CA2131664A1 - Process and device for the continuous production of peroxycarboxylic acids - Google Patents
Process and device for the continuous production of peroxycarboxylic acidsInfo
- Publication number
- CA2131664A1 CA2131664A1 CA 2131664 CA2131664A CA2131664A1 CA 2131664 A1 CA2131664 A1 CA 2131664A1 CA 2131664 CA2131664 CA 2131664 CA 2131664 A CA2131664 A CA 2131664A CA 2131664 A1 CA2131664 A1 CA 2131664A1
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- Prior art keywords
- acid
- reactor
- process according
- peroxycarboxylic
- reaction
- 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
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Classifications
-
- 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
- B01J19/0006—Controlling or regulating processes
-
- 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
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/26—Peracetic 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00065—Pressure measurement
-
- 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
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
-
- 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
- B01J2219/00051—Controlling the temperature
- B01J2219/0015—Controlling the temperature by thermal insulation means
- B01J2219/00155—Controlling the temperature by thermal insulation means using insulating materials or refractories
-
- 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
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
- B01J2219/0209—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of glass
-
- 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
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0277—Metal based
- B01J2219/0286—Steel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
The present invention is directed to a continuous process comprising: converting a carboxylic acid with hydrogen peroxide in an aqueous reaction medium in the presence of a catalyst at a temperature of 40°
to 60°C. The process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the reaction chamber, and after the reaction equilibrium has been achieved, the peroxycarboxylic acid thus formed is continuously withdrawn from the retention reactor.
The present invention is also directed to a device for carrying out the continuous process of the present invention. The device of the present invention comprises a retention reactor for holding the reaction medium, a heating element capable of heating the reaction medium to 40°to 60°C, and two feedlines, each of the feedlines being equipped with a return valve and metering pump capable of substantially continuously pumping a reaction component from a respective storage vessel into the respective feedline and into the retention reactor.
The present invention is directed to a continuous process comprising: converting a carboxylic acid with hydrogen peroxide in an aqueous reaction medium in the presence of a catalyst at a temperature of 40°
to 60°C. The process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the reaction chamber, and after the reaction equilibrium has been achieved, the peroxycarboxylic acid thus formed is continuously withdrawn from the retention reactor.
The present invention is also directed to a device for carrying out the continuous process of the present invention. The device of the present invention comprises a retention reactor for holding the reaction medium, a heating element capable of heating the reaction medium to 40°to 60°C, and two feedlines, each of the feedlines being equipped with a return valve and metering pump capable of substantially continuously pumping a reaction component from a respective storage vessel into the respective feedline and into the retention reactor.
Description
~ ~ 3 ~
28414/lOOOU
PROCESS AND DEVICE FOR T~E CONTINUOUS
PRODIJC TION OF PEROXYCARBOXYLIC AClDS
BAC~GRO~ OF T~E I~WENTION
S A. Field Of The Inventior~
The invention relates to a process for the continuous an~d controlled production of peroxycarboxylic acids, in particular, peroxyacetic acid, and to a device for carrying out this process.
B. Background Peroxycarboxylic acids are used in the laboratory and on an industrial scale for the production of epoxides according to the so-called Prilezhaev reaction (compare Trahaowsky, Oxidation in Organic Chemistry, Part C, p. 211 to 252, New York, Academic Press, 1978~ and for the hydroxylation, the Baeyer Villiger oxidation and special oxidation processes.
15 In addition, peroxycarboxylic acids a~e being increasingly used in the chemical and allied industries, e.g., in the food industry, the phannacelltical industry and the paper industry andl as a disinfectant in wa~er ~reatment.
In these branches of industry, there is a continuously increasing demand for disin~ectants for sterilizing production facilities. Disinfectants 2() used ~or this pulpose include sodium hypochlorite, chlorine dioxide, halogenat~d carboxylic acids, aldehydes, quaten ary ammonium compounds, hydrogen peroxide and peroxycarboxylic acids, in particular peroxyacetic acid, (peracetic acid).
Hydrogen peroxide and the peroxycarboxylic acids, such as 25 peroxyacetic acid, are not thermally stable and can undergo violent ~ ~ 2~3~
decomposition reaclions when subjected to excess heating or in the presence of contaminants, as a result of which serious problems arise during transportation and storage. Because peroxyacetic acid explodesl e.g., in the form of organic solutions of >50 percent by volume ("vol. %") and of aqueous solutions of ~ ;
:>70 vol. %, it is frequently prepared in the presence of acid in si~u, i.e., ~ :~
from acetic acid and ~22 .
However, handling low molecular peroxycarboxylic acids such as peroxyacetic acid causes problems to the user because these substances have a pungent odor and the vapors have a strongly corrosive effect on the eyes, the skin and the mucous membranes.
Ihe commercial quality peroxycarboxylic acids, such as peroxyacetic acid, which are usually used for disinfection purposes, consist of the so-called equilibrium peroxycarboxylic acids. The concentration of peroxycarboxylic acid in these disinfectants is usually between S and 15% by weight. In a peroxyacetic acid equilibrium concentrate, th~ concentrate contains the components hydrogen peroxide, acetic acid, peroxyacetic acid, water, acid catalyst and stabilizers, wherein the components hydrogen peroxide, acetic acid, peroxyacetic acid and water are in a chemical equilibrium according to the following equation:
[cat.3 ~T
CH3$:~001H ~ H202 ~ CH3COOOH + H20 ~3 acetic hydrogen per2cetic water acid peroxide acid - I'he content oî peroxyace~ic acid in equilibrium conse~uently depends on the concentration of ~he reactants, acetic acid and hydrogen .. .~
peroxide, as well as on the temperature. Adjusting the equilibrium is done by acid catalysis.
From EP-A-0269 345, a process and a device is known ~or dilu~ing a reaction product, in particular a peroxyacid, for the production of adisinfection solution. According to EP-A-0269 345, a reaction is carried out between two or more reactants in a reactor, and the reaction product is diluted.The concentration of the reaction product after dilution is monitored with an eiectrochemical sensor and the dilution of the reactioa product is controlled according to the values indicated by this sensor. In addition to re~uiring dilution of the resultant peroxyacid, the reactor of EP-A-0269 345 is not equipped with a device for heating the reaction mixture. Consequently, the reactor in EP-A-0269 345 cannot quickly and colltinuollsly provide a peroxy carboxylic aci~l by carrying out the process at ~m elevated ternperature for a more rapid adjustment of the equilibrium. For this reason, the present day requirements, such as those arising in connection with the production of pe~xyacetic acid, e.g., in large industrial operations in the food industry, could not be satisfied to a satisfactory degree by the process of EP-A-0269 345.
