CN101119928A - Process to prepare chlorine-containing compounds - Google Patents
Process to prepare chlorine-containing compounds Download PDFInfo
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- CN101119928A CN101119928A CNA2006800049257A CN200680004925A CN101119928A CN 101119928 A CN101119928 A CN 101119928A CN A2006800049257 A CNA2006800049257 A CN A2006800049257A CN 200680004925 A CN200680004925 A CN 200680004925A CN 101119928 A CN101119928 A CN 101119928A
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Abstract
The present invention relates to process to prepare a chlorine-containing compound using an aqueous salt solution containing at least 100 g/l of sodium chloride and a contaminating amount of polyvalent cations comprising the steps of (i) preparing an aqueous salt solution containing at least 100 g/l of sodium chloride and at least 0.01 ppm of polyvalent cations by dissolving a sodium chloride source in water, (ii) adding an effective amount of at least one positive retention enhancing component to the aqueous solution, (iii) subsequently subjecting the solution to a nanofiltration step, thereby separating the solution into a retentate which is enriched for polyvalent cations and a permeate which is the purified aqueous salt solution, (iv) reacting the chloride anions in the permeate to a chlorine- containing compound by an electrolysis step, and (v) recycling at least part of the retentate to dissolution step (i).
Description
The present invention relates to a kind of by containing the method that the salt brine solution of the polyvalent cation of 100g/l sodium-chlor and impurity level at least prepares chlorine-containing compound.
In the salt brine solution that contains 100g/l sodium-chlor at least, there are multiple negatively charged ion and positively charged ion such as magnesium, calcium, strontium, iron and sulfate ion from natural source.The preparation method of salt and wherein salt be that these negatively charged ion and the cationic overwhelming majority remain to be removed among the preparation method of product of raw material.Up to now, usually can not on significance degree, from salt brine solution, remove polyvalent ion such as calcium, magnesium, strontium, iron and/or sulfate ion, unless by the following method: a large amount of soda ash and concentrated NaOH solution are added salt brine solution, solution is carried out multiple settling step, subsequently salt brine solution is carried out multiple evaporation step.So the purer salt of producing can sell and constitute the suitable feedstock of other method, and wherein main method is for producing chlorine-containing compound such as chlorine and sodium chlorate.For the production method of these chlorine-containing compounds, salt is dissolved in the water once more and make chlorion by oxidation step as generating chlorine-containing compound by the electrolysis process reaction.
The processing method of above-mentioned preparation chlorine-containing compound comprises many steps that require large-scale reactor and settling vessel, has therefore reduced economic attractiveness.Also need a large amount of chemical such as soda ash and undesirable etching reagent.In addition, described processing method requires to pollute not too serious salt brine solution as raw material, purifies to enough degree because be clear that the salt brine solution that uses described processing method can not will comprise a large amount of impurity.
In addition, if can from the salt brine solution that contains 100g/l sodium-chlor at least, remove polyvalent ion substantially, only then no longer require in order it to be dissolved in the water again with further processing and at first prepare exsiccant salt in later step.If also can remove polyvalent ion to a greater extent from the aqueous solution that contains 100g/l sodium-chlor at least, then this aqueous solution can have than inferior quality, can contain undesirable polyvalent ion of higher amount, but still keeps being suitable for producing chlorine-containing compound.
Therefore, need a kind of method for preparing chlorine-containing compound on the market, wherein will comprise at least the salt brine solution of 100g/l sodium-chlor, especially strong brine and purify to and therefrom remove polyvalent ion substantially, should can further react the generation chlorine-containing compound by purification solution subsequently.
US 5,858, and 240 disclose a kind of chlor-alkali method, wherein will comprise at least the salts solution of 50g/l sodium-chlor and therefrom remove undesirable ion by nano-filtration step and purify, and make its reaction obtain chlorine or sodium chlorate by electrolysis step subsequently.Yet the reservation of disclosed calcium and magnesium still need improve in the document.Especially illustrated as the embodiment of this reference, when the amount of sodium-chlor in the salt brine solution increases, the reservation of calcium significantly reduces, wherein when sodium chloride concentration is 139.6g/l calcium be left 56.3%, and when sodium chloride concentration increases to 288.7g/l, have only 12.3%.Therefore increase with salt concn, from salt brine solution, remove these and do not wish the ionic purification step trouble more that becomes, because when higher salt concentrations, significantly increase with the salts solution (undesirably) of purification calcium ion by nanofiltration membrane.
