HIGH STRENGTH, LOW SALT HYPOCHLORITE PRODUCTION
20190023569 · 2019-01-24
Inventors
Cpc classification
C25B1/34
CHEMISTRY; METALLURGY
International classification
C25B1/34
CHEMISTRY; METALLURGY
Abstract
High strength, low salt solutions of alkali hypochlorite (e.g. sodium hypochlorite) can advantageously be produced in a system comprising a subsystem in which alkali hydroxide solution and chlorine are reacted to produce alkali hypochlorite and salt solids in a crystallizer, while drawing a vacuum in the crystallizer. In a system comprising a chlor-alkali plant, the alkali hydroxide solution and chlorine can be directly obtained (i.e. without concentrating) from the electrolyzer in the plant. A net energy savings in the system can be achieved and water consumption in the chlor-alkali plant can be substantially decreased by returning chlorinated condensate from the crystallizer to the recycle line in the chlor-alkali plant. Salt can be efficiently recovered by redissolving the salt solids produced in depleted brine and returning it directly to the electrolyzer. As a result, high strength, low salt hypochlorite can be produced without the need to evaporate caustic.
Claims
1. A process for producing a high strength, low salt solution of an alkali hypochlorite in a system comprising a subsystem for reacting an alkali hydroxide solution and chlorine to produce the alkali hypochlorite, the process comprising: providing the alkali hydroxide solution and chlorine to the subsystem; reacting the obtained alkali hydroxide solution and chlorine in a crystallizer to produce a mixture comprising the alkali hypochlorite solution and solids of an alkali chloride salt; drawing a vacuum in the crystallizer during the reacting; removing the alkali hypochlorite solution from the crystallizer, thereby producing the high strength, low salt solution; and separating the alkali chloride salt solids from the mixture.
2. The process of claim 1 wherein the alkali is sodium and the alkali hypochlorite is sodium hypochlorite.
3. The process of claim 1 wherein the system comprises a chlor-alkali plant comprising an electrolyzer and an alkali brine recycle line, the recycle line directs a stream of supply brine to an electrolyzer inlet and a stream of depleted brine from an electrolyzer outlet, and the subsystem is for reacting an alkali hydroxide solution and chlorine obtained from the electrolyzer to produce the alkali hypochlorite, the process comprising: providing the alkali hydroxide solution and chlorine obtained from the electrolyzer directly to the subsystem; and reacting the directly obtained alkali hydroxide solution and chlorine in the crystallizer to produce the mixture comprising the alkali hypochlorite solution and solids of an alkali chloride salt.
4. The process of claim 3 wherein the concentration of the directly provided alkali hydroxide solution obtained from the electrolyzer is about 32%.
5. The process of claim 3 comprising: dissolving the separated alkali chloride salt solids in a portion of the depleted brine stream from the electrolyzer outlet to create a recovered salt brine stream; and combining the recovered salt brine stream directly with the supply brine stream being directed to the electrolyzer inlet.
6. The process of claim 2 wherein the concentration of sodium hypochlorite is greater than or equal to 30% and the concentration of sodium chloride is less than or equal to 7% in the produced high strength, low salt solution.
7. The process of claim 3 wherein the produced high strength, low salt solution is essentially produced in a single stage.
8. The process of claim 7 wherein greater than 99.5% of the total produced high strength, low salt solution is essentially produced in a single stage.
9. A system for producing a high strength, low salt solution of an alkali hypochlorite comprising: a subsystem for reacting an alkali hydroxide solution and chlorine to produce the alkali hypochlorite; wherein the subsystem comprises apparatus for drawing a vacuum, and the subsystem is configured to operate according to the process of claim 1.
10. A system for producing a high strength, low salt solution of an alkali hypochlorite comprising: a chlor-alkali plant comprising an electrolyzer and an alkali brine recycle line, wherein the recycle line connects a stream of supply brine to an electrolyzer inlet and a stream of depleted brine to an electrolyzer outlet; and a subsystem for reacting an alkali hydroxide solution and chlorine obtained from the electrolyzer to produce the alkali hypochlorite; wherein the subsystem comprises apparatus for drawing a vacuum, and the subsystem is configured to operate according to the process of claim 3.
11. The system of claim 10 is absent a chlorine compressor for compressing the chlorine obtained from the electrolyzer to produce the alkali hypochlorite.
12. The system of claim 10 is absent a caustic evaporator for concentrating the alkali hydroxide solution obtained from the electrolyzer to produce the alkali hypochlorite.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
[0014]
[0015]
[0016]
[0017]
DETAILED DESCRIPTION
[0018] Unless the context requires otherwise, throughout this specification and claims, the words comprise, comprising and the like are to be construed in an open, inclusive sense. The words a, an, and the like are to be considered as meaning at least one and not limited to just one. Further, in a numerical context, the word about is to be construed as meaning plus or minus 10%.
[0019] Herein, a high strength sodium hypochlorite solution is defined as an aqueous solution whose [NaOCl] is greater than 25% (and is consistent with the aforementioned WO006/017234).
