Process for producing chlorine dioxide
18 claims: 15 independent, 3 dependent
- 1Zastrzeżenia patentowe 1. Sposób ciągłego wytwarzania dwutlenku chloru polegający na dostarczeniu do reaktora jonów chloranowych, kwasu i nadtlenku wodoru jako roztworów wodnych, zredukowaniu jonów chloranowych w reaktorze do dwutlenku chloru, z utworzeniem w reaktorze strumienia produktu zawierającego dwutlenek chloru, dostarczeniu wody przemysłowej do pompy strumieniowej parowej zawierającej dyszę, doprowadzeniu do przepływu wody przemysłowej przez dyszę i spowodowaniu ponadto jej przepływu przez pompę strumieniową parową, PL 200 136 B1 przeniesieniu strumienia produktu z reaktora do pompy strumieniowej parowej i zmieszaniu go z wodą przemysłową z wytworzeniem rozcieńczonego roztworu wodnego zawierającego dwutlenek chloru, i usunięciu rozcieńczonego roztworu wodnego zawierającego dwutlenek chloru z pompy strumieniowej parowej, znamienny tym, że powoduje się przepływ wody przemysłowej przez dyszę dla dalszego przepływu przez pompę strumieniową parową w sposób zasadniczo spiralny lub śrubowy.
- 2Sppsób weeług zastrz. 1, zr^c^r^i^r^^yy tym, że powoduje się ponaato przzpływ wocty przemysłowej przez pompę strumieniową parową w sposób zasadniczo spiralny lub śrubowy.
- 3Spooch wedłuu zaas^. 1 albo 2, zr^c^r^i^^r^yr tym, że doprowaada sśę do μ^θρ^^νο wody przemysłowej w przynajmniej częściowo spiralny lub śrubowy sposób za pomocą skręconych łopatek umieszczonych wewnątrz lub przed dyszą w pompie strumieniowej parowej.
- 4wedłuu zas^z. 1 albo 2, znamienny tym, że doprowaada sśę do wody przemysłowej w przynajmniej częściowo spiralny lub śrubowy sposób za pomocą wewnętrznego gwintowania wewnątrz lub przed dyszą w pompie strumieniowej parowej.
- 5Sppsób w^dtuuj zzate. 1 albo 2, z^c^r^i^r^oyr tym, 1ż ppmpa strzmieniowa parowa z^s^i ^-^ ponadto, w kierunku przepływu z dyszy, komorę ssącą, do której przenosi się z reaktora strumień produktu, i element zwężkowy, przez który usuwa się rozcieńczony roztwór wodny zawierający dwutlenek chloru.
- 6Sppsóó waeług zzasz. 1, zrinmieenn tym, żż 1esa chlo-zsawa dostarzcz sięZo 1zeSto-z ^Ιο roztwór wodny zawierający chloran metalu, a kwas dostarcza się do reaktora jako kwas nieorganiczny.
- 7Sposób według zastrz. 6, znamienny ty,, że kwasem nieorganicznym jest kwas siarkowy.
- 8Sppsób waeług zzssrz. 6, zznmieeny tym, że chloras ipp-oIu zlkoliccmeo i π^ι^ΟΙ^-^^-. wwdoru dostarcza się do reaktora w postaci wstępnie zmieszanego roztworu wodnego.
- 9Sposób wedU-iu zzssrz. 8, znamieenY tym, Zż watoęaie zmiedózsa 1zotwar wc^Oun zzwiera od około 1 do około 6,5 moli/dm 3 chloranu metalu alkalicznego, od około 1 do około 7 moli/dm 3 nadtlenku wodoru, co najmniej jeden spośród koloidu ochronnego, zmiatacza rodnikowego i środka kompleksującego na bazie kwasu fosfonowego oraz ma pH od około 0,5 do około 4.
- 10Sppoóó waełιłg zzssrz. z zlbb 6, zlbb 8, zlbb 9, zznmieenn tym, żż i boć jjonw zhlo-Zowayh dostarczana do reaktora wynosi poniżej około jednego % molowego Cl' z ClO3 _ .
