CA2007034A1 - Salt handling apparatus for a hypochlorous acid reactor - Google Patents
Salt handling apparatus for a hypochlorous acid reactorInfo
- Publication number
- CA2007034A1 CA2007034A1 CA002007034A CA2007034A CA2007034A1 CA 2007034 A1 CA2007034 A1 CA 2007034A1 CA 002007034 A CA002007034 A CA 002007034A CA 2007034 A CA2007034 A CA 2007034A CA 2007034 A1 CA2007034 A1 CA 2007034A1
- Authority
- CA
- Canada
- Prior art keywords
- solids
- reactor
- product
- alkali metal
- handling apparatus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 title abstract description 23
- 150000003839 salts Chemical class 0.000 title description 37
- 239000007787 solid Substances 0.000 claims abstract description 51
- 239000006227 byproduct Substances 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 31
- -1 alkali metal halide salt Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000003518 caustics Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 229910001902 chlorine oxide Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CGMWMYHEKGCISN-UHFFFAOYSA-N (2-chloro-6-fluorophenyl)hydrazine Chemical compound NNC1=C(F)C=CC=C1Cl CGMWMYHEKGCISN-UHFFFAOYSA-N 0.000 description 1
- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0073—Sealings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
- B01J2219/00193—Sensing a parameter
- B01J2219/00195—Sensing a parameter of the reaction system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
ABSTRACT OF THE INVENTION
An elongated, generally vertically extending reactor vessel (15) for the production of hypochlorous acid by the mixing and reaction of a liquid alkali metal hydroxide and a gaseous halogen is provided with solids discharge handling apparatus (45) connected to the bottom (19) to remove the solid by-product. The discharge handling apparatus (45) uses the solids to effect a seal to prevent the intrusion of outside air into the reactor (10) and the escape of halogen and product gas to the outside atmosphere. (Drawing Figure 3)
An elongated, generally vertically extending reactor vessel (15) for the production of hypochlorous acid by the mixing and reaction of a liquid alkali metal hydroxide and a gaseous halogen is provided with solids discharge handling apparatus (45) connected to the bottom (19) to remove the solid by-product. The discharge handling apparatus (45) uses the solids to effect a seal to prevent the intrusion of outside air into the reactor (10) and the escape of halogen and product gas to the outside atmosphere. (Drawing Figure 3)
Description
7~
~ALT HANDLING ~PP~RA'~S FOR ~ HY~OC~LOROUS ACIP REACTQ~
This invention relates generally to the solids discharge handling apparatus associated with a reactor vessel system and, more specifically to that apparatus associated with a reactor vessel for the production of hypohalo~enated acid by the mixing and reaction therein of an alkali metal hydroxide and a gaseous halogen. A preferred product acid is hypochlorous acid.
1~ Hypochlorous acid is used extensively in the preparation o chlorohydrin and chlorarnines.
Chloroisocyanurates are typical examples. Hypochlorous acid has been produced by several processes or techniques. The use of dilute hypochlorous acid and large quantities of halogen to produce hypohalites, such as sodium hypochlorite, is recent.
One technique employs the process in which chlorine, steam and air are bubbled through ~n aqueous solution of an alkali earth metal hypochlorite, such as 2~ calcium hypochlorite, to remove the resultiny hypochlorous acid in vapor form. The hypochlorous acid -1- ~.' , æ()~703~
is then condensed and stored for use. This process, however, produces a large volume of undesirable by-product, calcium chloride.
Another process uses a low concentration of aqueous caustic solution to scrub chlorine gas.
However, the solution has an available chlorine content of about only 5% and, because of the chloride ion content, the hypochlorous acid that is formed quickly decomposes, most preferably to chloric acid.
1~ Another related process prepares a solid mixture of alkali metal hypochlorite and alkali metal chloride by reacting chlorine gas with a spray of alkali metal hydroxide, while drying with a gas the reactants and product. Some cooling of the reacting chemicals and the drying gas may be done. The primary products of this process have very limited utility.
A more recent process, which produces hypochlorous acid vapor, sprays aqueous alkali metal hydroxide in droplet form or solid alkali metal 2~ hydroxide particles into gaseous chlorine. This approach attempts to utilize droplet sizes to attain the ma~imum surface to volume ratio possible. Droplets having an average diameter of less than about 1000 rnicrons are employed.
These previous processes, and the apparatus employed to produce these processes, have suffered from not achieving substantially complete reactions between the chlorine and the alkali metal hydroxide. A
critical factor in determining the complete reaction is 3~ the droplet size of the alkali metal hydroxide. It is also desirable that any hypochlorous acid produced and any water present be readily vaporizable. The salt particles produced as by-products in any process should be dry to facilitate handling and be continuously 20Q~7034 removable from the reaction while maintaining a seal to the atmosphere to prevent the gaseous product from escaping to the surrounding area and to prevent atmospheric gases from mi~ing with the gaseous product. The increased concentration of water and inert gases such as oxygen and nitrogen, in the reactor system when atmospheric gases intrude reduces the operating efficiency of the system. The salt particles should be sized so that they readily separate from the 1~ gaseous product mixture of hypochlorous acid.