GB2,395,946 relate to a kind of wherein by described solution is carried out nano-filtration step and the method for purification seawater.Seawater delivered to sodium ion or chlorion compare the nanofiltration technique that sulfate ion has higher repulsion.Subsequently, the penetrant of nanofiltration technique is delivered to hot desalinating process to increase the sodium chloride concentration in the water.At last, in crystallizer, be settled out sodium-chlor.Gained retentate after the nano-filtration step can be drained into outlet, maybe it can be delivered to and be used for the technology that the mineral such as the component of magnesium, vitriol or calcium reclaim.Also mentioned and to have guaranteed that in nanofiltration technique enough low brine concentration is to prevent the precipitation of lime carbonate.GB 2,395, and 946 not openly concentrated sodium chloride materials flows promptly comprise the nanofiltration of the salt brine solution of 100g/l sodium-chlor at least.
US 4,176,022 described a kind of in the electrolyzer that anolyte compartment and catholyte compartment are separated electrolytic alkali metal chloride brinish method, this method comprises that (i) keeps the salt solution of calcium ions to be alkalescence, (ii) will be selected from following phosphorylation thing and add described base brine and form and have stoichiometric equation (CaX
2) (Ca (PO
4)
2)
3Insoluble precipitate: phosphoric acid, sodium orthophosphate, sodium-metaphosphate, sodium polyphosphate, Rapisol and composition thereof, X in its Chinese style is selected from F, Cl and OH, (iii) make throw out and salt water sepn, (iv) will contain in the anolyte compartment that salt solution less than the 20ppb calcium ion infeeds electrolyzer and (v) make electric current pass through electrolyzer.In a word, this reference discloses a kind of method of removing calcium from salt solution, wherein additive is added salt solution, and wherein additive forms insoluble stoichiometry title complex with the calcium ion that is present in wherein, subsequently by removing by filter throw out and abandoning.Therefore but this reference does not relate to the wherein method of additive recirculation, and this makes this method have less economic attractiveness.In addition, found to be disclosed in US 4,176,022 charging is not suitable for carrying out nano-filtration step, because nanofiltration membrane is to the mechanical damage sensitivity of the top layer that caused by any solid that is present in the charging.
We have found a kind of preparation chlorine-containing compound, especially the method for chlorine and sodium chlorate, the reservation that is wherein containing polyvalent ion in the aqueous solution of 100g/l sodium-chlor at least such as calcium in a step can significantly increase, thereby can make the chlorion direct reaction obtain required chlorine-containing compound in later step.
More specifically, the invention provides a kind of use contain 100g/l sodium-chlor at least and at least the salt brine solution of 0.01ppm polyvalent cation prepare the method for chlorine-containing compound, it comprises the steps:
(i) by making sodium chloride source contain the 100g/l sodium-chlor and the salt brine solution of 0.01ppm polyvalent cation at least at least soluble in water the preparation,
(ii) the component that at least a raising of significant quantity is just being kept adds in the aqueous solution,
(iii) subsequently described solution is carried out nano-filtration step, thereby solution separating is become to be rich in the retentate of polyvalent cation and the penetrant of pure salt brine solution,
(iv) by electrolysis step make chlorion reaction in the penetrant generate chlorine-containing compound and
(v) make to the small part retentate and be recycled to dissolving step (i).
Term " improves the component that is just keeping " and is meant that the reservation that can cause calcium when its adding being comprised the aqueous solution of calcium ion and other polyvalent cation such as magnesium, strontium, iron, barium and/or aluminium increases, and any additives that preferably makes the reservation increase of one or more polyvalent cations that are selected from magnesium, strontium, iron, barium and aluminium when this solution is carried out nano-filtration step.For measuring the component (PREC) that raising that whether additive be suitable as the inventive method is just keeping, can use following test.
By will be available from 1 of Merck, the ultra-pure sodium-chlor of 120g be dissolved in 3, the synthetic salt solution of preparation in the 600g water.Subsequently, with 17.04g Na
2SO
4With 13.2g CaCl
2Be dissolved in the synthetic salt solution.To be called synthetic brinish gained salt solution infeeds and contains 0.036m
2Nanofiltration membrane Desal
The stacked M20 device in the DSS laboratory of 5DK (available from GE/Osmonics).Under 30 bar pressures and envrionment temperature with the cross-stream speed operation film device of 600l/h.Whole recirculation mode (retentate and penetrant are recycled to feed containers) operate devices 1 hour.Subsequently, the permeate sample of collection 50ml also keeps by using inductively coupled plasma-emission spectrometry (ICP-ES) measurement simultaneously to measure Ca with nitric acid acidifying and the Ca concentration of diluting back penetrant and retentate sample.This is a blank assay.In second experiment, the 300ppm additive is added in the described synthetic crude brine.If the precipitation of formation thinks that then this additive is not suitable for use in the PREC in the inventive method.Do not form if visually observe precipitation, then repeat described just now nanofiltration experiment.If compare with blank assay and to observe Ca and keep and definitely increased at least 5%, think that then additive is to improve the component that is just keeping.