- 11Spooób weełuu zas^z. 1, znnmiennn tym, ż^ s^umień produktu w reaktooze zawierającc dwutlenek chloru jest cieczą i pianą.
- 12według zas^z. 1, znamienny tym, że tempe-aStKę w reaktooze ιgrzymιge się od około 30 do około 60°C.
- 13SsPOóówaeOłg zzsSz. z 1 z znmieenn tym, żż w roeStooze zurz^z^r^L^^^ sśę ziśśierie zaoólujrιa od około 30 do około 100 kPa.
- 14Sppośó waeług zzaSz. z zllb z, zllb z, zllb 1 zllb z2, zllb z3, zznmieenn tym, zż jjSo reaktor stosuje się zasadniczo przelotowy, rurowy zbiornik lub przewód rurowy.
- 15Sposób według zastrz. 14, znamienny yy,, że reaktor umieszcza się zasadniczo pionowo.
- 16Sposób według zastrz. 14, znamienny yy,, że reaktor zawiera tarczę lub podobny element zaopatrzoną w otwory i umieszczoną wewnątrz reaktora, a chloran metalu i nadtlenek wodoru dostarcza się za tarczą, natomiast kwas dostarcza się przed tarczą i doprowadza się do przepływu przez otwory, a następnie miesza się z chloranem metalu i nadtlenkiem wodoru.
- 17Sposób według zastrz. 15, znamienny yy,, że główny kierunek przepływu jest ku górze.
- 18Urządzenie do ciągłego wytwarzania dwutlenku chloru zawierające reaktor zaopatrzony w linie zasilające dla jonów chloranowych, nadtlenku wodoru i kwasu, przy czym reaktor połączony jest z pompą strumieniową parową zaopatrzoną w dyszę do wody przemysłowej, znamienne yy,, że reaktor i pompa strumieniowa parowa są z materiału odpornego na nadtlenek wodoru, chloran sodowy, kwas siarkowy i dwutlenek chloru, a ponadto tym, że zawiera ono elementy powodujące dalszy przepływ wody przemysłowej przez pompę strumieniową parową w przynajmniej częściowo spiralny lub śrubowy sposób.
Independent claims18
60 paragraphs in 1 section, as filed
Description of the invention
The present invention relates to a method and an apparatus for the continuous production of chlorine dioxide.
It is a method and device for the production of chlorine dioxide from chlorate ions, acid and hydrogen peroxide.
Chlorine dioxide is used in a variety of applications such as pulp bleaching, fat bleaching, water purification, and the removal of organic material from industrial waste. Since chlorine dioxide is not storage stable, it must be produced on site.
Chlorine dioxide is usually produced by reacting an alkali metal chlorate or chloric acid with a reducing agent in an aqueous reaction medium. Chlorine dioxide can be removed from the reaction medium as a gas as described in US Pat. 5,091,166, 5,091,167 and EP 612686. Typically the gaseous chlorine dioxide is then absorbed in water to form an aqueous solution thereof.
In the production of chlorine dioxide in small scale units, such as water treatment plants or small bleaching plants, it is preferable not to separate the chlorine dioxide gas from the reaction medium, but to obtain the chlorine dioxide containing solution directly from the reactor, possibly after dilution with water. Such methods are described in US Pat. In Americas 2833624, 4534952, 5895638 and in WO 00/76916, and in recent years they have become used. However, there is still room for further improvement. In particular, it has been found difficult to obtain solutions with a sufficiently high concentration of chlorine dioxide as required for certain applications such as recycled paper bleaching, bagasse bleaching or small scale pulp bleaching. A high concentration of chlorine dioxide can also be useful in any application where it is important to reduce the water flow.
The object of the invention is to provide a process that enables the direct production of chlorine dioxide in a high concentration aqueous solution.
Another object of the invention is to provide a process for the direct production of chlorine dioxide in an aqueous solution with high production capacity.
Yet another object of the invention is to provide a device for carrying out the method.