Prior processes have produced oversized alkali metal hydroxide droplets that result in the undesired reaction of hypochlorous acid and the oversized particles to produce significant alkali metal chlorates. These oversized particles then retain excessive moisture so that caking results and the caked mass adheres to the reactor surfaces. These oversized particles can hamper the byproduct salt removal additionally. The presence of such alkali metal 2~ chlorates reflect reduced yields of the desired hypochlorous acid, while increasing the raw material and operatiny costs. Lastly, the presence of halogen gas in the porous solid by-product salt can cause the salt to clump or bind together, thereby plugging the salt handling apparatus.
These problems are solved in the design of the present invention wherein by-product salt handling apparatus is provided for a reactor vessel for the production of a hypohalogenated acid in which the 3~ mixing and reaction of alkali metal hydroxide and a gaseous halogen occurs.
It is an object of the present invention to provide a solids discharge system for use within a system employing a reactor vessel within which a gas phase controlled reaction occurs to produce a , hypohalogenated acid.
; A
J
703~
It is another object of the present invention to provide a solid by-product salt handling apparatus for a reactor vessel in which both a liquid-gas reaction and drying occur to produce a gaseous product and the solid by-product.
It is a feature of the present invention that a gas seal is provided in the salt handliny apparatus from both the atmosphere and the system components to preclude the escape of gaseous product into the 1~ surrounding atmosphere and the intrusion of atmospheric gases into the system.
It is another feature of the present invention that the salt handling apparatus connected to reactor vessel has a valving arrangement to control the release of the by-product salt from the salt handling apparatus and minimize the amount of halogen gas and stripping air leakage.
It is still another feature of the present invention that a halogen stripper is located in the 2~ salt handling apparatus to remove any trapped gaseous halogen frorn the porous solid by product salt by the injection of air.
It is yet another feature of the present invention that the solid by-product salt can be continuously removed in dry form from the reactor vessel and the salt handling apparatus.
It is still another feature of the present invention that the gas seal is providsd by a bed or leg of salt wlthin the salt handling apparatus.
3~ It is an advantage of the present invention that the production of oversized alkali metal hydro~ide droplets are avoided and that undesirable secondary reactions are minimized, while permitting the solid by-product salt to be removed rom the system.
It is another advantage of the present invention that ~he removal of the solid by-product salt in dry form from the system provides inexpensive flexibility in the desired end use of such a product.
These and other objects, features and advantages are provided in solid discharge handling system including by-product salt handling apparatus associated with a reactor vessel for the production of a hypohalogenated acid from the mixing and reaction of 1~ an alkali metal hydroxide and gaseous halogen in the reactor vessel. The salt handling apparatus permits the continuous removal of the solids discharge from the system and specifically permits salt to be removed in dry form.
The advantages of this invention will become apparent upon consideration of the following detailed disclosure of the invention, especially when it is taken in conjunction with the drawings wherein:
FIGURE l is a side elevational view of the 2~ reactor vessel;
FIGURE 2 is a bottom perspective view of the ellipsoid inlet for the exhaust duct.
FIGURE 3 is side elevational view of the salt handling apparatus.
FIGURE l shows the reactor, indicated generally by the numeral 10, which reacts th~ uid alkali metal hydroxide, such as caustic, supplied by feed line 11 with the gaseous halogen, such as chlorine, to produce the solid salt crystals and the 3~ gaseous product, such as HOCl. Although the reactor will be discussed in terms of producing hypochlorous acid, it is to be understood that any halogen could be employed to produce hypohalogenated acid, for example, hypobromous or hypofluorous acid. Ths HOCl is -5- .
2(:~7~)3~
condensed to produce liquid hypochlorous acid which, for example, can be mixed with a lime slurry to produce calcium hypochlorite. Gaseous chlorine, along with some chlorine monoxide in the recycle system, is fed into reactor 10 via gas infeed 12 in the top 14.
Top 14 is in the shape of an inverted funn~l, that can be constructad of a suitable corrosion resistant material, such as titanium; coated titanium; an alloy of nickel, chrome, molybdenum, iron and other 1~ materials; tantalum; and lined carbon steel or lined fiberglass reinforced plastic. The lining can be a suitable polyfluoro-polymer.
Reactor vessel 15 has a perforated plate 16 at the top between the reactor top 14 and the vessel 15. The plate 16 is also made of a suitable corrosion resistant material, such as polytetrafluoroethylene or one of the above mentioned materials with respect to top 14, and serves to create a straight cocurrent flow 2~ path for the ch1orine gas flowing down from the top 14. Ethylene chlorotrifluoroethylene has also been used as a construction material for reactor vessel 15.