Surprisingly have been found that when using aforesaid method, compare with the method that wherein makes the aqueous solution identical but that do not contain the component that raising just keeping carry out this nano-filtration step, observe step (iii) in calcium keep definitely increase at least 5%, preferred 7%, most preferably at least 10%.For whole salt brine solutions required for protection, promptly sodium chloride concentration is saturated until its sodium chloride concentration from 100g/l, even oversaturated solution, can obtain at least 5% absolute reservation that increases.It should be noted if the aqueous solution that does not comprise the component that raising just keeping is carried out in the method for nano-filtration step (promptly in blank assay), the reservation of viewed calcium has been 90-97%, then use the inventive method will cause the increase that keeps, yet absolute increase will be less than 5% but at least 1%.It should be noted if surpass 97% then add the reservation increase that improves after the component that is just keeping and still can expect, but this will no longer have practical use for the reservation of blank assay calcium.Therefore preferably the inventive method is used for wherein that calcium is left 2-97% under the situation of the component that does not exist raising just keeping, more preferably 4-90%, the most preferably salt solution of 5-75%.
It should be noted that in addition usually also observing the reservation that is present in other polyvalent cation in the salt brine solution such as magnesium, strontium, iron, barium and/or aluminium increases.The absolute increase of viewed reservation also surpasses 5% usually.
Used in the methods of the invention PREC is preferably selected from poly carboxylic acid, polyacrylic ester, polymaleic acid, oligopeptide, polypeptide has the polymkeric substance of two or more ester groups or carboxyalkyl and optional phosphate radical, phosphonate radical, phosphino-, sulfate radical and/or sulfonate group; Carbohydrate, for example functionalized or not functionalized monose, disaccharides and polysaccharide; Ferrocyanide salt; Quaternary ammonium salt; Cyclodextrin; Urea; Have amino polymkeric substance; The polymkeric substance that has one or more alcohol radicals; The polymkeric substance that has quaternary ammonium group; The polymkeric substance that comprises nitrogenous aliphatic series ring; The sodium salt that has the polymkeric substance of anionic group; The chloride salt that has the polymkeric substance of cation group; Tensio-active agent from natural source such as disproportionated rosin acid soap; Lactic acid; Phosphatide; The suspension of yeast cell; The suspension of algae; The maleic anhydride homopolymer; Amylase; Proteolytic enzyme; Trisodium Citrate; Citric acid; Nonanoly acyloxy benzene sulfonate; Poly-epoxy succinic acid; Polyacrylamide; Sodium ethylene diamine tetracetate; Ethylenediamine tetramethylene phosphonic acid; The sulfonated Soxylat A 25-7; Lipid acid; Orange juice; Sucus Mali pumilae; And the iron complex of Fe (II) or one of Fe (III) and above-claimed cpd.
More preferably PREC is selected from and does not contain or contain the very following component of small amount of nitrogen: poly carboxylic acid, polyacrylic ester, polymaleic acid has the polymkeric substance of two or more ester groups or carboxyalkyl and optional phosphate radical, phosphonate radical, phosphino-, sulfate radical and/or sulfonate group; Carbohydrate, for example functionalized or not functionalized monose, disaccharides and polysaccharide; Cyclodextrin; The polymkeric substance that has one or more alcohol radicals; The sodium salt that has the polymkeric substance of anionic group; Tensio-active agent from natural source such as disproportionated rosin acid soap; Lactic acid; The suspension of yeast cell; The suspension of algae; The maleic anhydride homopolymer; Trisodium Citrate; Citric acid; The sulfonated Soxylat A 25-7; Lipid acid; Orange juice; Sucus Mali pumilae; And the iron complex of Fe (II) or one of Fe (III) and above-claimed cpd.More not preferred nitrogen component is because because NCl
3Formation they will cause the electrolysis procedure difficulty.Especially work as NCl
3During accumulation, if chlorine as it usually in electrolysis operations liquefaction this accumulation will come true, this is very undesirable, because products therefrom is volatile.
In addition preferred embodiment in, PREC is selected from the component of environmental health: (gathering) carboxylic acid, phosphine carboxylic acid, polyacrylic acid, polymaleic acid, glucose, sucrose (sucrose), sucrose (saccharose) or other carbohydrate, and Sunmorl N 60S.
Most preferably PREC is selected from following macromolecular cpd: phosphine carboxylic acid, the preferred 40%Belsperse that uses available from JianghaiChemical Co.
164 aqueous solution; Polymaleic acid, the preferred 50%Drewsperse that uses available from Ashland Inc
The 747A aqueous solution.