It is the object of the present invention to avoid the disadvantages and problems detailed above which are connected with the production, treatment and use of peroxycarboxylic acids, in palticular the pungent odor and thF risk of irritation and corrosion of the eyes, the skin and the mucous membranes of the operatives and to make a process and a device a~vailable by means of which a rapid adjus~ment of the reaction equilibrium and consequently a satisfactory continuous execution of the process is possible.
2 ~
SUI~L~RY OF THE IIYVENTION
The object of the present invention is achieved by way of a continuous process and a device for the production of peroxycarboxylic acids, and in parlicular, peroxyacetic acid, in which the peroxyca~boxylic acid is S produced in a closed facility, only when directly re~uired and in the desired quantity. Direct contact wi~h personnel is avoided during the manufacture of the peroxycarboxylic a~ids and during their use, e.g., as a disinfectant.
In particular, the continuous process of the present invention comprises the step of: converting a carboxylic acid with hydrogen peroxide in 10 an aqueous medium in the presence of a catalyst, at a temperature of 40 to 60C. The process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the retention reactor, and after the reaction equilibrium has been adjusted, the peroxycarboxylic acid that is formed is continuously withdrawn from the 15 retention reactor.
The present invention is also dire ted to a device for carrying ut the continuous process of the present invention. ~he device of the present invention comprises a retention reactor for holding tbe reaction medium; a heating element capable of heating the reaction me~ium to 40 to 60C; and 20 two feedlines, wherein each of the ~eedlines is equipped with a returll valve and a metering punnp capable of substantially continuously pumping a reaction component from its storage vessel into the feedline and into the retention reactor.
21316~
IBÆF DESCRIPTION OF THE FIGURES -FIGURE I is a graph plot of " % peroxyacid" (y axis) versus "reaction time" hl minutes (x axis) as a function of three different temperatures. The three temperatures reflect the effect of temperature on the S time required to achieve reaction equilibrium.
FIGURE 2 is a diagrammatic representation of one embodiment of a device of the present invention ~or continuously producing the peroxycarboxylic acid.
, ~, ., . " ~.
~ 2~3~
I:2ETAILED DESCRIPTIOIY OF TH!E I~WENTION
The present invention has two aspects. In its first aspect, the invention is directed to a continuous process for producing a peroxycarboxylic acid. The process of the present invention comprises the step of converting a 5 carboxylic acid with hydrogen peroxide in an aqueous reaction medium in the presence of a catalyst at a temperature of 40 to 60C. l~e process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the reaction chamber, and after the reaction equilibrium has been achieved, ~he peroxycarboxylic acid thus 10 formed is continuously withdrawn from the retention reactor.
The effect of the reaction temperature on the reaction equilibrium and the results obtained are showrl in the following Figure 1. The measured values are based on a mixture of 14 7% hyclrogerl peroxide, 37.5%
acetic acid, û.S% stabilizer, 11.25% suiphuric acid and 36.05% water. Figure 15 I shows that by heating the reaction mixture to approximately 50C, the reactiorl equilibrium, i.e., the optimum concentration of desired peroxyacetic acid, is achieved after only approximately thirty minutes. At room temperature or lower temperatures (e.g., at 5C in an unheated room in ~:
winter), the equilibriurn is reached much later, narne1y a~ter a period which is 20 too long ~or a contimlous process in order to satis~y the requirement of peroxyacetic acid, Çor exarnple, for disinfecting purposes in a modem clean~ng facility ~e.g., a bonle cleaning facility in the beverage industry) or ~n a pros~uction ~acility (e.g., tank disinfection in breweries).
The subject matter of the invention is a process for the 25 continuous production of peroxycarboxylic acids by converting a ca~oxylic acid with hydrogen peroxide in an aqueous medium in the presence of a 3 ~
catalyst. charact~r~ed in that the conversion is carried out at a temperature in the range of ~0 to 60C and further characterized in that the peroxycarboxylic aid so produced does not require dilution.
According to an appropriate embodiment of the process 5 accordin~, to the invention, the hydrogen peroxide and the carbo~ylic acid/catalyst mixture are passed continuously to a retention reactor for receiving the reaction mixture in two separate feedlines and the peroxycarboxylic acid formed is continuous!y withdrawn from the retention reactor after adjusting the reaction equilibrium.
The hydrogen peroxide used according to the process is preferably a hydrogen peroxide with a concentration of 30 to 50% by weight.
As catalyst, any common catalyst known as suitable for the produc~ion of peroxycarboxylic acids by conver!ing a carboxylic acid with hydrogen peroxide can be used. Catalysts used according to the invention are prefe~bly mineral acids such as phosphoric acid or nitric acid and in particular, sulphuric acid. Hydrochloric acid is not suitable for use as mineral acid because it can easily lead to decomposition reactions. Basically, however, any organic (e.g., phosphonic acid) or inorganic acid can be used as catalyst provided that it is stable vis-a-vis the oxidizing medium and does not promote 2û the decomposition of the active oxygen carrier.
The conve~sion is camed out at a temperature in the region of 40 to 6ûC, and preferably a~ a temperature of approxirnately S0 to 60C.
The concentration of the peroxycarboxylic acid in the reac~ior medium can be varied within a wide range. Preferably, the concentration is 10 to 30%; more preferably, 10 to 25% by weight; and most preferably, 13 to 15% by weight.
~:~3~6~
In general, the reaction temperature is in the region of 40 to 60, particularly, in the region of 50 to 55C. Typically, the reaction is carried out at a temperature of approximately 50C.
If temperatures above 60C are used, the decomposition of the S peroxycarboxylic acids is accelerated in an undesirable manner. If a ~emperatuse of less than 40C is used, the reaction equilibrium is reached after a time which is unsuitably long for a continuous execution of the process.
In the process of the present invention, the carboxylic acid used is preferably a C~ - C6 carboxylic acid or an oligocarboxylic acid, and in 10 particular, ~ormic acid or acetic acid.
According to a preferred embodiment of the process of the invention, ~he peroxycarboxylic acid (e.g., peroxyacRtic acid~ that is withdrawn from the retention reactor is passed directly to the application, e.g., directly to a line to be disinfected or to a bottle cleaning plant in the beverage 15 industry or directly to a production facility to be disinfected e.g., the fermentation, storage and pressure tanks in a breweryt or directly to any other disinfectant circuit. In this way, contact with the peroxycarboxylic acid , harTnful to heal~h or its vapors and the associated problems such as irritation and corTosion of the eyes, the mucous membranes and the skin can be avoided 20 by controllin~ the process lcontrolling ~he quantities of peroxycarboxylic acid conc~ntJate produced) and by using a closed circui~ up to the intended application, e.g., up to the plant or line to be disin~ected.