A method of continuous production of chlorine dioxide consisting in supplying the reactor with chlorate ions, acid and hydrogen peroxide as aqueous solutions, reducing chlorate ions in the chlorine dioxide reactor, creating a product stream containing chlorine dioxide in the reactor, supplying industrial water to a steam jet pump containing a nozzle, making process water flow through the nozzle and further causing it to flow through the steam jet pump, transferring the product stream from the reactor to the steam jet pump and mixing it with the process water to form a dilute aqueous solution containing chlorine dioxide, and removing the dilute aqueous solution containing chlorine dioxide from a steam jet pump, according to the invention, is characterized by that the process water is caused to flow through the nozzle for further flow through the steam jet pump in a substantially helical or helical manner.
Furthermore, the process water is preferably caused to flow through the steam jet pump in a substantially helical or helical manner.
Preferably, the process water is brought to flow in an at least partially helical or helical manner by means of twisted blades arranged inside or in front of the nozzle in a steam jet pump.
The process water is preferably brought to the flow in an at least partially helical or helical manner by means of internal threading inside or upstream of the nozzle in a steam jet pump.
Preferably, the steam jet pump further comprises, downstream of the nozzle, a suction chamber into which the product stream is transferred from the reactor, and an orifice device through which the dilute aqueous solution containing chlorine dioxide is removed.
Preferably, the chlorate ions are fed to the reactor as an aqueous solution containing metal chlorate, and the acid is fed to the reactor as inorganic acid.
Preferably, the inorganic acid is sulfuric acid.
Preferably, the alkali metal chlorate and hydrogen peroxide are fed to the reactor as a pre-mixed aqueous solution.
PL 200 136 B1
Preferably, the premixed aqueous solution contains from about 1 to about 6.5 moles / dm<sup>3</sup> alkali metal chlorate, from about 1 to about 7 moles / dmr<sup>3</sup> hydrogen peroxide, at least one of a protective colloid, a radical scavenger, and a phosphonic acid complexing agent, and has a pH of from about 0.5 to about 4.
Preferably, the amount of chloride ions supplied to the reactor is less than about one mole% of Cl from ClO3<sup>_</sup>.
Preferably, the product stream in the reactor containing chlorine dioxide is a liquid and a foam.
Preferably, the temperature in the reactor is maintained at about 30 to about 60 ° C.
Preferably, the reactor is maintained at an absolute pressure of from about 30 to about 100 kPa absolute.
Preferably, an essentially straight-through tubular vessel or tubing is used as the reactor.
Preferably the reactor is placed substantially vertically.
Preferably, the reactor comprises a target or the like provided with holes and positioned inside the reactor, and the metal chlorate and hydrogen peroxide are supplied behind the target, and the acid is supplied in front of the target and fed through the holes, and then mixed with the metal chlorate and hydrogen peroxide. .
Preferably, the main flow direction is upward.
A device for the continuous production of chlorine dioxide comprising a reactor provided with feed lines for chlorate ions, hydrogen peroxide and acid, the reactor being connected to a steam jet pump provided with an industrial water nozzle, and the invention is characterized in that the reactor and the steam jet pump are made of a material resistant to hydrogen peroxide, sodium chlorate, sulfuric acid and chlorine dioxide, and moreover, that it comprises means for causing the process water to continue to flow through the steam jet pump in an at least partially helical or helical manner.
The chlorate ions may be supplied to the reactor as an aqueous solution containing chloric acid and / or a metal chlorate, preferably an alkali metal chlorate. The alkali metal can be, for example, sodium, potassium or mixtures thereof, sodium being the most preferred. If chloric acid is not used, another acid should be fed to the reactor, preferably an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid, of which sulfuric acid is most preferred. The mole ratio of H 2 O 2 to CO 3 supplied to the reactor is suitable in the range from about 0.2: 1 to about 2: 1, preferably from about 0.5: 1 to about 1.5: 1, most preferably from about 0.5: 1 to about 1: 1. Metal chlorate and chloric acid always contain some chloride as impurity, but it is entirely possible to feed more chloride into the reactor, such as metal chloride or hydrochloric acid. However, to minimize chlorine formation, it is preferable to keep the amount of chloride ions supplied to the reactor low, suitably less than about 1 mole%, preferably less than about 0.1 mole%, more preferably less than about 0.05 mole%, most preferably less than about 1 mole%. than about 0.02 mole% of Cl from ClO3.