Vessel 15, similarly can be made from any suitable corrosion resistant material, such as carbon steel with a liner or coating of a suitable perfluoropolymer, such as that sold under the tradenarne TEFLON(R) PFA.
Reactor vessel 15 has a generally elongated cylindrical central section 18 which tapers to a conically shaped funnel bottom 19 to permit solid 3~ alkali metal halide salt, such as NaCl, product to discharge out through a standpipe, not shown, for further processing. Vessel 15 has a caustic feed line 11 that enters through its side and provides the caustic to an atomizer nozzle 21. Nozzle 21 is mounted , ~
~01~7034 along the center line 22 of the vessel 15 about six (06~ inches below the top of ve8sel 15. Nozzle 21 creates caustic droplets o~ a desired size between about 50 to 200 microns which are of sufficient size to absorb virtually all of the gaseous chlorine feed while the chlorine and caustic react fast to produce the gaseous and solid products as shown in the equation:
NaOH + C12 ? HOCl + NaCl l~\
The reaction occurs at a pH of about 4 to about 6 with a stochiometric ratio of about 30 to 1 chlorine to caustic. The gaseous HOCl is condensed between about 0 to about 10C ater e~iting the reactor to recover a concentrated HOCl solution.
Recycled gases, such as chlorine and chlorine monoxide, are exhausted from the vessel 15 through exhaust duct 24 and are fed back into reactor 10 via a recirculation loop, after passing through a heat 2~ exchanger (not shown) to achieve the necessary heat, when combined with the heat of reaction to evaporate the hypohalogenated acid, such as hypochlorous acid, and water phase to leave a dry sodium chloride or salt solid by-product. The desired reaction temperature ranges from about 80 to about 100 centigrade.
The recycled gases are also used as reactant gases in the production of the hypohalogenated acid.
The recycled gases, for example chlorine and chlorine monoxide, enter the reactor vessel lS, 3~ disperse outwardly in the inverted funnel top 14 and pass through the flow directing means or perforated plate 16 to enter the reactor vessel 15 in a generally vertical flow orientation. Fresh halogen gas, for example chlorine, is fed in through chlorine feed line 20 through the reactor top 14 and is directed down over ~ the nozzle or atomizer 21.
D7~
Nozzle 21 may be a single fluid atomizer, a two fluid nozzle or a wheel atomizer dep~ndent upon the viscosity and density of the alkali metal hydroxide being atomized and the amount of pressure to which the liquid is subjected. The materials of construction of the nozzle must be capable of withstanding the harshness ~f the environment within the reactor.
The vessel 15 has an outlet or exhaust duct 24 at the bottom of the dryiny zone 26 just above the 1~ funnel or conically shaped bottom 19 to remove the product gas, the unreacted halogen gas and some by-product into the recirculation loop as previously described. Outlet or exhaust duct 24 exits through the side of vessel 15 generally horizontally and has an inlet 28 that is undercut such that the top overhangs or overlies and covers the bottom to preclude solid alkali metal chloride by-product, for example sodium chloride, from falling directly into it. The preferred shape of the inlet 28 is an undercut ellipsoid, as seen 2~ in FIGURE 2.
The vessel 15 has its central section 18 preferably cylindrically shaped, but it could also be polygonal, as appropriate. The cylindrical lesign has a desired diameter and length. The length extends from the top at the perforated plate 16 to the bottorn oE the drying zone 26, just above the fl~nnel bottom 19. The dimensions of the length and the diameter can be selected so that the length to diameter ratio, l/d, can range from about 1 to 1 to about 1 to 5.
3~ In operation the halogen gas, for e~ample chlorine, is fed into the reactor 10 through feed line 20 and is directed generally vertically downward over nozzle 21. Recycled yases are fed in from the recirculation system via gas infeed 12 into the reactor 3~
top 14 and are directionalized by perforated plate 16 down into reactor vessel 15. Vessel 15 has an elongate cylindrical section 18 which has a spraying and drying zone 25 adjacent the top surrounding nozzle 21 and a drying zone 26 therebelow.
The reacted gases e~it the reactor 10 through outlet or exhaust duct 24 for processing and recirculation, as appropxiate. The solid by-product alkali metal halide, such as sodium chloride, e~its the 1~ vessel 15 through the conically shaped funnel bottom 19 for processing. Bottom 19 is connected by conventional flanging to connecting pipes (not shown).
The solid by-product alkali metal halogen is dried as it passes down through the drying zone 26.
The overhanging top portion of exhaust duct 24 prevents substantial quantities of the solid by-product from being drawn out through the undercut ellipsoid inlet 28 with the product HOCl gas and the recycle gases.