Usually, effectively (promptly compare 5% of the reservation that realizes polyvalent cation calcium at least definitely increases with the blank assay) total amount that needs to add the step PREC (ii) of the inventive method is 15ppm at least.Preferably the total amount of the PREC that adds in (ii) in the step of present method is 25ppm at least, more preferably 35ppm at least, most preferably 50ppm at least.Preferably the total amount of the PREC that adds in (ii) in the step of the inventive method is less than 5, and 000ppm is more preferably less than 1,000ppm, even be more preferably less than 500ppm, most preferably less than 350ppm.PREC can be added in the salt brine solution with pure form (solid or liquid) or as the aqueous solution.
The extra advantage of the inventive method be for also can removing the sulfate ion that is present in the salt brine solution in nano-filtration step, because this has benefited from being suitable for the sulfate radical retention property of excellence of the nanofiltration membrane of the inventive method usually.The low sulfate radical content of the salt brine solution (being the inventive method step penetrant (iii)) of purifying has following advantage.At first, it is less that electrolysis step receives the interference of sulfate ion of obstruction.Secondly, last oxidation step, promptly the purge flow of electrolysis step significantly reduces.For example in the method for producing chlorine, effluent brine is recycled to salt solution unit is saturated to preferred about 310g/l again so that come from the salt solution of electrolyzer.The recycle stream of effluent brine has the shortcoming of accumulation of foreign matter in technology usually in ordinary method, and this requires to exist and cleans.Usually the size of purge flow is by the concentration decision for the treatment of sulfate radical in the recirculation effluent brine.Compare with the described processing method that does not comprise nano-filtration step, nanofiltration method of the present invention can reduce the amount of sulfate radical in the solution that carries out electrolysis step.Therefore, reduced purge flow, made this method even have more magnetism economically.
For removing above-mentioned polyvalent cation, do not need subsequently crystallisation step or to other processing of penetrant.
Because aforesaid method, by step (iii) the salt brine solution of the purification of gained have and can be directly used in later step (iv), promptly produce the purity of chlorine-containing compound, step (iv) in the salt brine solution of purification be raw material.
Can comprise chlorine and sodium chlorate by the chlorine-containing compound of the inventive method preparation.Sodium chlorate NaClO
3Crystalline solid for white, moisture absorption.Quick growth to the sodium chlorate demand in 10 years is owing to introduce the ClO 2 bleaching that comes from oxymuriate on pulp and paper industry to a great extent in the past.Its second mainly be applied as intermediate as the oxymuriate of producing other metal (for example be used for match and explosive Potcrate, be used for the barium chlorate of pyrotechnics and as the calcium chlorate of weedicide).Other purposes is as the oxygenant of metallurgical operations with as the additive of agricultural prods and dyestuff.
According to the present invention, sodium chlorate by to the inventive method step (iii) the gained penetrant carry out the conventional electrolysis step and prepare to produce chlorine, sodium hydroxide and hydrogen.Chlorine and sodium hydroxide reaction form clorox, preferably make it be converted into oxymuriate and muriate under the controlled condition of pH and temperature then, and this is well-known in the art.Preferably before carrying out electrolysis step, penetrant at first make it be slightly acidic with the production sodium chlorate.In addition, solution preferably contains small amounts agent such as the hydrogen reducing oxymuriate of potassium bichromate to prevent to discharge in electrolysis.Also well-known in the art is the solid oxymuriate to be isolated from the electrolyzer effluent by fractional crystallization.
Most preferably prepare chlorine.According to the present invention, chlorine prepares to produce chlorine, sodium hydroxide and hydrogen by the (iii) middle gained penetrant of the inventive method step is carried out electrolysis step, the cell design that wherein will preferably carry out electrolysis step therein gets the reaction that can prevent between chlorine and the caustic alkali, and this also is well-known in the art.Electrolysis step of the present invention comprises electrolysis process such as film electrolysis, diaphragm electrolysis, chlorate electrolysis and mercury electrolysis.Film electrolysis step most preferably.
Can choose wantonly in the methods of the invention and purify (polish) step.In preferred embodiments, this additional purification step (iii) and is (iv) carried out in the step of present method.Purifying step can comprise the aqueous solution is infeeded ion exchange process to remove last trace polyvalent ion from system.Especially when step (iv) comprises the film electrolysis step, very preferably (iii) and the additional ions exchange step of step between (iv) in step.It should be noted and removing so many polyvalent ion in the salt brine solution of gained in (iii), to such an extent as to the ion-exchange step of can low-down chemical cost choosing wantonly by the step of the inventive method.