In a particularly preferred embodiment of the invention, the alkali metal chlorate and hydrogen peroxide are supplied to the reactor in the form of a pre-mixed aqueous solution, for example the composition described in WO 00/76916. Such a composition may be an aqueous solution containing from about 1 to about 6.5 mol / L<sup>3</sup>, preferably from about 3 to about 6 moles / dmr<sup>3</sup> alkali metal chlorate, from about 1 to about 7 moles / dmF, preferably from about 3 to about 5 moles / dmF hydrogen peroxide, and at least one of a protective colloid, radical scavenger and complexing agent based on phosphonic acid, the pH of the aqueous solution being suitably from about 0.5 to about 4, preferably from about 1 to about 3.5, most preferably from about 1.5 to about 3. Preferably at least one phosphonic acid complexing agent is present, preferably in an amount from about 0.1 to about 5 mmol / dmr.<sup>3</sup>, most preferably from about 0.5 to about 3 mmol / L. If a protective colloid is present, its concentration is preferably from about 0.001 to about 0.5 moles / L, most preferably from about 0.02 to about 0.05 moles / L. When a radical scavenger is present, its concentration is preferably from about 0.01 to about 1 mole / liter, most preferably from about 0.02 to about 0.2 mole / liter. Particularly preferred compositions contain at least one phosphonic acid complexing agent selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra acid ( methylenephosphonic acid), hexamethylene diaminetetra (methylenephosphonic acid), diethylene triamine penta (methylenephosphonic acid), diethylenetriaminohexa (methylenephosphonic acid) and 1-aminoalkane-1,1-diphosphonic acids such as morpholinomethane diphosphonic acid, N, N-dimethylaminodimethyldiphosphonic acid, aminomethyl diphosphonic acid or the same
Salts, preferably sodium salts. Useful protective colloids include tin compounds such as alkali metal tinate, especially sodium stannate (Na2 (Sn (OH)<sub>6</sub>). Useful radical scavengers include pyridine carboxylic acids such as pyridine 2,6-dicarboxylic acid. The appropriate amount of chloride ions is below 50 mmol / dm<sup>3</sup>, preferably less than about 5 mmol / dm<sup>3</sup>, most preferably less than about 0.5 mmol / L.
When sulfuric acid is used as the feed, it preferably has a concentration from about 70 to about 96 wt%, most preferably from about 75 to about 85 wt%. and preferably a temperature from about 0 to about 80 ° C, most preferably from about 20 to about 60 ° C, as then it may be possible to conduct the process substantially adiabatically. Preferably, from about 2 to about 6 kg H2SO4 are provided, most preferably from about 3 to about 5 kg H2SO4 per kg ClO2 produced. Alternatively, an equivalent amount of another mineral acid can be used.
The total reaction resulting in the production of chlorine dioxide can be represented by the formula:
2ClO3 + 2H + + H2O2 2ClO<sub>2</sub> + 2H<sub>2</sub>O + O<sub>2</sub>
The exact mechanism is complex and is believed to involve the first reaction between chlorate and chloride (even if not added separately, always present in sufficient quantity as an impurity in chlorate) leading to chlorine dioxide and chlorine followed by chlorine reacting with peroxide hydrogen leading back to chloride. However, considering the total reaction, hydrogen peroxide is usually considered as the reducing agent reactive with the chlorate ions.
The reduction of chlorate ions to chlorine dioxide results in the production of a product stream in the reactor, usually consisting of both liquid and foam, and containing chlorine dioxide, oxygen and, in most cases, some remaining unreacted chemical feeds. Chlorine dioxide and oxygen can be present both dissolved in the liquid and gas bubbles. When metal chlorate and inorganic acid are used as feed chemicals, the product stream will then contain, in addition to chlorine dioxide and oxygen, a metal salt of the inorganic acid and usually also some residual metal chlorate and inorganic acid. It has been found possible to achieve a degree of conversion of chlorate ions to chlorine dioxide from about 75% to 100%, preferably from about 80% to 100%, most preferably from about 95% to 100%.