[0020] Herein, a low salt sodium hypochlorite solution is defined as an aqueous solution whose [NaCl] is less than 9.5% (and is also consistent with the aforementioned WO2006/017234).
[0021] System for Production of Low Strength Sodium Hypochlorite Solution
[0022] A simplified schematic of a prior art system for producing low strength hypochlorite is shown in
[0023] The chlor-alkali plant in system 101 comprises electrolyzer 150 and alkali brine recycle line 102 which directs an appropriately treated stream of supply brine to electrolyzer inlet 150a and recycles a stream of depleted brine from electrolyzer outlet 150b. The alkali brine here is an aqueous solution of NaCl and it undergoes electrolysis in electrolyzer 150 to produce primary products Cl.sub.2 gas (at the anode or anodes) and NaOH and hydrogen gas (at the cathode or cathodes). The product Cl.sub.2, NaOH, and H.sub.2 are removed at outlets 150c, 150d, and 150e respectively. As shown in
[0024] The depleted brine stream from electrolyzer outlet 150b then undergoes two stages of dechlorination. First, the depleted brine stream is directed to primary dechlorination unit 160 in which residual chlorine is stripped, for instance, into air which is directed through unit 160. The amount of chlorine in the chlorine/air mixture is typically quite low (less than 0.5%). Then, the depleted brine stream is directed to secondary dechlorination unit 170 in which sodium sulfite and sodium hydroxide are reacted with any remaining chlorine to produce sodium sulfate, sodium chloride, and water.
[0025] The concentration of NaCl in the brine stream is then brought back up to the desired level. This is accomplished by addition of NaCl and water to the dechlorinated depleted brine stream in saturator unit 110. The reconcentrated brine stream then undergoes two stages of treatment to remove impurities which may be present in the added salt and added water. A first treatment involves reacting with a combination of primary treatment chemicals in primary treatment unit 120 to produce precipitates which are filtered out with the addition of precoat filter aid. The brine stream is then directed to secondary treatment unit 130 where further purification takes place. NaOH, HCl and water are added for regeneration purposes producing two effluents; one which can be recovered and another one (unrecoverable) for disposal. The now treated and purified brine stream is directed to storage and conditioning unit 140 ready for electrolysis in electrolyzer 150.
[0026] The chlor-alkali plant in system 101 also comprises chlorine scrubbing system 180 which is used to scrub chlorine from the low concentration chlorine and air mixture coming from primary dechlorination unit 160. This mixture is provided to chlorine scrubbing system 180 at inlet 180c. The by-products of such scrubbing are a modest amount of low concentration sodium hypochlorite solution and inert gas which are provided from outlets 180d and 180e respectively. However, chlorine scrubbing subsystem 180 can essentially be used as a subsystem for producing a significant amount of sodium hypochlorite if additional Cl.sub.2 and NaOH reactants are provided. This is the case in
[0027] In commercial systems, additional processes and associated equipment are frequently employed. For instance, sodium sulfate impurity typically is present in the process salt provided and can undesirably increase in concentration in the recycling brine stream unless it is continually removed. Although not shown in
[0028] System for two stage production of high strength sodium hypochlorite solution
[0029]
[0030] Hypochlorite production system 201 in
[0031] The process of WO2008/082626 also requires the chlorine reactant to be provided at a higher pressure than is produced from electrolyzer 150. (As later shown in
[0032] As in
[0033] High strength ([NaOCl] of 30%), low salt ([NaCl] of 7%) hypochlorite solution product is obtained from hypochlorite reactor subsystem 210 at outlet 210f. Recovered NaCl salt solids are redissolved in hypochlorite reactor subsystem 210 and a solution of this recovered salt is obtained at outlet 210d. The recovered salt solution is dechlorinated in dechlorination unit 220 and is then directed back into recycle line 102 for secondary treatment at point 102a (between primary treatment unit 120 and secondary treatment unit 130).
[0034] As shown in more detail in
[0035]
[0036] Hypochlorite reactor subsystem 210 provides for the second stage production of hypochlorite and associated subsequent processing. The function and interaction of all the components therein are described in detail in WO2008/082626. Main components in subsystem 210 are crystallizer 40 (in which the hypochlorite production reaction takes place and in which NaCl salt crystals of appropriate size are formed) and the recycling apparatus for the solution therein. Importantly, crystallizer 40 is designed to function as a surface cooled crystallizer. Further, the recycling rate, locations of the recycle inlet and outlet, and temperature difference of the recycling solution between the inlet and outlet are all important aspects of the process and require careful design and/or control.
[0037] Hypochlorite production system 201 produces quality high strength, low salt hypochlorite product but requires significant energy input to condition the NaOH and chlorine reactants from the electrolyzer for the second stage of the hypochlorite production. By-product crystallized salt can be recovered to some extent and returned to the recycle line of the chlor-alkali plant for re-use.