Preferred salt brine solution in the methods of the invention comprises 150g/l at least, more preferably 200g/l at least, even more preferably 250g/l at least, even more preferably 300g/l sodium-chlor at least also; Most preferably saturated sodium chloride solution.
In the replacement embodiment of the inventive method, can be after component that at least a raising is just being kept adds the aqueous solution or while and in the step of nano-filtration step before (iii), sodium chloride concentration is adjusted to 100g/l at least.
It should be noted that the term " Yanyuan " that uses at this paper is meant wherein above 25 weight % all salt as NaCl in the whole text.Preferred this salt contains and surpasses 50 weight %NaCl.More preferably salt contains and surpasses 75 weight %NaCl, and most preferably contains the salt that surpasses 90 weight %NaCl.Salt can be solar salt shan (by using the salt of solar heat vaporize water gained from salt solution), rock salt and/or subterraneous salt deposit.When comprising the salt brine solution of 100g/l sodium-chlor at least when described Yanyuan is dissolved in the water with generation, it will comprise total amount and be the polyvalent cation impurity of 0.01ppm at least.One or more the present invention of aequum are just being improved in the aqueous solution of component adding preparation like this.Yet, also PREC can added Yanyuan or was adding in the entry before dissolving step before the dissolving step.The combination of these programs also is fine.
The preferred subterraneous salt deposit of Yanyuan for exploiting by solution mining.If Yanyuan is rock salt or solar salt shan, then preferably be transported to added entry salt solution unit to prepare salt brine solution of the present invention.Water can be from any water source that is usually used in this such as well water or surface water.
Near small part retentate is recycled to dissolving step (i).Therefore, be recirculated to salt solution unit or subterraneous salt deposit.Retentate is recycled to dissolver or subterraneous salt deposit has following advantage.The salt brine solution that carries out nano-filtration step comprises the component (PREC) that at least a raising is just keeping.Therefore retentate has reduced the amount that needs to add the PREC in the described salt brine solution to the recirculation of dissolver.In addition, because polyvalent ion impurity is significantly kept by nanofiltration membrane, these impurity will be accumulated in the salt solution that is recycled to dissolver or subterraneous salt deposit.At last, they will reach its solubility limit and therefore be deposited on the bottom, cave of dissolver bottom or subterraneous salt deposit with the form of dehydrated gyp-or polyhalite, wherein can easily remove them via mud in the dissolver bottom.
One or more for example can be described in conventional retarding agent among the EP 1 404 614 in this embodiment and add dissolver or subterraneous salt deposit are present in the impurity in the Yanyuan of waiting to be dissolved in the salt brine solution with further minimizing amount.
In another embodiment, polyvalent cation also comprises polyvalent cation magnesium, strontium, iron, barium, aluminium or two or more these cationic mixtures except calcium.In another embodiment, the impurity level of the polyvalent cation in the aqueous solution of pending nano-filtration step is less than 20, and 000ppm and 0.01ppm at least are more preferably less than 10,000ppm, even be more preferably less than 4, and 000ppm, most preferably less than 2,000ppm.Preferred impurity level is 0.1ppm at least, even more preferably 10ppm at least, most preferably 100ppm at least.
In another embodiment of the inventive method, the calcium in the salt brine solution of pending nano-filtration step or the amount of magnesium are less than 2,000ppm, and preferably less than 1,800ppm is more preferably less than 1,600ppm, most preferably less than 1,400ppm.More preferably the amount of the merging of calcium and magnesium is less than 2,500ppm, and preferably less than 2,000ppm.
In the another preferred embodiment of the inventive method, the amount of the sulfate anion in the salt brine solution of pending nano-filtration step is less than 75, and 000ppm is preferably less than 50,000ppm is more preferably less than 25, and 000ppm is most preferably less than 10,000ppm, most preferably less than 8,000ppm.
It should be noted to be positioned over and be meant that in " nanofiltration membrane " of specification sheets in the whole text being designed to selectivity repels divalence and other multivalent anions and have 100Da at least in the film nanofiltration device, the preferred any conventional nanofiltration membrane of 150Da molecular weight intercepting value at least, wherein molecular weight intercepting value is at the most 25,000Da, preferably at the most 10,000Da, more preferably at the most 2,500Da, most preferably at the most 1,000Da.The nanofiltration system preference uses the semipermeable partition of nanofiltration type, and for example those are with FilmTec
NF270 (TheDow Chemical Company), DESAL
5DK, DESAL
5DL, DESAL
5HL (being GE/Osmonics), NTR
7250 (Nitto Denko Industrial Membranes) and AFC
The film that-30 (PCI Membrane Systems LTD) sell.Be suitable for these films of the inventive method and all dianions, especially sulfate radical and the carbonate that similar film effectively repels high percentage composition,, handling 1g/L MgSO as in complete recirculation operation
4Observed sulfate radical keeps and surpasses 80% in the process of soften aqueous solution, preferably surpass 90%, allow all monovalent anions of high percentage composition simultaneously, especially chlorion and bromide anion pass through film, as in complete recirculation operation, the chlorion reservation is lower than 80% in the process of handling 1g/L NaCl soften aqueous solution, preferably is lower than 70%.The test of these solution should be carried out at ambient temperature, and wherein the throughput of film is 20-30l/m
2H, and the intersection flow velocity should be avoided strong concentration polarization.Sodium-chlor and sal epsom reservation can be used the calibrated conductivity test and measure in these tests.Although the film type of semipermeable partition as formerly mentioning of preferred nanofiltration-type, commercially available the obtaining and alternative use of other nanofiltration membrane with these high divalent ion repellencies.