The temperature in the reactor is suitably kept below the boiling point of the reactants and the product stream at the existing pressure, preferably from about 20 to about 80 ° C, most preferably from about 30 to about 60 ° C. The pressure maintained inside the reactor is suitably a slight negative pressure, preferably from about 30 to about 100 kPa (absolute pressure), most preferably from about 65 to about 95 kPa (absolute pressure).
The reactor may comprise one vessel or several vessels, for example vertically, horizontally or obliquely. The reactants can be fed directly to the reactor or through a separate mixing device. Accordingly, the reactor is preferably a substantially flow-through tubular vessel or tubing, most preferably containing means for mixing the reactants in a substantially uniform manner. Such means may include a target or the like provided with holes located inside the reactor, to which the metal chlorate and hydrogen peroxide are supplied behind the target and acid is supplied in front of the target and allowed to flow through the holes and then mixed with the metal chlorate. and hydrogen peroxide. It has been found that such an arrangement provides for uniform mixing and stable operation of the process, as well as the possibility of varying the production rate while maintaining high chemical efficiency, especially in substantially vertical reactors with the main flow direction upwards. However, it is also possible to simply feed one of the reactants, e.g. an acid, to the feed line for another reactant or mixture of reactants, e.g. a mixture of a metal chlorate and hydrogen peroxide.
The used length (main flow direction) of the reactor is preferably from about 50 to about 800 mm, most preferably from about 350 to about 650 mm. It has been found advantageous to use a substantially tubular reactor with an inside diameter of from about 25 to about 300 mm, preferably from about 70 to about 200 mm. It is especially preferred to use a substantially tubular reactor with a preferred length to ID ratio of from about 12: 1 to about 1: 1, most preferably from about 8: 1 to about 4: 1. A suitable average residence time in the reactor is from about 1 in most cases. to about 1000 seconds, preferably from about 2 to about 40 seconds.
The steam jet pump creates a suction force by bringing the product stream, including the liquid, foam and gas it contains, to flow to the steam jet pump and to be mixed with the water
Industrially to form a dilute solution containing chlorine dioxide. The industrial water is brought to flow in an at least partially helical or helical manner by suitable means such as twisted blades, internal threading or the like, which may be integral with or separate from the nozzle and may be placed inside or in front of the nozzle. The nozzle may be of any suitable type and may have one or more orifices.
The steam jet pump suitably further comprises, downstream of the nozzle, a suction chamber into which the product stream is transferred from the reactor, and an orifice device through which the dilute aqueous solution containing chlorine dioxide is then withdrawn. Steam jet pumps with more than one nozzle can also be used.
It has been found that the at least partially helical or helical flow of process water increases the yield of chlorine dioxide production for a given industrial water flow, thus enabling the production of a product solution with a chlorine dioxide concentration greater than the concentration previously possible only by separating chlorine dioxide gas from the environment reaction followed by its absorption in water, steps, which is not necessary in the present invention. Thus, it is possible to prepare aqueous solutions containing from about 1 to about 4 g / dm3<sup>3</sup> chlorine dioxide, preferably from about 1.5 to about 3.5 g / dm3<sup>3</sup> chlorine dioxide.
The process of the invention is particularly suitable for small-scale production of chlorine dioxide, for example, from about 0.1 to about 100 kg / hr, preferably from about 0.1 to about 50 kg / hr. in one reactor. For many applications, a preferred chlorine dioxide production capacity is from about 0.1 to about 25 kg / hr, most preferably from about 0.5 to about 10 kg / hr. in one reactor. A typical small scale production unit usually comprises only one reactor, although it is possible to arrange several, for example up to about 15 or more reactors in parallel, for example as a bundle of tubes.
The invention further relates to a device for producing chlorine dioxide according to the above-described method. The apparatus comprises a reactor provided with feed lines for chlorate ions, hydrogen peroxide and acid, the reactor being connected to a steam jet pump provided with an industrial water nozzle and means further for causing the industrial water to flow through the steam jet pump in an at least partially helical or helical manner.