Figure 3 shows the solids discharge handling 2~ apparatus preferably for granular solids indicated generally by the numeral 45, connected to the bottom 19 of reactor vessel 15 via connecting pipe 20. Pipe 20 is connected to the salt handling standpipe 29 by flanges 44.
Solid salt by-product is retained in the standpipe 29 by valve means 41 that selectively discharges the dry by-product while ensuring sufficient quantity of solid salt by-product remains in the solids discharge handling apparatus 45 to maintain a seal to 3~ the atmosphere, as previously described. Apparatus 45 initially can be seeded with the required amount of solid by-product to establish the seal. Valve means 41 can be any appropriate system that is halogen impervious and suitably sealable to prevent the escape 200t7~3g~
of the gaseous product to the surrounding atmosphere and the intrusion of atmospheric gases into the system. A double valve airlock system has been employed using, for example, a disk valve and a knife valve.
The desired by-product salt level within the standpipe 29 is shown by numeral 31. This is at the level or height of level controller 30 that has a feed-forward connection to the valve means 41 to signal when the valve means 41 should be opened for discharge. Level controller 30 can be a microwave level transmitter~sensor, as well as a point level probe. One method of employing the feed forward system has employed a solenoid valve as a pneumatic control for the opening or closiny of valve means 41.
A stripping section, indicated generally by the numeral 33, is connected to standpipe 29 by a standpipe annulus 32. Annulus 32 consists of a standpipe jacket 35 that is appropriately fastened to 2~ standpipe 29, such as by welding, and four exhaust ports 34 90 apart in jacket 35 for carrying chlorine gas and air to an exhaust manifold and scrubber (both not shown). Stripper pipe 36 inserts within the lower outwardly tapered portion of standpipe jacket 3S to thereby form an annular chamber 37 from which the chlorine and gas mixture is drawn off as a result of a negative pressure system through the scrubber.
Stripping section 33 includes vertically extending stripper pipe 36, stripper jacket 38 that 3~ extends about the periphery of pipe 36, stripper air inlet 39 and perforated pipe sidewall section 40.
Stripping air is forced into the jac~et 38 under pressure and is distributed into the solid salt by-product by the perforati~ns in the sidewall of pipe --10-- , :., Z1~7~3~
36 within the jacket 38. A 2-5 inch water pressure drop across the bed of salt in standpipes 29 and 36 ensures 9OOa stripping of gases from the solid by-product salt. Flow and pressure meters can be employed to measure this pressure drop to verify that successful stripping is occurring. The stripping air ideally is introduced to the jacket 38 through a dessicant to avoid the introduction of moisture into salt. The porous solid salt by-product must be 1~ stripped of halogen, such as chlorine, because of the tendency of the halogenated salt to clump together and clog the standpipe and the handling apparatus.
Stripper pipe 36 is fastened with a gas tight seal via flange 42 to valve means 41.
The solids discharge handling apparatus could equally well be connected to a cyclone separator ~not shown) employed within the process system to separate out solids.
While the preferred structure in which the 2~ principles of the present invention have been incorporated is shown and described above, it is to be understood that the invention is not to be limited to the particular details thus presented, but, in fact, widely different means may be employed in the practice of the broader aspects of this invention. The scope of the appended claims is intended to encompass all obvious changes in the details, materials, and arrangement of parts which will occur to one of skill in the art upon a reading of the disclosure.
,, .,
~ALT HANDLING ~PP~RA'~S FOR ~ HY~OC~LOROUS ACIP REACTQ~
This invention relates generally to the solids discharge handling apparatus associated with a reactor vessel system and, more specifically to that apparatus associated with a reactor vessel for the production of hypohalo~enated acid by the mixing and reaction therein of an alkali metal hydroxide and a gaseous halogen. A preferred product acid is hypochlorous acid.
1~ Hypochlorous acid is used extensively in the preparation o chlorohydrin and chlorarnines.
Chloroisocyanurates are typical examples. Hypochlorous acid has been produced by several processes or techniques. The use of dilute hypochlorous acid and large quantities of halogen to produce hypohalites, such as sodium hypochlorite, is recent.
One technique employs the process in which chlorine, steam and air are bubbled through ~n aqueous solution of an alkali earth metal hypochlorite, such as 2~ calcium hypochlorite, to remove the resultiny hypochlorous acid in vapor form. The hypochlorous acid -1- ~.' , æ()~703~
is then condensed and stored for use. This process, however, produces a large volume of undesirable by-product, calcium chloride.
Another process uses a low concentration of aqueous caustic solution to scrub chlorine gas.
However, the solution has an available chlorine content of about only 5% and, because of the chloride ion content, the hypochlorous acid that is formed quickly decomposes, most preferably to chloric acid.
1~ Another related process prepares a solid mixture of alkali metal hypochlorite and alkali metal chloride by reacting chlorine gas with a spray of alkali metal hydroxide, while drying with a gas the reactants and product. Some cooling of the reacting chemicals and the drying gas may be done. The primary products of this process have very limited utility.