The inventive method further specifies by following embodiment.
Embodiment
Use in an embodiment as giving a definition:
Keep={ 1-(in the penetrant in concentration of component/retentate concentration of component) } * 100%
Embodiment 1
Use following two types film to experimentize: 4-inch screw winding NF
270 polyamide layer NF films are (available from DOW Chemical Company FilmTec
TM) and 4-inch screw winding Desal
5DK polymeric amide NF film (available from GE/Osmonics), the surface-area of its film is respectively 7.6m
2And 8.4m
2Parallel testing membrane module in experimental installation, described device is about 3m at each membrane module
3Under the intersection flow velocity of/h with the operation mode of continuously feeding and discharging.To infeed device by the mother liquor of sodium chloride crystallizer gained.Use dense (35%) H
2SO
4Solution is reduced to 10.7 with the pH of mother liquor.In addition, by adding the Drewsperse of 202ppm available from Ashland Inc.
747A, promptly 50% aqueous solution of polymaleic acid improves the component that is just keeping with 101ppm and adds mother liquor.In delivering to film experimental installation mother liquid obtained, except that other composition, also contain 280g/l NaCl, 0.25meq/L calcium, 0.06meq/L strontium and 1,190meq/L SO
4 2-Most of retentate is recycled to film feeding line (cross-flow operation), and simultaneously wash section retentate and penetrant are to obtain about 1.3 the enrichment factor ratio of the retentate stream of cleaning (fresh feed flow with).For Desal
5DK and NF
270, obtain in the membrane filtration processes under 32 bar pressures and 40 ℃ that 99% calcium keeps and 88% strontium reservation.
Comparative Examples 2
Use following two types film to carry out another experiment: dull and stereotyped NF
270 polyamide layer NF films are (available from DOW Chemical Company FilmTec
TM) and dull and stereotyped Desal
5DK polymeric amide NF film (available from GE/Osmonics).In the stacked laminator of DSS laboratory, test the film of described type simultaneously, described stacked laminator under the intersection flow velocity of 600L/h with the operation mode of continuously feeding and discharging.The film surface-area of being set up is total up to 0.144m
2The mother liquor that will obtain from sodium chloride crystallizer infeeds in the device.Use dense H
2SO
4Solution is reduced to 10.8 with the pH of mother liquor.Do not add the component that raising is just keeping.In delivering to DSS device mother liquid obtained, except that other composition, also contain 1,150meq/L SO
4 2-, 296g/l NaCl, 1.3mg/l Ca
2+With 655mg/l Br
-Membrane filtration carries out under the pressure of 50 crust and 32 ℃ temperature.Most of retentate is recycled to film feeding line (cross-flow operation), and simultaneously wash section retentate and penetrant are to obtain about 1.3 enrichment factor.Described film shows that the reservation of calcium is lower than 32%.
Comparative Examples 3
Use following two types film to carry out another experiment: dull and stereotyped NF
270 polyamide layer NF films (available from DOW Chemical Company FilmTecTM) and dull and stereotyped Desal
5DK polymeric amide NF film (available from GE/Osmonics).In the stacked laminator of DSS laboratory, test the film of described type simultaneously, described stacked laminator under 600L/h intersects flow velocity with whole recirculation mode operations (whole retentates and penetrant are recycled to film to infeed in the container).The film surface-area of being set up is total up to 0.36m
2The crude brine that will obtain from saline source infeeds in the device.Do not add the component that raising is just keeping.In the crude brine of delivering to DSS laboratory stacked laminator, except that other composition, also contain 1.21meq/L SO
4 2-, 273g/l NaCl, 3.3mg/l strontium, 10.3mg/l magnesium and 494mg/l Ca
2+Membrane filtration carries out under the pressure of 21 crust and 22 ℃ temperature.Desal
5DK and NF
270 show that respectively 36% and 24% calcium keeps, and the strontium reservation is lower than 59%.And discovery Desal
5DK and NF
270 magnesium reservation is respectively 68% and 66%.Find Desal
5DK and NF
270 sulfate radical reservation is respectively 94.2% and 95.9%.