By controlling the reaction temperature according to the present i~i~tention, it is also possible to achieve the reaction equilibrillm in a time 25 sufficiently brielF for a con~im30us easily controllable execution of the process, e.g., in approximately thirty minutes as a result of wSIich the process is easy to ~ ~ 3 ~
~ontrol and it is thus possible to adjust the quantities produced according to the process to the requirement concerned, and to consequently avoid funher treatment of the peroxycarboxylic acids hannful to health connected with intennediate storage.
S In its second aspect, the subject matter of the present invention also includes a device which is suitable for the continuous production of peroxycarboxylic acid according to the process of the invention and comprises:
a retention reactor for receiving the reaction medium, the retention reactor being equipped with a heating device and two supply lines equipped with return valves, which lines are each equipped with a metering pump for supplying the reaction components from the storage vessel to the supply lines and into the retention reactor.
The volume of the retention reactor depends mainly on the perforrnance required (e.g., the output of peroxycarboxylic acid concentrate per hour). Heating of the reaction mLxture can take place by way of internal heating, e.g., in the fonn of an elec~nc heating coil, or by external heating, ~-~
e.g., in the fonn of a hollow jacket surrounding the reactor through which a heating liquid or steam is passed. If the reactor consists of a material with a low thermal conductivi~y, e.g., of a material resistant to the components of thereaction mi%ture, such as a polymer, heating talces place preferably via an internal heating unit.
Passing the reaction components (e.g., hydrogen peroxide and acetic acid) from the storage vessel into the supply lines and into the retention se~ctor ~akes place via metering pumps with flow controls. The suction "lances" into the S~otage vessel ate eqoipped with "empty" indieatots.
~ ~ - 2 ~
In the device and process of the present invention, the hydrogen peroxide is stor~d separately from the carboxylic acid component.
Preferably, the device according to the invention is equipped with a pressure sensor situated at the outlet of the retention reactor.
S Appropriately, this pressure sensor is coupled with a device which douses the device automatically w;th water once a maximum pressure has been exceeded.
In this way, it is possible to guarantee a high level of operational safety because the device can be doused automatically with water via the pressure sensor and the facility coupled with it if a pressure limit is exceeded which can iO be caused e.g., by an unexpected decomposition reaction.
Appropriately, the device is also equipped with a mechanical pressure relief valve by way of which a decrease in pressure in the reactor can take place even ~n the case of a power failure.
For proper and simple maintenallce of the facility, it is appropriate to equip the device with a ventlng valve and a discharge valve for ventin~ and/or draining respectively and with a valve for dousing with water.
The discharge of the peroxycarboxylic acid ejectecl by ~he water douse via the discharge valve takes place appropriately via a neutralization vessel colmected to the device.
According to a par~icularly appropriate embodimeot, tbe device is equipped with suitable facilities for directly metering tihe peroxycarboxylicacid withdrawn from the retention reactor to the site of application. In this way, it is possible by a suitable controi of the process, i.e., of the output ofperoxycarboxylic acid concentrate per hour and direct dispatch to the site of application (e.g., bottle cleaning facilities to be disin~cted with peroxycarboxylic acid in the beverage industry, production f~ilities, e.g., 211 3~ 6~
fennentation stordge and pressure tanks in breweries etc.) to avoid any intermediate storage and disect contact between the peroxycarboxylic acid that is hannful to health and the operating personnel. lFor this reason, the peroxycarboxylic acid concentrate is usually metered directly, e.g., into the 5 lines to be disinfected or into a disinfection circuit, the metering operation being controlled via the controls of the process for the production of the peroxycarboxylic acids (output of peroxycarboxylic acid concentrate per hour) coupled with electrochemical sensors.
In the device according to the invention, at least those parts 10 coming into contact with the starting or the end products (carboxylic acid, hydrogen peroxide" mineMI acid catalyst, peroxycarboxylic acid) consist of materials resistant to corrosion vis-a-vis these substances. Such materials are e.g., polymers, in particular polyvinylidene fluoride (PVDF) and/or polytetrafluoroethylene ~PDFE), glass or corrosion-resistant steel and/or non-15 fierrous metal, if necess~ry additionally provided with a corrosion-resistant coating by a suitable passivating measure, such as are hlown to the art.
The retention reactor, particularly, if i~ is equipped with interna~
heating, is provided with a heat insulating jacket, e.g., a hollow jacket filled, if necessasy, with thennal insulating material, or a coating of a thermally 20 insulating material. The heating of the retention reactor can appropriately be controlled in an infinitely variable manner. A standard heat exchanger or retentiorl reactor known and suitable for this purpose can be used, it being possible ~or the retention reactor to be subdivided into a temperature-controlled he~ting section and a thennally insulated residence section.
~5 It is also within the scope of the device of the present invention that the electronic control, regula~ion and overflow control ~acility be provided 2~L3~6~
by way of a member selected from the group consisting of a memory-progfammable control, a single-board microcomputer, ~ microcomputer development system, a personal computer havin~ digital and analog input and output boards and discreet electronic or electromechanical circuits, and a S combination ~hereof.
Figure 2 contains a diagrammatic representation of one embodiment of a device according to the invenCion. The present invention will now be explained in further detail on the basis of the device illustrated in Figure 2 without being limited thereto in terms of its scope. The embodimen~
10 illustrated in Figure 2 is a device for the execution of the process according to the invention for the continuous production peroxycarboxylic acid by converting a carboxylic acid with hydrogen peroxide in the presence of a catalyst, the device comprising a retention reactor I for receiving the reaction medium. The retention reactor is equipped wilLh an el~ctrical internal heater 15 10 which is controlled in an infinitely variable marmer. The retention reactor is connected with ~wo feedlines 2,2 equipped with re~um valves 9,9, each line being equipped with a metering pump 3,3 for respectively supplying the reaction components (components I and 2) from the storage vessels 11, 12 to lines 2,2. The retention reactor is provided with a thermal insulation jacket 20 13. At the reactor outlet, there is a pressure sensor 4 (not illustrated) as an excess pressure control; this is connected to a magnetic valve 17 which opens when a pressure limit is exceeded, as a result of which the device is automatically doused with water. The device is also equipped with a n1echanical pressure relief valve 20 which is capable of e~fecting a decrease in 25 pressure in the reactor even in the c2se of a power fai~ure (e.g., failure of the mains powsr supply). The device is also equipped with a venting valve 5 and a discharge valve 6 for v~nting or discharging. It is additionally equipped with a neutralization vessel 7 via which the discharge of the peroxycarboxylic acid ejected by the water douse via the pressure relief valve 20 or discharged via the discharge valve 6 takes place. The neutrali~ation vessel has the form of an S overflow vessel. Metering of the peroxycarboxylic acid takes place in line with the user's requirements by controlling the magnetic valve 14 and the metering pumps 3,3 which suck the components from containers 11, 12 via suction iances with filling level sensors 15, 15. The storage vessels 11 and 12 are designed according to an ernbodiment used as an example as containers ~ ~.