Preferred embodiments of the device emerge from the above description of the method and the following description with reference to the drawings. The invention is not limited to the embodiments illustrated in the drawings, however, and includes many other variants within its scope.
The subject matter of the invention is explained in more detail in the drawing in which Fig. 1 shows a process diagram according to the present invention, Fig. 2 shows a schematic view of the reactor, and Figs. 3a and 3b schematically show a steam jet pump and elements causing the flow of industrial water in at least partially helical or helical manner.
With reference to Fig. 1, the vertical straight-through tubular reactor 3 is fed sulfuric acid via feed line 1 and a pre-mixed aqueous solution of sodium chlorate and hydrogen peroxide via line 2. In reactor 3, the feed streams are mixed and reacted to form a liquid product stream. , foam and gas containing chlorine dioxide, oxygen, sodium sulfate and some residual sulfuric acid and sodium chlorate. Steam jet pump 6 is fed with industrial water via feed line 5 and a slight vacuum is created to drive the product stream from reactor 3 via line 4 to steam jet pump 6 where it is mixed with industrial water to form a dilute aqueous product solution. This dilute solution contains chlorine dioxide and another component from reactor 3 and is removed as end product via line 8. The automatic control system of the continuous technological process including a Programmable Controller (PLC), a chlorine dioxide analyzer 9, a pressure transducer (PT) and a transducer and flow meter (FT) controls the feed pumps 10 for chemicals directed to the reactor 3 and industrial water directed to the steam jet pump 6.
With reference to Fig. 2, a distribution disc 21 provided with openings is placed in the lower part of the reactor 3, but above the inlet from the sulfuric acid feed line. The feed line 2 for the pre-mixed solution of sodium chlorate and hydrogen peroxide terminates at a distribution nozzle 20 located in the center of the cross section of the reactor just above the distribution disc. The solution of sodium chlorate and sodium peroxide is then sprayed across the cross section inside reactor 3, while sulfuric acid flows upward through the openings in the distribution disk and is mixed with sodium chlorate and hydrogen peroxide above the distribution disk 21. After stirring, the reaction begins.
PL 200 136 B1 produces chlorine dioxide, and a product stream of liquid, froth and gas is formed, which stream is withdrawn through an outlet 22 at the top of reactor 3.
Referring to Figs. 3a and 3b, the steam jet pump 6 comprises a suction chamber 25, one orifice 26 nozzle with an insert 27 (shown in view through the nozzle in Fig. 3b) containing twisted blades 28 and an orifice 29. Industrial water is supplied from feed line 5 through nozzle 26 and insert 27. The twisted vanes 28 of the insert 27 cause the water to continue to flow in an at least partially helical or helical manner through the suction chamber 25 where it mixes with the product stream flowing through line 4 from the reactor 3 (see Fig. 1) to form a dilute chlorine dioxide containing solution withdrawn from the steam jet pump 6 through the orifice 29. Flow through the steam jet pump creates a vacuum sufficient to cause the product stream to flow from the reactor to the steam jet pump.
The process equipment including reactor 3 and steam jet pump 6 is suitably made of materials resistant to hydrogen peroxide, sodium chlorate, sulfuric acid and chlorine dioxide. Such materials include, for example, glass, tantalum, titanium, glass fiber reinforced plastics, chlorinated and fluorocarbon plastics such as PVDF (polyvinylidene fluoride), CPVC (chlorinated polyvinyl chloride), PTFE ( poly (tetrafluoroethylene)), PFA (perfluoroalkoxy polymer), ECTFE (ethylene chlorotrifluoroethylene) or FEP (fluorinated ethylene-propylene copolymer) or the use of these materials as a cladding material for a structural material, such as steel or stainless steel. Suitable chlorinated and fluorocarbon plastics are sold under the trademarks Kynar®, Teflon® or Halar®.
The invention is further illustrated by the following examples.