Embodiment 4
Use following two types film to experimentize: 4-inch screw winding NF
270 polyamide layer NF films are (available from DOW Chemical Company FilmTec
TM) and 4-inch screw winding Desal
5DK polymeric amide NF film (available from GE/Osmonics), the surface-area of its film is respectively 7.6m
2And 8.4m
2Parallel testing membrane module in experimental installation, described device is to NF
270 and Desal
Each membrane module of 5DK is 3.1m
3/ h and 2.6m
3Under the intersection flow velocity of/h with the operation mode of continuously feeding and discharging.To infeed device by the mother liquor that sodium chloride crystallizer obtains.Use dense (35%) H
2SO
4Solution is reduced to 10.6 with the pH of mother liquor.In addition, by adding 192ppmDrewsperse
747A (referring to embodiment 1) improves the component that is just keeping with 96ppm and adds mother liquor.In delivering to film experimental installation mother liquid obtained, except that other composition, also contain the consoluet calcium of 280g/l NaCl, 0.046meq/L and 1,125meq/L SO
4 2-Most of retentate is recycled to film feeding line (cross-flow operation), and simultaneously wash section retentate and penetrant are with to NF
270 and Desal
5DK obtains about 1.3 and 1.2 enrichment factor respectively.At 32 bar pressures, for NF
270 and Desal
5DK is respectively in the membrane filtration processes under 34 ℃ and 39 ℃ Desal
5DK and NF
270 obtain 96% and 97% calcium reservation respectively.
Embodiment 5
Use following two types film and from Comparative Examples 3 in the crude brine of identical sources of explanation carry out another experiment: dull and stereotyped NF
270 polyamide layer NF films are (available from DOW Chemical CompanyFilmTec
TM) and dull and stereotyped Desal
5DK polymeric amide NF film (available from GE/Osmonics).In addition, by adding 600ppm Drewsperse
747A (referring to embodiment 1) improves the component that is just keeping with 300ppm and adds in the crude brine.In the stacked laminator of DSS laboratory, test the film of described type simultaneously, described stacked laminator under the intersection flow velocity of 600L/h with whole recirculation mode (whole retentates and penetrant are recycled to film to infeed in the container) operation.The film surface-area of being set up is total up to 0.216m
2To infeed in the device by the crude brine that saline source obtains.In the crude brine of delivering to DSS laboratory stacked laminator, except that other composition, also contain 1.11g/l SO
4 2-, 289g/l NaCl, 3.0mg/l strontium, 10.1mg/l magnesium and 490mg/l Ca
2+Membrane filtration carries out under the pressure of 31 crust and 21 ℃ temperature.Desal
5DK and NF
270 show that respectively 79% and 50% calcium keeps, and 90% and 70% strontium keeps, and 93% and 79% magnesium keeps.Two kinds of films show that all 0.6% chlorion keeps.Desal
5DK and NF
270 show that respectively 96.8% and 98.5% sulfate radical keeps.
Comparative Examples 6
Use the lab membrane electrolyzer to carry out electrolytic experiment, wherein the penetrant that Comparative Examples 3 is produced is as incoming flow.Under the constant current of 5A between anode and negative electrode, experimentize.After about 3 hours, stop electrolysis process, because the potential difference on the film surpasses 4V.
Embodiment 7
Use and electrolyzer identical described in the Comparative Examples 6 and identical processing condition, but use the penetrant that produces among the embodiment 5 to carry out electrolytic experiment now.Operate after 6 hours, the experimental installation still potential difference on running and film is lower than 4V.
As described in above-mentioned embodiment, compare with the method that before carrying out nano-filtration step, will not improve the component adding salt brine solution that is just keeping, use the calcium of the inventive method and the reservation of strontium ion significantly to increase, so the gained salt brine solution can directly and be suitable for making in electrolysis process the chlorion reaction to generate chlorine.
Claims (12)
1. use and contain the method that the salt brine solution of the polyvalent cation of 100g/l sodium-chlor and impurity level at least prepares chlorine-containing compound, it comprises the steps:
(i) by making sodium chloride source contain the 100g/l sodium-chlor and the salt brine solution of 0.01ppm polyvalent cation at least at least soluble in water the preparation,
(ii) the component that at least a raising of significant quantity is just being kept adds in the described aqueous solution,
(iii) subsequently described solution is carried out nano-filtration step, thereby described solution separating is become to be rich in the retentate of polyvalent cation and the penetrant of pure salt brine solution,
(iv) by electrolysis step make chlorion reaction in the penetrant generate chlorine-containing compound and
(v) make to the small part retentate and be recycled to dissolving step (i).
