | 2022-12-12 | 2023-06-02 | 浙江津膜环境科技有限公司 | Salt separation method of high-salt mixture |
| CN118145738A (en) * | 2024-05-11 | 2024-06-07 | 山东海化集团有限公司 | Low-ammonia low-salt alkali filter washing water production process |
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| CN1849263A (en) * | 2004-08-24 | 2006-10-18 | 旭硝子株式会社 | Method for producing alkali metal hydrogencarbonate |
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| 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 |
| 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 |
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- 2012-02-21 FR FR1251555A patent/FR2984298A1/en not_active Withdrawn
- 2012-02-21 DE DE102012003487A patent/DE102012003487B3/en not_active Expired - Fee Related
- 2012-02-27 NL NL2008357A patent/NL2008357C2/en not_active IP Right Cessation
- 2012-03-07 IT IT000351A patent/ITMI20120351A1/en unknown
- 2012-03-14 PT PT106209A patent/PT106209B/en active IP Right Grant
- 2012-03-15 TR TR2012/02944A patent/TR201202944A2/en unknown
- 2012-05-31 BE BE2012/0367A patent/BE1023372B1/en not_active IP Right Cessation
- 2012-12-20 CN CN2012105857021A patent/CN103172090A/en active Pending
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| 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 |
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| CN109790042A (en) * | 2016-09-30 | 2019-05-21 | 威立雅水务技术支持公司 | The method of silica is removed from sodium bicarbonate production waste water |
| CN108996526A (en) * | 2017-06-07 | 2018-12-14 | 中国科学院过程工程研究所 | A kind of preparation method of bulky grain heavy sodium bicarbonate |
| CN111201199A (en) * | 2017-08-29 | 2020-05-26 | 赛德环境公司 | Method for value-added utilization of gaseous effluent produced by alcoholic fermentation |
| CN111201199B (en) * | 2017-08-29 | 2022-08-09 | 赛德环境公司 | Method for value-added utilization of gaseous effluent produced by alcoholic fermentation |
| CN111908489A (en) * | 2020-08-25 | 2020-11-10 | 湖南省银桥科技有限公司 | Feed additive sodium bicarbonate system and process thereof |
| CN116199243A (en) * | 2022-12-12 | 2023-06-02 | 浙江津膜环境科技有限公司 | Salt separation method of high-salt mixture |
| CN118145738A (en) * | 2024-05-11 | 2024-06-07 | 山东海化集团有限公司 | Low-ammonia low-salt alkali filter washing water production process |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2984298A1 (en) | 2013-06-21 |
| TR201202944A2 (en) | 2012-07-23 |
| PT106209A (en) | 2013-06-20 |
| NL2008357C2 (en) | 2014-02-18 |
| PT106209B (en) | 2013-12-20 |
| BE1023372B1 (en) | 2017-02-23 |
| ITMI20120351A1 (en) | 2013-06-21 |
| DE102012003487B3 (en) | 2013-06-20 |
| NL2008357A (en) | 2013-06-24 |
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