10 with an 800 liter capacity and according to another ernbodiment provided as an example as drums with a 200 liter capacity. A~ magnetic valve 17 and a ball return valve 18 are connected downstream of the water connection. Between the metering pumps 3,3 and the retum valves 9,9, there is a device (19,19) for flow control.
The device illustrated in Pigure 2 was used to carry out the ;~
process according to the invention with a reactor output of 44 g peroxyacetic acid per hour or 2.76 kg of a 15% peroxyacetic acid concentrate forrned continuously by the reactor within one hour. The temperature of the heating section was approximately 50C as a result of which an equilibrium mixture 20 was obtained within approximately 30 minutes with an approximaiely 15%
peroxyacetic acid. rhe reactor volume was only I.5 Iiters, however, this was sufficient for the reactor perfonnance of 400 g peroxyacetic acid per hour indicated.
- By increasing the temperature andlor the concentlatioll of the 25 reactants further, it is possible to achieve a further acceleration of the reaction ~ ~ 3 ~
(shortest time to reach the equilibrium reaction mixhlre) an~d, if necessary, a filrther reduction of the reactor volume.
By utilizing the process and device according to the invention, it is thus possible, clepending on the selection and the concentration of the 5 cornponents and the choice of the reaction temperature, to continuously produce aqueous concentrates of peroxycarboxylic acids having the same or - -different concentrations as added to satisfy any demand. In this way, it is .
possible to continuously satisfy the requirement for peroxycarboxylic acids, particularly, peroxyacetic acid as disinfectant m the chemical industry and 10 allied branches of industry, e.g., in the food industry, the paper industry and in particular, in beverage operations and breweries. In average operations, such as mineral water wells and breweries, peroxyacetic acid is used as a disinfectant for sterilizing the rinsing areas of the bottle cleaning facilities.
These facilities res~uire a continuous, uni~olm dosage of approximately 10-20 15 mg peroxyacetic acid per Liter fresh water supplied. In the bottle cleaning facilities of the usual size, approximately 10-20m3 fresh water are consumed per hour. On ~his basis, a maximum requirement of 400 g peroxyacetic acid per hour can be calculated which, as indicated above, can be easily provided in a controlled manner by way of the process according to the invention and 20 the device according to the inven~ion in a closed circuit which is safe even for the operating personnel, while avoiding intermediate stolage.
28414/lOOOU
PROCESS AND DEVICE FOR T~E CONTINUOUS
PRODIJC TION OF PEROXYCARBOXYLIC AClDS
BAC~GRO~ OF T~E I~WENTION
S A. Field Of The Inventior~
The invention relates to a process for the continuous an~d controlled production of peroxycarboxylic acids, in particular, peroxyacetic acid, and to a device for carrying out this process.
B. Background Peroxycarboxylic acids are used in the laboratory and on an industrial scale for the production of epoxides according to the so-called Prilezhaev reaction (compare Trahaowsky, Oxidation in Organic Chemistry, Part C, p. 211 to 252, New York, Academic Press, 1978~ and for the hydroxylation, the Baeyer Villiger oxidation and special oxidation processes.
15 In addition, peroxycarboxylic acids a~e being increasingly used in the chemical and allied industries, e.g., in the food industry, the phannacelltical industry and the paper industry andl as a disinfectant in wa~er ~reatment.
In these branches of industry, there is a continuously increasing demand for disin~ectants for sterilizing production facilities. Disinfectants 2() used ~or this pulpose include sodium hypochlorite, chlorine dioxide, halogenat~d carboxylic acids, aldehydes, quaten ary ammonium compounds, hydrogen peroxide and peroxycarboxylic acids, in particular peroxyacetic acid, (peracetic acid).
Hydrogen peroxide and the peroxycarboxylic acids, such as 25 peroxyacetic acid, are not thermally stable and can undergo violent ~ ~ 2~3~
decomposition reaclions when subjected to excess heating or in the presence of contaminants, as a result of which serious problems arise during transportation and storage. Because peroxyacetic acid explodesl e.g., in the form of organic solutions of >50 percent by volume ("vol. %") and of aqueous solutions of ~ ;
:>70 vol. %, it is frequently prepared in the presence of acid in si~u, i.e., ~ :~
from acetic acid and ~22 .
However, handling low molecular peroxycarboxylic acids such as peroxyacetic acid causes problems to the user because these substances have a pungent odor and the vapors have a strongly corrosive effect on the eyes, the skin and the mucous membranes.
Ihe commercial quality peroxycarboxylic acids, such as peroxyacetic acid, which are usually used for disinfection purposes, consist of the so-called equilibrium peroxycarboxylic acids. The concentration of peroxycarboxylic acid in these disinfectants is usually between S and 15% by weight. In a peroxyacetic acid equilibrium concentrate, th~ concentrate contains the components hydrogen peroxide, acetic acid, peroxyacetic acid, water, acid catalyst and stabilizers, wherein the components hydrogen peroxide, acetic acid, peroxyacetic acid and water are in a chemical equilibrium according to the following equation:
[cat.3 ~T
CH3$:~001H ~ H202 ~ CH3COOOH + H20 ~3 acetic hydrogen per2cetic water acid peroxide acid - I'he content oî peroxyace~ic acid in equilibrium conse~uently depends on the concentration of ~he reactants, acetic acid and hydrogen .. .~
peroxide, as well as on the temperature. Adjusting the equilibrium is done by acid catalysis.
From EP-A-0269 345, a process and a device is known ~or dilu~ing a reaction product, in particular a peroxyacid, for the production of adisinfection solution. According to EP-A-0269 345, a reaction is carried out between two or more reactants in a reactor, and the reaction product is diluted.The concentration of the reaction product after dilution is monitored with an eiectrochemical sensor and the dilution of the reactioa product is controlled according to the values indicated by this sensor. In addition to re~uiring dilution of the resultant peroxyacid, the reactor of EP-A-0269 345 is not equipped with a device for heating the reaction mixture. Consequently, the reactor in EP-A-0269 345 cannot quickly and colltinuollsly provide a peroxy carboxylic aci~l by carrying out the process at ~m elevated ternperature for a more rapid adjustment of the equilibrium. For this reason, the present day requirements, such as those arising in connection with the production of pe~xyacetic acid, e.g., in large industrial operations in the food industry, could not be satisfied to a satisfactory degree by the process of EP-A-0269 345.