According to the process of claim 1 wherein can will improve step that the component that is just keeping adds the described aqueous solution (ii) after or simultaneously and in the step of nano-filtration step before (iii) sodium chloride concentration is adjusted to 100g/l at least.
3. according to the method for claim 1 or 2, the wherein said aqueous solution comprises 150g/l at least, preferred 200g/l at least, even more preferably 300g/l sodium-chlor at least, most preferably saturated sodium chloride solution.
4. according to each method among the aforementioned claim 1-3, wherein improve positive retained fraction and be selected from poly carboxylic acid, polyacrylic ester, polymaleic acid, oligopeptide, polypeptide has the polymkeric substance of two or more ester groups or carboxyalkyl and optional phosphate radical, phosphonate radical, phosphino-, sulfate radical and/or sulfonate group; Carbohydrate, for example functionalized or not functionalized monose, disaccharides and polysaccharide; Ferrocyanide salt; Quaternary ammonium salt; Cyclodextrin; Urea; Have amino polymkeric substance; The polymkeric substance that has one or more alcohol radicals; The polymkeric substance that has quaternary ammonium group; The polymkeric substance that comprises nitrogenous aliphatic series ring; The sodium salt that has the polymkeric substance of anionic group; The chloride salt that has the polymkeric substance of cation group; Tensio-active agent from natural source such as disproportionated rosin acid soap; Lactic acid; Phosphatide; The suspension of yeast cell; The suspension of algae; The maleic anhydride homopolymer; Amylase; Proteolytic enzyme; Trisodium Citrate; Citric acid; Nonanoly acyloxy benzene sulfonate; Poly-epoxy succinic acid; Polyacrylamide; Sodium ethylene diamine tetracetate; Ethylenediamine tetramethylene phosphonic acid; The sulfonated Soxylat A 25-7; Lipid acid; Orange juice; Sucus Mali pumilae; And the iron complex of Fe (II) or one of Fe (III) and above-claimed cpd.
5. according to each method among the aforementioned claim 1-3, wherein improve the component that is just keeping and be selected from (gathering) carboxylic acid, phosphine carboxylic acid, polyacrylic acid, polymaleic acid, glucose, sucrose (sucrose), sucrose (saccharose) and Sunmorl N 60S.
6. according to each method among the aforementioned claim 1-6, wherein with 15ppm at least, preferred 25ppm at least, most preferably the amount of 50ppm adds and improves the component that is just keeping at least.
7. according to each method among the aforementioned claim 1-5, wherein with less than 5,000ppm is more preferably less than 1, and 000ppm most preferably adds less than the amount of 350ppm and improves the reagent that is just keeping.
8. according to each method among the aforementioned claim 1-7, wherein except calcium, described polyvalent ion also comprises magnesium, strontium, iron, barium and/or aluminium.
9. method according to Claim 8, wherein calcium or magnesium is with less than 2,000ppm, preferably less than 1,800ppm is more preferably less than 1,600ppm, most preferably less than 1, the amount of 400ppm is present in the described aqueous solution.
10. according to each method among the aforementioned claim 1-9, the amount of sulfate anion is less than 75 in the wherein said salt brine solution, 000ppm, and preferably less than 50,000ppm is more preferably less than 25,000ppm, most preferably less than 8,000ppm.
11. according to each method among the aforementioned claim 1-10, wherein said sodium chloride source surpasses 75 weight %NaCl for containing, and most preferably surpasses the natural Yanyuan of 90 weight %NaCl.
12. according to each method among the aforementioned claim 1-11, wherein said chlorine-containing compound is chlorine or sodium chlorate.
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| CN201510053349.6A CN104692327B (en) | 2005-02-18 | 2006-02-13 | The method for preparing chlorine-containing compound |
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| US65407805P | 2005-02-18 | 2005-02-18 | |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106418433A (en) * | 2016-10-11 | 2017-02-22 | 温县兴发生物科技有限公司 | Preparation method of adult type organic and nutritious low-sodium salt |
| CN107406267A (en) * | 2015-03-02 | 2017-11-28 | 索尔维公司 | Method for manufacturing sodium-chloride water solution |
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2006
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107406267A (en) * | 2015-03-02 | 2017-11-28 | 索尔维公司 | Method for manufacturing sodium-chloride water solution |
| CN106418433A (en) * | 2016-10-11 | 2017-02-22 | 温县兴发生物科技有限公司 | Preparation method of adult type organic and nutritious low-sodium salt |
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