A more recent process, which produces hypochlorous acid vapor, sprays aqueous alkali metal hydroxide in droplet form or solid alkali metal 2~ hydroxide particles into gaseous chlorine. This approach attempts to utilize droplet sizes to attain the ma~imum surface to volume ratio possible. Droplets having an average diameter of less than about 1000 rnicrons are employed.
These previous processes, and the apparatus employed to produce these processes, have suffered from not achieving substantially complete reactions between the chlorine and the alkali metal hydroxide. A
critical factor in determining the complete reaction is 3~ the droplet size of the alkali metal hydroxide. It is also desirable that any hypochlorous acid produced and any water present be readily vaporizable. The salt particles produced as by-products in any process should be dry to facilitate handling and be continuously 20Q~7034 removable from the reaction while maintaining a seal to the atmosphere to prevent the gaseous product from escaping to the surrounding area and to prevent atmospheric gases from mi~ing with the gaseous product. The increased concentration of water and inert gases such as oxygen and nitrogen, in the reactor system when atmospheric gases intrude reduces the operating efficiency of the system. The salt particles should be sized so that they readily separate from the 1~ gaseous product mixture of hypochlorous acid.
Prior processes have produced oversized alkali metal hydroxide droplets that result in the undesired reaction of hypochlorous acid and the oversized particles to produce significant alkali metal chlorates. These oversized particles then retain excessive moisture so that caking results and the caked mass adheres to the reactor surfaces. These oversized particles can hamper the byproduct salt removal additionally. The presence of such alkali metal 2~ chlorates reflect reduced yields of the desired hypochlorous acid, while increasing the raw material and operatiny costs. Lastly, the presence of halogen gas in the porous solid by-product salt can cause the salt to clump or bind together, thereby plugging the salt handling apparatus.
These problems are solved in the design of the present invention wherein by-product salt handling apparatus is provided for a reactor vessel for the production of a hypohalogenated acid in which the 3~ mixing and reaction of alkali metal hydroxide and a gaseous halogen occurs.
It is an object of the present invention to provide a solids discharge system for use within a system employing a reactor vessel within which a gas phase controlled reaction occurs to produce a , hypohalogenated acid.
; A
J
703~
It is another object of the present invention to provide a solid by-product salt handling apparatus for a reactor vessel in which both a liquid-gas reaction and drying occur to produce a gaseous product and the solid by-product.
It is a feature of the present invention that a gas seal is provided in the salt handliny apparatus from both the atmosphere and the system components to preclude the escape of gaseous product into the 1~ surrounding atmosphere and the intrusion of atmospheric gases into the system.
It is another feature of the present invention that the salt handling apparatus connected to reactor vessel has a valving arrangement to control the release of the by-product salt from the salt handling apparatus and minimize the amount of halogen gas and stripping air leakage.
It is still another feature of the present invention that a halogen stripper is located in the 2~ salt handling apparatus to remove any trapped gaseous halogen frorn the porous solid by product salt by the injection of air.
It is yet another feature of the present invention that the solid by-product salt can be continuously removed in dry form from the reactor vessel and the salt handling apparatus.
It is still another feature of the present invention that the gas seal is providsd by a bed or leg of salt wlthin the salt handling apparatus.
3~ It is an advantage of the present invention that the production of oversized alkali metal hydro~ide droplets are avoided and that undesirable secondary reactions are minimized, while permitting the solid by-product salt to be removed rom the system.
It is another advantage of the present invention that ~he removal of the solid by-product salt in dry form from the system provides inexpensive flexibility in the desired end use of such a product.
These and other objects, features and advantages are provided in solid discharge handling system including by-product salt handling apparatus associated with a reactor vessel for the production of a hypohalogenated acid from the mixing and reaction of 1~ an alkali metal hydroxide and gaseous halogen in the reactor vessel. The salt handling apparatus permits the continuous removal of the solids discharge from the system and specifically permits salt to be removed in dry form.
The advantages of this invention will become apparent upon consideration of the following detailed disclosure of the invention, especially when it is taken in conjunction with the drawings wherein:
FIGURE l is a side elevational view of the 2~ reactor vessel;
FIGURE 2 is a bottom perspective view of the ellipsoid inlet for the exhaust duct.
FIGURE 3 is side elevational view of the salt handling apparatus.
FIGURE l shows the reactor, indicated generally by the numeral 10, which reacts th~ uid alkali metal hydroxide, such as caustic, supplied by feed line 11 with the gaseous halogen, such as chlorine, to produce the solid salt crystals and the 3~ gaseous product, such as HOCl. Although the reactor will be discussed in terms of producing hypochlorous acid, it is to be understood that any halogen could be employed to produce hypohalogenated acid, for example, hypobromous or hypofluorous acid. Ths HOCl is -5- .