It is the object of the present invention to avoid the disadvantages and problems detailed above which are connected with the production, treatment and use of peroxycarboxylic acids, in palticular the pungent odor and thF risk of irritation and corrosion of the eyes, the skin and the mucous membranes of the operatives and to make a process and a device a~vailable by means of which a rapid adjus~ment of the reaction equilibrium and consequently a satisfactory continuous execution of the process is possible.
2 ~
SUI~L~RY OF THE IIYVENTION
The object of the present invention is achieved by way of a continuous process and a device for the production of peroxycarboxylic acids, and in parlicular, peroxyacetic acid, in which the peroxyca~boxylic acid is S produced in a closed facility, only when directly re~uired and in the desired quantity. Direct contact wi~h personnel is avoided during the manufacture of the peroxycarboxylic a~ids and during their use, e.g., as a disinfectant.
In particular, the continuous process of the present invention comprises the step of: converting a carboxylic acid with hydrogen peroxide in 10 an aqueous medium in the presence of a catalyst, at a temperature of 40 to 60C. The process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the retention reactor, and after the reaction equilibrium has been adjusted, the peroxycarboxylic acid that is formed is continuously withdrawn from the 15 retention reactor.
The present invention is also dire ted to a device for carrying ut the continuous process of the present invention. ~he device of the present invention comprises a retention reactor for holding tbe reaction medium; a heating element capable of heating the reaction me~ium to 40 to 60C; and 20 two feedlines, wherein each of the ~eedlines is equipped with a returll valve and a metering punnp capable of substantially continuously pumping a reaction component from its storage vessel into the feedline and into the retention reactor.
21316~
IBÆF DESCRIPTION OF THE FIGURES -FIGURE I is a graph plot of " % peroxyacid" (y axis) versus "reaction time" hl minutes (x axis) as a function of three different temperatures. The three temperatures reflect the effect of temperature on the S time required to achieve reaction equilibrium.
FIGURE 2 is a diagrammatic representation of one embodiment of a device of the present invention ~or continuously producing the peroxycarboxylic acid.
, ~, ., . " ~.
~ 2~3~
I:2ETAILED DESCRIPTIOIY OF TH!E I~WENTION
The present invention has two aspects. In its first aspect, the invention is directed to a continuous process for producing a peroxycarboxylic acid. The process of the present invention comprises the step of converting a 5 carboxylic acid with hydrogen peroxide in an aqueous reaction medium in the presence of a catalyst at a temperature of 40 to 60C. l~e process of the present invention is characterized in that the hydrogen peroxide and the carboxylic acid are continuously passing into the reaction chamber, and after the reaction equilibrium has been achieved, ~he peroxycarboxylic acid thus 10 formed is continuously withdrawn from the retention reactor.
The effect of the reaction temperature on the reaction equilibrium and the results obtained are showrl in the following Figure 1. The measured values are based on a mixture of 14 7% hyclrogerl peroxide, 37.5%
acetic acid, û.S% stabilizer, 11.25% suiphuric acid and 36.05% water. Figure 15 I shows that by heating the reaction mixture to approximately 50C, the reactiorl equilibrium, i.e., the optimum concentration of desired peroxyacetic acid, is achieved after only approximately thirty minutes. At room temperature or lower temperatures (e.g., at 5C in an unheated room in ~:
winter), the equilibriurn is reached much later, narne1y a~ter a period which is 20 too long ~or a contimlous process in order to satis~y the requirement of peroxyacetic acid, Çor exarnple, for disinfecting purposes in a modem clean~ng facility ~e.g., a bonle cleaning facility in the beverage industry) or ~n a pros~uction ~acility (e.g., tank disinfection in breweries).
The subject matter of the invention is a process for the 25 continuous production of peroxycarboxylic acids by converting a ca~oxylic acid with hydrogen peroxide in an aqueous medium in the presence of a 3 ~
catalyst. charact~r~ed in that the conversion is carried out at a temperature in the range of ~0 to 60C and further characterized in that the peroxycarboxylic aid so produced does not require dilution.
According to an appropriate embodiment of the process 5 accordin~, to the invention, the hydrogen peroxide and the carbo~ylic acid/catalyst mixture are passed continuously to a retention reactor for receiving the reaction mixture in two separate feedlines and the peroxycarboxylic acid formed is continuous!y withdrawn from the retention reactor after adjusting the reaction equilibrium.
The hydrogen peroxide used according to the process is preferably a hydrogen peroxide with a concentration of 30 to 50% by weight.
As catalyst, any common catalyst known as suitable for the produc~ion of peroxycarboxylic acids by conver!ing a carboxylic acid with hydrogen peroxide can be used. Catalysts used according to the invention are prefe~bly mineral acids such as phosphoric acid or nitric acid and in particular, sulphuric acid. Hydrochloric acid is not suitable for use as mineral acid because it can easily lead to decomposition reactions. Basically, however, any organic (e.g., phosphonic acid) or inorganic acid can be used as catalyst provided that it is stable vis-a-vis the oxidizing medium and does not promote 2û the decomposition of the active oxygen carrier.
The conve~sion is camed out at a temperature in the region of 40 to 6ûC, and preferably a~ a temperature of approxirnately S0 to 60C.
The concentration of the peroxycarboxylic acid in the reac~ior medium can be varied within a wide range. Preferably, the concentration is 10 to 30%; more preferably, 10 to 25% by weight; and most preferably, 13 to 15% by weight.
~:~3~6~
In general, the reaction temperature is in the region of 40 to 60, particularly, in the region of 50 to 55C. Typically, the reaction is carried out at a temperature of approximately 50C.
If temperatures above 60C are used, the decomposition of the S peroxycarboxylic acids is accelerated in an undesirable manner. If a ~emperatuse of less than 40C is used, the reaction equilibrium is reached after a time which is unsuitably long for a continuous execution of the process.
In the process of the present invention, the carboxylic acid used is preferably a C~ - C6 carboxylic acid or an oligocarboxylic acid, and in 10 particular, ~ormic acid or acetic acid.