[0038] Inventive System for Single Stage Production of High Strength Sodium Hypochlorite Solution
[0039]
[0040] Hypochlorite production system 301 in
[0041] In
[0042] In
[0043] In system 301, a portion of the depleted brine stream from electrolyzer 150 is diverted at point 102d from recycle line 102 and is directed to inlet 310n of subsystem 310. As shown in more detail in
[0044] As in
[0045]
[0046] The recycle aspects and temperatures employed in crystallizer 320 are similar to those already used in the art. Chlorine and NaOH reactants are provided directly from electrolyzer 150 to subsystem inlets 310a and 310b respectively where they merge with slurry recycling from crystallizer 320 in recycle line 324. Slurry is pumped by recycle pump 314 and recycles in a large loop from outlet 320b and returns at inlet 320c.
[0047] In crystallizer 320, NaOCl solution and solid NaCl crystals are formed and a slurry is created. While a portion of that slurry is recycled in recycle line 324, another portion is pumped via slurry pump 325 to centrifuge 326 where the salt solids are centrifuged out. Wash solution for the centrifuge operation can be obtained from chlorinated condensate tank 323 (not shown in
[0048] A primarily liquid fraction is obtained near quieting baffle 320f in crystallizer 320 and is removed at outlet 320d. The primarily liquid fraction is pumped through fines destruction pump 329. A portion of the liquid fraction is then withdrawn as high strength, low salt hypochlorite product at outlet 310f. The remaining portion of the liquid fraction is passed through two heat exchangers in series. The first of these is chlorine cooler 330 where heat is exchanged with chlorine coming from electrolyzer 150. The second of these is depleted brine heat exchanger 331 which exchanges heat with depleted brine obtained from point 102d in recycle line 102. From the heat exchange, this portion of the liquid fraction is heated and the salt fines are redissolved. The heat exchanged portion of the liquid fraction is then merged with the recycling slurry in recycle line 324.
[0049] Heat exchanged depleted brine from heat exchanger 331 is then provided to salt dissolver unit 312 and serves as solvent for the recovered salt from centrifuge 326. The recovered salt solution is then pumped via brine pump 332 to merge with brine in recycle line 102 at point 102b and thus for re-use in electrolyzer 150.
[0050] As mentioned above chlorinated condensate can be used as wash water in centrifuge 326. Also, the chlorinated condensate may be employed as make up water elsewhere in the system for concentration adjustment of hypochlorite streams. Advantageously however, it can be returned as make up water to the main brine stream in recycle line 102 of the component chlor-alkali plant to displace otherwise required make up water supplied to saturator unit 110. To do this, chlorinated condensate pump 333 pumps chlorinated condensate from tank 323 to point 102c in recycle line 102. By comparison with the process shown in
[0051] The exemplary inventive system above provides several advantages over the aforementioned two stage system for producing high strength sodium hypochlorite solution and the single stage system for producing low strength sodium hypochlorite solution.
[0052] Because the NaOH solution and chlorine reactants for the hypochlorite production can be used directly as obtained from electrolyzer 150, neither caustic evaporator 240 nor chlorine compressor 250 in hypochlorite reactor subsystem 210 are required. Consequently, the energy required to operate these devices is not required either. A modest amount of energy is required to operate the additional vacuum pump 321. However, this is substantially less than the energy required for caustic concentration or chlorine compression. Thus, there is substantial energy savings associated with use of hypochlorite reactor subsystem 310. (The energy input required to continuously evaporate water in crystallizer 320 is essentially provided via chlorine cooler 330 and heat exchanger 331. This energy is available already and is obtained from elsewhere in the system.)
[0053] Further, the arrangement for the recovered salt solution in the inventive embodiment of
[0054] Alternatively, an existing low strength hypochlorite production system (like system 101 in
[0055] Another advantage of hypochlorite production system 301 in
[0056] The hypochlorite reactor subsystem of the invention may be used in construction of new hypochlorite production systems employing a chlor-alkali plant. The associated brine system can be made smaller. And the reduced salt consumption associated therewith allows for greater options with regards to sourcing salt supply. For instance, a more expensive but higher quality salt supply may be considered if the cost is offset by a reduction or even elimination in primary and secondary treatment of the brine stream. Further, the hypochlorite reactor subsystem of the invention may be used in a retrofit situation of an existing hypochlorite production system employing a chlor-alkali plant. For instance, an existing system like that shown in
[0057] Further still, consideration may even be given to retrofitting a system like that shown in
[0058] And while the preceding description is mainly directed towards the production of sodium hypochlorite in a system comprising a chlor-alkali plant, other alternative uses and embodiments of the invention may be contemplated. For instance, while not as common perhaps, the process and systems could alternatively be used to produce other alkali hypochlorites.
[0059] Further, the disclosed improved subsystem for producing hypochlorite may be used in situations where the alkali hydroxide solution and chlorine reactants are not obtained from, or directly from, an electrolyzer in a chlor-alkali plant (e.g. in discrete blender operations). In this case, the recovered salt can be further processed to allow for sale of the salt.
[0060] All of the above U.S. patents, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification, are incorporated herein by reference in their entirety.
[0061] While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood, of course, that the invention is not limited thereto since further modifications may be made by those skilled in the art without departing from the spirit and scope of the present disclosure, particularly in light of the foregoing teachings. Such modifications are to be considered within the purview and scope of the claims appended hereto.