2(:~7~)3~
condensed to produce liquid hypochlorous acid which, for example, can be mixed with a lime slurry to produce calcium hypochlorite. Gaseous chlorine, along with some chlorine monoxide in the recycle system, is fed into reactor 10 via gas infeed 12 in the top 14.
Top 14 is in the shape of an inverted funn~l, that can be constructad of a suitable corrosion resistant material, such as titanium; coated titanium; an alloy of nickel, chrome, molybdenum, iron and other 1~ materials; tantalum; and lined carbon steel or lined fiberglass reinforced plastic. The lining can be a suitable polyfluoro-polymer.
Reactor vessel 15 has a perforated plate 16 at the top between the reactor top 14 and the vessel 15. The plate 16 is also made of a suitable corrosion resistant material, such as polytetrafluoroethylene or one of the above mentioned materials with respect to top 14, and serves to create a straight cocurrent flow 2~ path for the ch1orine gas flowing down from the top 14. Ethylene chlorotrifluoroethylene has also been used as a construction material for reactor vessel 15.
Vessel 15, similarly can be made from any suitable corrosion resistant material, such as carbon steel with a liner or coating of a suitable perfluoropolymer, such as that sold under the tradenarne TEFLON(R) PFA.
Reactor vessel 15 has a generally elongated cylindrical central section 18 which tapers to a conically shaped funnel bottom 19 to permit solid 3~ alkali metal halide salt, such as NaCl, product to discharge out through a standpipe, not shown, for further processing. Vessel 15 has a caustic feed line 11 that enters through its side and provides the caustic to an atomizer nozzle 21. Nozzle 21 is mounted , ~
~01~7034 along the center line 22 of the vessel 15 about six (06~ inches below the top of ve8sel 15. Nozzle 21 creates caustic droplets o~ a desired size between about 50 to 200 microns which are of sufficient size to absorb virtually all of the gaseous chlorine feed while the chlorine and caustic react fast to produce the gaseous and solid products as shown in the equation:
NaOH + C12 ? HOCl + NaCl l~\
The reaction occurs at a pH of about 4 to about 6 with a stochiometric ratio of about 30 to 1 chlorine to caustic. The gaseous HOCl is condensed between about 0 to about 10C ater e~iting the reactor to recover a concentrated HOCl solution.
Recycled gases, such as chlorine and chlorine monoxide, are exhausted from the vessel 15 through exhaust duct 24 and are fed back into reactor 10 via a recirculation loop, after passing through a heat 2~ exchanger (not shown) to achieve the necessary heat, when combined with the heat of reaction to evaporate the hypohalogenated acid, such as hypochlorous acid, and water phase to leave a dry sodium chloride or salt solid by-product. The desired reaction temperature ranges from about 80 to about 100 centigrade.
The recycled gases are also used as reactant gases in the production of the hypohalogenated acid.
The recycled gases, for example chlorine and chlorine monoxide, enter the reactor vessel lS, 3~ disperse outwardly in the inverted funnel top 14 and pass through the flow directing means or perforated plate 16 to enter the reactor vessel 15 in a generally vertical flow orientation. Fresh halogen gas, for example chlorine, is fed in through chlorine feed line 20 through the reactor top 14 and is directed down over ~ the nozzle or atomizer 21.
D7~
Nozzle 21 may be a single fluid atomizer, a two fluid nozzle or a wheel atomizer dep~ndent upon the viscosity and density of the alkali metal hydroxide being atomized and the amount of pressure to which the liquid is subjected. The materials of construction of the nozzle must be capable of withstanding the harshness ~f the environment within the reactor.
The vessel 15 has an outlet or exhaust duct 24 at the bottom of the dryiny zone 26 just above the 1~ funnel or conically shaped bottom 19 to remove the product gas, the unreacted halogen gas and some by-product into the recirculation loop as previously described. Outlet or exhaust duct 24 exits through the side of vessel 15 generally horizontally and has an inlet 28 that is undercut such that the top overhangs or overlies and covers the bottom to preclude solid alkali metal chloride by-product, for example sodium chloride, from falling directly into it. The preferred shape of the inlet 28 is an undercut ellipsoid, as seen 2~ in FIGURE 2.
The vessel 15 has its central section 18 preferably cylindrically shaped, but it could also be polygonal, as appropriate. The cylindrical lesign has a desired diameter and length. The length extends from the top at the perforated plate 16 to the bottorn oE the drying zone 26, just above the fl~nnel bottom 19. The dimensions of the length and the diameter can be selected so that the length to diameter ratio, l/d, can range from about 1 to 1 to about 1 to 5.