According to a preferred embodiment of the process of the invention, ~he peroxycarboxylic acid (e.g., peroxyacRtic acid~ that is withdrawn from the retention reactor is passed directly to the application, e.g., directly to a line to be disinfected or to a bottle cleaning plant in the beverage 15 industry or directly to a production facility to be disinfected e.g., the fermentation, storage and pressure tanks in a breweryt or directly to any other disinfectant circuit. In this way, contact with the peroxycarboxylic acid , harTnful to heal~h or its vapors and the associated problems such as irritation and corTosion of the eyes, the mucous membranes and the skin can be avoided 20 by controllin~ the process lcontrolling ~he quantities of peroxycarboxylic acid conc~ntJate produced) and by using a closed circui~ up to the intended application, e.g., up to the plant or line to be disin~ected.
By controlling the reaction temperature according to the present i~i~tention, it is also possible to achieve the reaction equilibrillm in a time 25 sufficiently brielF for a con~im30us easily controllable execution of the process, e.g., in approximately thirty minutes as a result of wSIich the process is easy to ~ ~ 3 ~
~ontrol and it is thus possible to adjust the quantities produced according to the process to the requirement concerned, and to consequently avoid funher treatment of the peroxycarboxylic acids hannful to health connected with intennediate storage.
S In its second aspect, the subject matter of the present invention also includes a device which is suitable for the continuous production of peroxycarboxylic acid according to the process of the invention and comprises:
a retention reactor for receiving the reaction medium, the retention reactor being equipped with a heating device and two supply lines equipped with return valves, which lines are each equipped with a metering pump for supplying the reaction components from the storage vessel to the supply lines and into the retention reactor.
The volume of the retention reactor depends mainly on the perforrnance required (e.g., the output of peroxycarboxylic acid concentrate per hour). Heating of the reaction mLxture can take place by way of internal heating, e.g., in the fonn of an elec~nc heating coil, or by external heating, ~-~
e.g., in the fonn of a hollow jacket surrounding the reactor through which a heating liquid or steam is passed. If the reactor consists of a material with a low thermal conductivi~y, e.g., of a material resistant to the components of thereaction mi%ture, such as a polymer, heating talces place preferably via an internal heating unit.
Passing the reaction components (e.g., hydrogen peroxide and acetic acid) from the storage vessel into the supply lines and into the retention se~ctor ~akes place via metering pumps with flow controls. The suction "lances" into the S~otage vessel ate eqoipped with "empty" indieatots.
~ ~ - 2 ~
In the device and process of the present invention, the hydrogen peroxide is stor~d separately from the carboxylic acid component.
Preferably, the device according to the invention is equipped with a pressure sensor situated at the outlet of the retention reactor.
S Appropriately, this pressure sensor is coupled with a device which douses the device automatically w;th water once a maximum pressure has been exceeded.
In this way, it is possible to guarantee a high level of operational safety because the device can be doused automatically with water via the pressure sensor and the facility coupled with it if a pressure limit is exceeded which can iO be caused e.g., by an unexpected decomposition reaction.
Appropriately, the device is also equipped with a mechanical pressure relief valve by way of which a decrease in pressure in the reactor can take place even ~n the case of a power failure.
For proper and simple maintenallce of the facility, it is appropriate to equip the device with a ventlng valve and a discharge valve for ventin~ and/or draining respectively and with a valve for dousing with water.
The discharge of the peroxycarboxylic acid ejectecl by ~he water douse via the discharge valve takes place appropriately via a neutralization vessel colmected to the device.
According to a par~icularly appropriate embodimeot, tbe device is equipped with suitable facilities for directly metering tihe peroxycarboxylicacid withdrawn from the retention reactor to the site of application. In this way, it is possible by a suitable controi of the process, i.e., of the output ofperoxycarboxylic acid concentrate per hour and direct dispatch to the site of application (e.g., bottle cleaning facilities to be disin~cted with peroxycarboxylic acid in the beverage industry, production f~ilities, e.g., 211 3~ 6~
fennentation stordge and pressure tanks in breweries etc.) to avoid any intermediate storage and disect contact between the peroxycarboxylic acid that is hannful to health and the operating personnel. lFor this reason, the peroxycarboxylic acid concentrate is usually metered directly, e.g., into the 5 lines to be disinfected or into a disinfection circuit, the metering operation being controlled via the controls of the process for the production of the peroxycarboxylic acids (output of peroxycarboxylic acid concentrate per hour) coupled with electrochemical sensors.
In the device according to the invention, at least those parts 10 coming into contact with the starting or the end products (carboxylic acid, hydrogen peroxide" mineMI acid catalyst, peroxycarboxylic acid) consist of materials resistant to corrosion vis-a-vis these substances. Such materials are e.g., polymers, in particular polyvinylidene fluoride (PVDF) and/or polytetrafluoroethylene ~PDFE), glass or corrosion-resistant steel and/or non-15 fierrous metal, if necess~ry additionally provided with a corrosion-resistant coating by a suitable passivating measure, such as are hlown to the art.
The retention reactor, particularly, if i~ is equipped with interna~
heating, is provided with a heat insulating jacket, e.g., a hollow jacket filled, if necessasy, with thennal insulating material, or a coating of a thermally 20 insulating material. The heating of the retention reactor can appropriately be controlled in an infinitely variable manner. A standard heat exchanger or retentiorl reactor known and suitable for this purpose can be used, it being possible ~or the retention reactor to be subdivided into a temperature-controlled he~ting section and a thennally insulated residence section.
~5 It is also within the scope of the device of the present invention that the electronic control, regula~ion and overflow control ~acility be provided 2~L3~6~
by way of a member selected from the group consisting of a memory-progfammable control, a single-board microcomputer, ~ microcomputer development system, a personal computer havin~ digital and analog input and output boards and discreet electronic or electromechanical circuits, and a S combination ~hereof.
Figure 2 contains a diagrammatic representation of one embodiment of a device according to the invenCion. The present invention will now be explained in further detail on the basis of the device illustrated in Figure 2 without being limited thereto in terms of its scope. The embodimen~
10 illustrated in Figure 2 is a device for the execution of the process according to the invention for the continuous production peroxycarboxylic acid by converting a carboxylic acid with hydrogen peroxide in the presence of a catalyst, the device comprising a retention reactor I for receiving the reaction medium. The retention reactor is equipped wilLh an el~ctrical internal heater 15 10 which is controlled in an infinitely variable marmer. The retention reactor is connected with ~wo feedlines 2,2 equipped with re~um valves 9,9, each line being equipped with a metering pump 3,3 for respectively supplying the reaction components (components I and 2) from the storage vessels 11, 12 to lines 2,2. The retention reactor is provided with a thermal insulation jacket 20 13. At the reactor outlet, there is a pressure sensor 4 (not illustrated) as an excess pressure control; this is connected to a magnetic valve 17 which opens when a pressure limit is exceeded, as a result of which the device is automatically doused with water. The device is also equipped with a n1echanical pressure relief valve 20 which is capable of e~fecting a decrease in 25 pressure in the reactor even in the c2se of a power fai~ure (e.g., failure of the mains powsr supply). The device is also equipped with a venting valve 5 and a discharge valve 6 for v~nting or discharging. It is additionally equipped with a neutralization vessel 7 via which the discharge of the peroxycarboxylic acid ejected by the water douse via the pressure relief valve 20 or discharged via the discharge valve 6 takes place. The neutrali~ation vessel has the form of an S overflow vessel. Metering of the peroxycarboxylic acid takes place in line with the user's requirements by controlling the magnetic valve 14 and the metering pumps 3,3 which suck the components from containers 11, 12 via suction iances with filling level sensors 15, 15. The storage vessels 11 and 12 are designed according to an ernbodiment used as an example as containers ~ ~.