Example:
Chlorine dioxide is produced according to the invention in the apparatus shown in Figures 1 to 3. A vertical tubular reactor 3 with an internal diameter of 75 mm and a length of 610 mm was continuously fed with sulfuric acid at a concentration of 78% by weight. and an aqueous solution of 40 wt.%. % sodium chlorate and 10 wt. hydrogen peroxide stabilized with a phosphonic acid complexing agent. The reactor was maintained at a temperature of about 40-50 ° C and at an absolute pressure of about 84 kPa absolute (about 17 kPa below atmospheric pressure), a vacuum was created by feeding the steam jet pump 6 with industrial water at an absolute pressure of 790 kPa.
As a comparison, chlorine dioxide was produced in the same manner except that the steam jet pump used did not include a nozzle insert for causing the industrial water to flow in an at least partially helical or helical manner.
The results are presented in the table below:
<td>Steam jet pump type</td><td>Industrial water flow (dirr / min)</td><td>ClO2 production capacity (<sup>k</sup>g<sup>/</sup>at )</td><td>ClO2 concentration in the final product (mg / dm<sup>3</sup>)</td>
<td>with insert (invention)</td><td> 48,1</td><td> 9,1</td><td> 3135</td>
<td>without insert (comparison)</td><td> 45,4</td><td> 3,9</td><td> 1450</td>
It appears that the process of the invention gives a significant increase in both the ClO2 production yield and the ClO2 concentration in the end product solution removed from the steam jet pump.
3 sheets
Sheet 1 Sheet 2 Sheet 3
25 members in 15 offices
Priority claims11
| Document | Office | Kind | Date |
|---|---|---|---|
| 88726401 | United States of America | A | |
| 88726401 | United States of America | A | |
| 01850116 | European Patent Office (EPO) | A | |
| 01850116 | European Patent Office (EPO) | A | |
| 0201068 | Sweden | W | |
| 0201068 | Sweden | W | |
| 018501163 | – | – | – |
| 09887264 | – | – | – |
| EP20010850116 | – | – | – |
| US20010887264 | – | – | – |
| WO2002SE01068 | – | – | – |
Members25
| Document | Office | Kind | |
|---|---|---|---|
| WO03000586A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2003007899A1 | United States of America | A1 | |
| KR20040012889A | Republic of Korea | A | |
| MXPA03010884A | Mexico | A | |
| EP1399383A1 | European Patent Office (EPO) | A1 | |
| BR0210340A | Brazil | A | |
| CN1520378A | China | A | |
| US6790427B2 | United States of America | B2 | |
| JP2004530626A | Japan | A | |
| PL364357A1 | Poland | A1 | |
| RU2004101962A | Russian Federation | A | |
| US2005084429A1 | United States of America | A1 | |
| CN1221469C | China | C | |
| RU2268241C2 | Russian Federation | C2 | |
| KR100590345B1 | Republic of Korea | B1 | |
| MY130748A | Malaysia | A | |
| JP4006019B2 | Japan | B2 | |
| PL200136B1This record | Poland | B1 | |
| EP1399383B1 | European Patent Office (EPO) | B1 | |
| AT465972T | Austria | T | |
| ATE465972T1 | Austria | T1 | |
| DE60236154D1 | Germany | D1 | |
| PT1399383E | Portugal | E | |
| ES2345185T3 | Spain | T3 | |
| BRPI0210340B1 | Brazil | B1 |
Numbers
- Publication
- 200136
- Publication, DOCDB
- 200136
- Publication, EPODOC
- PL200136B
- Application
- 364357
- Application, DOCDB
- 36435702
- Application, EPODOC
- PL20020364357
Titles2
- English
- PROCESS FOR PRODUCING CHLORINE DIOXIDE
- Polish
- Sposób i urządzenie do ciągłego wytwarzania dwutlenku chloru
Classification
- CPC, 11
- C01B11/026
- B01F23/23763
- C01B11/02
- B01J19/26
- B01J2219/00162
- B01J2219/00164
- B01F25/3121
- B01F25/31243
- B01F25/70
- B01F23/2376
- B01F23/237612
- IPC, 4
- C01B9 00
- C01B11 02
- B01F25 70
- B01J19 26