3~ In operation the halogen gas, for e~ample chlorine, is fed into the reactor 10 through feed line 20 and is directed generally vertically downward over nozzle 21. Recycled yases are fed in from the recirculation system via gas infeed 12 into the reactor 3~
top 14 and are directionalized by perforated plate 16 down into reactor vessel 15. Vessel 15 has an elongate cylindrical section 18 which has a spraying and drying zone 25 adjacent the top surrounding nozzle 21 and a drying zone 26 therebelow.
The reacted gases e~it the reactor 10 through outlet or exhaust duct 24 for processing and recirculation, as appropxiate. The solid by-product alkali metal halide, such as sodium chloride, e~its the 1~ vessel 15 through the conically shaped funnel bottom 19 for processing. Bottom 19 is connected by conventional flanging to connecting pipes (not shown).
The solid by-product alkali metal halogen is dried as it passes down through the drying zone 26.
The overhanging top portion of exhaust duct 24 prevents substantial quantities of the solid by-product from being drawn out through the undercut ellipsoid inlet 28 with the product HOCl gas and the recycle gases.
Figure 3 shows the solids discharge handling 2~ apparatus preferably for granular solids indicated generally by the numeral 45, connected to the bottom 19 of reactor vessel 15 via connecting pipe 20. Pipe 20 is connected to the salt handling standpipe 29 by flanges 44.
Solid salt by-product is retained in the standpipe 29 by valve means 41 that selectively discharges the dry by-product while ensuring sufficient quantity of solid salt by-product remains in the solids discharge handling apparatus 45 to maintain a seal to 3~ the atmosphere, as previously described. Apparatus 45 initially can be seeded with the required amount of solid by-product to establish the seal. Valve means 41 can be any appropriate system that is halogen impervious and suitably sealable to prevent the escape 200t7~3g~
of the gaseous product to the surrounding atmosphere and the intrusion of atmospheric gases into the system. A double valve airlock system has been employed using, for example, a disk valve and a knife valve.
The desired by-product salt level within the standpipe 29 is shown by numeral 31. This is at the level or height of level controller 30 that has a feed-forward connection to the valve means 41 to signal when the valve means 41 should be opened for discharge. Level controller 30 can be a microwave level transmitter~sensor, as well as a point level probe. One method of employing the feed forward system has employed a solenoid valve as a pneumatic control for the opening or closiny of valve means 41.
A stripping section, indicated generally by the numeral 33, is connected to standpipe 29 by a standpipe annulus 32. Annulus 32 consists of a standpipe jacket 35 that is appropriately fastened to 2~ standpipe 29, such as by welding, and four exhaust ports 34 90 apart in jacket 35 for carrying chlorine gas and air to an exhaust manifold and scrubber (both not shown). Stripper pipe 36 inserts within the lower outwardly tapered portion of standpipe jacket 3S to thereby form an annular chamber 37 from which the chlorine and gas mixture is drawn off as a result of a negative pressure system through the scrubber.
Stripping section 33 includes vertically extending stripper pipe 36, stripper jacket 38 that 3~ extends about the periphery of pipe 36, stripper air inlet 39 and perforated pipe sidewall section 40.
Stripping air is forced into the jac~et 38 under pressure and is distributed into the solid salt by-product by the perforati~ns in the sidewall of pipe --10-- , :., Z1~7~3~
36 within the jacket 38. A 2-5 inch water pressure drop across the bed of salt in standpipes 29 and 36 ensures 9OOa stripping of gases from the solid by-product salt. Flow and pressure meters can be employed to measure this pressure drop to verify that successful stripping is occurring. The stripping air ideally is introduced to the jacket 38 through a dessicant to avoid the introduction of moisture into salt. The porous solid salt by-product must be 1~ stripped of halogen, such as chlorine, because of the tendency of the halogenated salt to clump together and clog the standpipe and the handling apparatus.
Stripper pipe 36 is fastened with a gas tight seal via flange 42 to valve means 41.
The solids discharge handling apparatus could equally well be connected to a cyclone separator ~not shown) employed within the process system to separate out solids.
While the preferred structure in which the 2~ principles of the present invention have been incorporated is shown and described above, it is to be understood that the invention is not to be limited to the particular details thus presented, but, in fact, widely different means may be employed in the practice of the broader aspects of this invention. The scope of the appended claims is intended to encompass all obvious changes in the details, materials, and arrangement of parts which will occur to one of skill in the art upon a reading of the disclosure.
,, .,
Claims (15)
1. A reactor vessel system including a reactor (10) having a top (22) and an opposing bottom (19), for the production of a gaseous product and a solid by-product from the mixing and reaction of an alkali metal hydroxide and a gaseous halogen characterized by solids discharge handling apparatus (45) connected to the opposing bottom (19) of the reactor (10) at the top of the apparatus and having a valve means (41) at the bottom to selectively control the release of solids from the apparatus (45), the apparatus including a stripping section (33) to remove gas from the solids within the apparatus and a seal formed by the solids within the apparatus to prevent the intrusion of atmospheric gases and the escape of the gaseous product and the gaseous halogen.