10 with an 800 liter capacity and according to another ernbodiment provided as an example as drums with a 200 liter capacity. A~ magnetic valve 17 and a ball return valve 18 are connected downstream of the water connection. Between the metering pumps 3,3 and the retum valves 9,9, there is a device (19,19) for flow control.
The device illustrated in Pigure 2 was used to carry out the ;~
process according to the invention with a reactor output of 44 g peroxyacetic acid per hour or 2.76 kg of a 15% peroxyacetic acid concentrate forrned continuously by the reactor within one hour. The temperature of the heating section was approximately 50C as a result of which an equilibrium mixture 20 was obtained within approximately 30 minutes with an approximaiely 15%
peroxyacetic acid. rhe reactor volume was only I.5 Iiters, however, this was sufficient for the reactor perfonnance of 400 g peroxyacetic acid per hour indicated.
- By increasing the temperature andlor the concentlatioll of the 25 reactants further, it is possible to achieve a further acceleration of the reaction ~ ~ 3 ~
(shortest time to reach the equilibrium reaction mixhlre) an~d, if necessary, a filrther reduction of the reactor volume.
By utilizing the process and device according to the invention, it is thus possible, clepending on the selection and the concentration of the 5 cornponents and the choice of the reaction temperature, to continuously produce aqueous concentrates of peroxycarboxylic acids having the same or - -different concentrations as added to satisfy any demand. In this way, it is .
possible to continuously satisfy the requirement for peroxycarboxylic acids, particularly, peroxyacetic acid as disinfectant m the chemical industry and 10 allied branches of industry, e.g., in the food industry, the paper industry and in particular, in beverage operations and breweries. In average operations, such as mineral water wells and breweries, peroxyacetic acid is used as a disinfectant for sterilizing the rinsing areas of the bottle cleaning facilities.
These facilities res~uire a continuous, uni~olm dosage of approximately 10-20 15 mg peroxyacetic acid per Liter fresh water supplied. In the bottle cleaning facilities of the usual size, approximately 10-20m3 fresh water are consumed per hour. On ~his basis, a maximum requirement of 400 g peroxyacetic acid per hour can be calculated which, as indicated above, can be easily provided in a controlled manner by way of the process according to the invention and 20 the device according to the inven~ion in a closed circuit which is safe even for the operating personnel, while avoiding intermediate stolage.
Claims (28)
1. A process for the substantially continuous production of peroxycarboxylic acids comprising converting a carboxylic acid with hydrogen peroxide in an aqueous medium in the presence of a catalyst, characterized in that the conversion is carried out at a temperature range of 40° to 60°.
2. The process according to Claim 1 characterized in that the hydrogen peroxide and the carboxylic acid are continuously passed to a retention reactor in two separate feedlines, and the peroxycarboxylic acid formed is withdrawn continuously from the retention reactor after the reaction equilibrium has been attained.
3. The process according to Claim 2 characterized in that the concentration of the hydrogen peroxide is 30% to 50% by weight.
4. The process according to Claim 3 wherein the catalyst is a mineral acid.
5. The process according to Claim 4 wherein the mineral acid is a member selected from the group consisting of sulphuric acid, phosphoric acid and nitric acid.
6. The process according to Claim 5 wherein the mineral acid is sulphuric acid.
7. The process according to Claim 6 wherein the conversion is carried out at a temperature of 50 to 60°C.
8. The process according to Claim 7 wherein the conversion is carried out at a temperature of about 50°C.
9. The process according to Claim 8 wherein the concentration of the carboxylic acid in the reaction medium is 10% to 50% by weight.
10. The process according to Claim 9 wherein the concentration of the peroxycarboxylic acid in the withdrawn reaction medium is 1% to 30% by weight.
11. The process according to Claim 10 wherein the carboxylic acid is a member selected from the group consisting of a C1-C6 monocarboxylic acid and a oligocarboxylic acid.
12. The process according to Claim 11 wherein the C1-C6 monocarboxylic acid is a member selected from the group consisting of formic acid and acetic acid.
13. The process according of Claim 12 further comprising the step of passing the peroxycarboxylic acid withdrawn from the retention reactor directly into a pipeline to be treated or to a disinfectant circuit.
14. A device for carrying out the process according to Claim 1 comprising: a retention reactor for holding the reaction medium, the retention reactor being equipped with a heating element capable of heating the reaction medium to 40° to 60°C, two feedlines equipped with return valves, each of the feedlines being equipped with a metering pump for pumping a reaction component from a respective storage vessel into the respective feedline and into the retention reactor.
15. The device according to Claim 14 wherein the heating element of the retention reactor is a member selected from the group consisting of an electric heating coil and an external heating jacket surrounding the reactor.
16. The device according to Claim 15 further including a pressure sensor at the reactor outlet.
17. The device according to Claim 16 wherein the pressure sensor is coupled with a magnetic valve which triggers the automatic dousing of the device with water once a pressure limit is exceeded.
18. The device according to Claim 17 further comprising a mechanical pressure relief valve to reduce the pressure in the reactor.
19. The device according to Claim 18 further comprising a venting valve and a discharge valve for venting or discharging.
20. The device according to Claim 19 further comprising a neutralization vessel through which the discharge of the peroxycarboxylic acid discharged or ejected by the water douse can be effected.
21. The device according to Claim 20 further comprising a suitable facility for directly metering the amount of peroxycarboxylic acid withdrawn from the retention reactor and transferred to the site of application.
22. The device according to Claim 21 wherein those parts of the device coming into physical contact with a chemical member selected from the group consisting of a carboxylic acid, a hydrogen peroxide, a catalyst, and a peroxycarboxylic acid, consist of a material which is corrosion-resistant to said members.