2. The apparatus according to Claim 1 characterized in that the valve means (41) in the solids discharge handling apparatus further includes a double airlock system.
3. The apparatus according to Claim 2 characterized in that the stripping section (33) includes a generally elongated vertically extending stripper pipe (36) that has a lower portion about the periphery of which extends a jacket (38) that is pervious to a stream of stripping air.
4. The apparatus according to Claim 3 characterized in that the stripper pipe (36) beneath the jacket (38) has a perforated sidewall (40) through which the stream of stripping air is distributed into the solids forming the seal within the stripper pipe (36).
5. The apparatus according Claim 4 characterized in that the stripper pipe (36) has an upper portion about which extends an annulus (32) that connects the stripper pipe to the top of the solids discharge handling apparatus (45).
6. The apparatus according to Claim 5 characterized in that the top of the solids discharge handling apparatus (45) further comprises an elongated generally vertically extending standpipe (29).
7. The apparatus according to Claim 6 in characterized in that the annulus (32) has a stripping air outlet (34) and the jacket (38) has a stripping air inlet (39) to direct flow of the stream of striping air into and out of the stripping section (33).
8. The apparatus according to Claim 1 characterized in that the seal formed by the solids is retained in place by the valve means (41) and builds in height vertically within the solids discharge handling apparatus (45) as the reactor (10) produces solid by-product.
9. The apparatus according to Claim 8 characterized in that a level controller (30) is used to measure the level of the solids in the solids discharge handling apparatus.
10. The apparatus according to Claim 9 characterized in that the level controller (30) senses the level of the solids and signals the valve means (41) to discharge solids from the solids discharge handling apparatus (45).
11. The apparatus according to Claim 10 characterized in that the reactor (10) further comprises gaseous halogen infeed means (20) above alkali metal hydroxide indeed means (11) and flow directing means (16) below the gaseous halogen infeed means (20) to direct the gaseous halogen into the alkali metal hydroxide.
12. The apparatus according to Claim 11 characterized in that the reactor (10) further comprises a spraying and reaction zone (25) beneath the alkali metal hydroxide infeed means (21).
13. The apparatus according to Claim 12 characterized in that the reactor (10) further comprises a drying zone (26) beneath the spraying and reaction zone (25) to dry the reaction products.
14. The apparatus according to Claim 13 characterized in that the gaseous product produced in the reactor (10) is a hypohalogenated acid.
15. The apparatus according to claim 14 characterized in that the solid by-product produced in the reactor (10) is an alkali metal halide salt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US29372789A | 1989-01-05 | 1989-01-05 | |
US293,727 | 1989-01-05 |
Publications (1)
Publication Number | Publication Date |
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CA2007034A1 true CA2007034A1 (en) | 1990-07-05 |
Family
ID=23130313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002007034A Abandoned CA2007034A1 (en) | 1989-01-05 | 1990-01-03 | Salt handling apparatus for a hypochlorous acid reactor |
Country Status (4)
Country | Link |
---|---|
CN (1) | CN1046139A (en) |
AU (1) | AU5049190A (en) |
CA (1) | CA2007034A1 (en) |
WO (1) | WO1990007370A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1995014636A1 (en) * | 1993-11-23 | 1995-06-01 | The Dow Chemical Company | Manufacture of low-chlorides hypochlorous acid |
CN105879798A (en) * | 2016-05-23 | 2016-08-24 | 张�浩 | Gas-liquid flash reaction process |
CN110508180B (en) * | 2019-08-27 | 2021-10-29 | 广州泰道安医疗科技有限公司 | Production process of chlorine-containing disinfectant fluid |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4146578A (en) * | 1977-12-27 | 1979-03-27 | Olin Corporation | Hypochlorous acid process |
US4527714A (en) * | 1983-02-18 | 1985-07-09 | White River Technologies, Inc. | Pressure responsive hopper level detector system |
JPS62129164A (en) * | 1985-11-28 | 1987-06-11 | Mitsui Toatsu Chem Inc | Method for separating polymer powder and carrier gas |
US4853003A (en) * | 1987-09-18 | 1989-08-01 | Shell Oil Company | Removal of particulates from synthesis gas |
-
1990
- 1990-01-02 AU AU50491/90A patent/AU5049190A/en not_active Abandoned
- 1990-01-02 WO PCT/US1990/000076 patent/WO1990007370A1/en unknown
- 1990-01-03 CA CA002007034A patent/CA2007034A1/en not_active Abandoned
- 1990-01-05 CN CN90100743A patent/CN1046139A/en active Pending
Also Published As
Publication number | Publication date |
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AU5049190A (en) | 1990-08-01 |
WO1990007370A1 (en) | 1990-07-12 |
CN1046139A (en) | 1990-10-17 |
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