23. The device according to Claim 22 wherein the material is polymer.
24. The device according to Claim 23 wherein the polymer is a member selected from the group consisting of polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
25. The device according to Claim 22 wherein the corrosion-resistant material is glass.
26. The device according to Claim 22 wherein the corrosion-resistant material is a member selected from the group consisting of a corrosion-resistant steel and a corrosion-resistant non-ferrous metal uncoated or coated with a polymer of glass.
27. The device according to Claim 22 wherein the corrosion resistant material is a steel or a non-ferrous metal that has been made resistant to corrosion by a suitable passivation measure.
28. The device according to Claim 21 wherein the electronic control, regulation and overflow control facility is provided by way of a member selected from the group consisting of a memory-programmable control, a single-board microcomputer, a microcomputer development system, a personal computer having digital and analog input and output boards and discreet electronic or electromechanical circuits, and a combination thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934330465 DE4330465A1 (en) | 1993-09-08 | 1993-09-08 | Process and device for the continuous production of peroxycarboxylic acids |
| DEP4330465.5 | 1993-09-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2131664A1 true CA2131664A1 (en) | 1995-03-09 |
Family
ID=6497201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2131664 Abandoned CA2131664A1 (en) | 1993-09-08 | 1994-09-08 | Process and device for the continuous production of peroxycarboxylic acids |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0641777A1 (en) |
| CA (1) | CA2131664A1 (en) |
| DE (1) | DE4330465A1 (en) |
Cited By (8)
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|---|---|---|---|---|
| EP2678436B1 (en) | 2011-02-24 | 2020-11-04 | Kemira OYJ | Method for preventing bacterial infection in a fermentation process |
| US10899707B2 (en) | 2014-12-18 | 2021-01-26 | Ecolab Usa Inc. | Methods for forming peroxyformic acid and uses thereof |
| US11026420B2 (en) | 2016-12-15 | 2021-06-08 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning in energy services |
| US11040902B2 (en) | 2014-12-18 | 2021-06-22 | Ecolab Usa Inc. | Use of percarboxylic acids for scale prevention in treatment systems |
| US11071301B2 (en) | 2016-10-21 | 2021-07-27 | Ecolab Usa Inc. | Anti-microbial agent to control biomass accumulation in SO2 scrubbers |
| US11117172B2 (en) | 2015-12-16 | 2021-09-14 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning |
| US11241009B2 (en) | 2016-04-15 | 2022-02-08 | Ecolab Usa Inc. | Performic acid biofilm prevention for industrial CO2 scrubbers |
| US11352649B2 (en) | 2012-06-21 | 2022-06-07 | Ecolab Usa Inc. | Methods for reducing and/or eliminating microbial populations in a fermentation process |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1004576A1 (en) * | 1998-11-23 | 2000-05-31 | SOLVAY (Société Anonyme) | Process for producing peracetic acid |
| EP1016657B1 (en) * | 1998-12-15 | 2002-01-30 | Akzo Nobel N.V. | Method for producing peracetic acid |
| DE10048513A1 (en) | 2000-09-29 | 2002-04-11 | Degussa | Process for the continuous production of substance and reaction mixtures and device for carrying it out |
| FI116466B (en) * | 2001-10-30 | 2005-11-30 | Kemira Oyj | Process for the preparation of percarboxylic acid |
| CN104271549B (en) | 2012-05-03 | 2017-07-04 | 帝斯曼知识产权资产管理有限公司 | It is a kind of new to prepare vitamin B6Midbody compound |
| US11925914B2 (en) * | 2020-03-09 | 2024-03-12 | Kemira Oyj | Performic acid production systems and methods |
| CN115837258A (en) * | 2023-02-22 | 2023-03-24 | 凯莱英生命科学技术(天津)有限公司 | Continuous preparation device and continuous preparation method of anhydrous peroxyacetic acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE630363A (en) * | 1962-04-04 | |||
| DE3638552A1 (en) * | 1986-11-12 | 1988-05-26 | Benckiser Gmbh Joh A | Apparatus for preparing and metering peroxo-acids |
| SU1668358A1 (en) * | 1989-05-16 | 1991-08-07 | Предприятие П/Я В-2304 | Method for obtaining aqueous peracetic acid |
| JP3046628B2 (en) * | 1991-01-23 | 2000-05-29 | 日本パーオキサイド株式会社 | Method for producing peracetic acid composition |
-
1993
- 1993-09-08 DE DE19934330465 patent/DE4330465A1/en not_active Withdrawn
-
1994
- 1994-08-29 EP EP94113464A patent/EP0641777A1/en not_active Withdrawn
- 1994-09-08 CA CA 2131664 patent/CA2131664A1/en not_active Abandoned
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2678436B1 (en) | 2011-02-24 | 2020-11-04 | Kemira OYJ | Method for preventing bacterial infection in a fermentation process |
| US11352649B2 (en) | 2012-06-21 | 2022-06-07 | Ecolab Usa Inc. | Methods for reducing and/or eliminating microbial populations in a fermentation process |
| US10899707B2 (en) | 2014-12-18 | 2021-01-26 | Ecolab Usa Inc. | Methods for forming peroxyformic acid and uses thereof |
| US11040902B2 (en) | 2014-12-18 | 2021-06-22 | Ecolab Usa Inc. | Use of percarboxylic acids for scale prevention in treatment systems |
| US11772998B2 (en) | 2014-12-18 | 2023-10-03 | Ecolab Usa Inc. | Use of percarboxylic acids for scale prevention in treatment systems |
| US11117172B2 (en) | 2015-12-16 | 2021-09-14 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning |
| US11241009B2 (en) | 2016-04-15 | 2022-02-08 | Ecolab Usa Inc. | Performic acid biofilm prevention for industrial CO2 scrubbers |
| US11882826B2 (en) | 2016-04-15 | 2024-01-30 | Ecolab Usa Inc. | Performic acid biofilm prevention for industrial CO2 scrubbers |
| US11071301B2 (en) | 2016-10-21 | 2021-07-27 | Ecolab Usa Inc. | Anti-microbial agent to control biomass accumulation in SO2 scrubbers |
| US11844349B2 (en) | 2016-10-21 | 2023-12-19 | Ecolab Usa Inc. | Anti-microbial agent to control biomass accumulation in SO2 scrubbers |
| US11026420B2 (en) | 2016-12-15 | 2021-06-08 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning in energy services |
| US11647747B2 (en) | 2016-12-15 | 2023-05-16 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning in energy services |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0641777A1 (en) | 1995-03-08 |
| DE4330465A1 (en) | 1995-03-09 |
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