4th period, 1989 - 2015: development of flow-through electrochemical diaphragm reactors with coaxial electrodes with consideration of optimal size and materials

1-experimental model of the EKHATRON-K device for the production of gaseous hydrogen chloride – an effective agent for saccharification of straw. Made according to the technical assignment of prof. Kalunyants K.A. For the first time, the device uses reactors RPE-10L (4) with FEM-1 elements (3). Moscow, Moscow Technological Institute of Food Industry, 1989.
2 – an electrochemical reactor made of two hydraulically parallel connected FEM-1 elements. Moscow, VNIIIMT, 1989.

The first STEL installations and electrochemical reactors with PEM-2 elements, which have a number of advantages in comparison with PEM-1 elements. In total, the Laboratory of Electrotechnology (LLC “LET”) produced several thousand PEM-1 elements and several tens of thousands of PEM-2 elements in the period from 1989 to 1995.
Moscow, LLC “LET”, JV “EMERALD”, VNIIIMT, 1994.

With the advent of the flow-through electrochemical element PEM-3 (1995), a period of intensive development of the design of electrochemical devices of the widest range of applications, both small and large unit capacity, began. The possibility of parallel, sequential and mixed both hydraulic and electrical connection of PEM-3 elements in one reactor provided flexibility and ease of implementation of various technological processes of electrochemical conversion of water and aqueous solutions of various electrolytes. In total, in the period from 1995 to 2009, Laboratory of Electrotechnology LLC produced more than 1 million elements of PEM-3. 1995.

The principle of joining flow-through electrochemical modular elements (FEM) into high-capacity reactors is borrowed from wildlife. The combination into a single system of compact, reliable, high-performance, easily replaceable, unpretentious to external influences and resistant to overloads, simple in design elements results in easy solution of problems that are currently being solved with the help of heavy, bulky elements, inertial in operation, sensitive to the slightest deviations from optimal conditions of systems (industrial electrolysers), or have not been resolved to date due to the lack of adequate technical systems.

The hydraulically parallel joining of FEM-3 elements into a unified reactor in 1998 – 1999 was experimentally tested on AQUACHLOR devices with a chlorine capacity of 1 kg/h. Extremely harsh conditions of the ion-selective electrolysis process in AQUACHLOR devices required the development of electrochemical cells of a different type than FEM-3, which in its parameters did not correspond to the operating conditions in AQUACHLOR devices

Searching for optimal designs for the implementation of the ion-selective electrolysis process is associated with the development of new reactor designs. 1 – 4 – design options for reactors of AQUACHLOR systems based on FEM elements with a diaphragm 11 mm in diameter. 5 – A reactor of 40 FEM-3 elements with a capacity of 400 grams of a gaseous mixture of oxidants per hour. Power consumption is 800 watts. Moscow, VNIIIMT; Saint Louis, Monsanto (USA), 1997.

Tests of experimental models of AQUACHLOR devices, manufactured under a license agreement by Monsanto, at an industrial facility – a cooling water supply system of the American Pacific Corporation Power Plant in Nevada, USA, have revealed design flaws, but have also demonstrated very promising technological properties of the oxidant solution: unsurpassed antimicrobial activity with no corrosive effects. For the first time in many years, biofilm has been removed from the interior of the cooling system, resulting in improved heat transfer efficiency and significant cost savings. USA, 1997.

Installation of STEL – 1000 – SK with a capacity of 1000 liters per hour on an anolyte of ANC for feed silage. The installation uses two RPE-20M reactors of 20 PEM-3 elements in each reactor. The power consumption is 2.5 kW. Moscow, 1994. In the period from 1990 to 1994, the STEL-1000-SK installation used a reactor made of two graphite monoblocks in titanium housings (right).

1, 2 – modifications of the STEL-10N-120-01 device (models 1000-05, -06) for the production of anolyte ANK with a capacity of 1000 liters per hour from an initial solution of sodium chloride with a concentration of 5 g/l. The concentration of oxidants in the anolyte ANK is 500 mg/l, the power consumption is 3.5 kW. The devices were used at large agricultural complexes and industrial enterprises. 1995.
3 – STEL-10N-120-01 device, STEL-NERL-2500-03 model with anolyte ANK capacity of 2500 l/h. Devices of this modification were used to disinfect water applied to displace oil from productive strata. 1995.

Electrochemical blocks RPE-26 for universal use, consisting of twenty-six FEM-3 elements for use in AQUACHLOR and STEL devices.The supply voltage of the elements and the current strength in each of them in such a unit could vary from 5 volts and 8 amperes to 24 volts and 4 amperes. In the volt-ampere range 5 – 8, the AQUACHLOR units allowed to obtain up to 260 – 270 grams of chlorine per hour, which made it possible to disinfect up to 200 – 250 cubic meters of natural water per hour.The operation of the blocks in the volt-ampere range 24 – 4 was used in modified STEL-10N-120-01 devices to obtain low-mineralized (1.3 – 1.5 g/l) anolyte ANK with an oxidant concentration of 500 – 550 mg/l at a capacity of 250 liters per hour.STEL and AQUACHLOR devices with RPE-26 electrochemical units were used mainly for industrial purposes: at small water treatment plants, in agricultural production, in food industry.Moscow, Institute of Medical Technology (VNIIIMT), 1997

1 – installation for the production of electrochemically activated anolyte for disinfection, pre-sterilization cleaning and sterilization of STEL-4N-60-02M. The capacity is 60 liters per hour according to an anolyte of ANC. The electric power consumption is 300 watts. The electrochemical reactor RPE-6L consists of four elements of PEM-2. Developed at VNIIIMT in 1994, the container for concentrated salt solution is made transparent and placed in the back of the unit, which increases the ease of use of the unit. One filling of the tank with saline solution is enough to obtain 750 liters of an anolyte.

2 – installation of STEL-10N-120-01, model 80-01 with a capacity of 80 liters per hour according to an anolyte. Moscow, VNIIIMT, 1998. 3 – installation of STEL-10N-120-01. model 60-01 with a capacity of 60 l / h according to an anolyte ANC. Moscow, NPO Khimavtomatika, 1995. 4 – installation of STEL-10N-120-01 with a capacity of 120 liters per hour for an anolyte of ANC. The basic model for STEL installations of this type. Moscow, VNIIIMT, 1995.

1, 5 – STEL-80 installations. 2, 3, 4 – stages of production of the STEL-120 installation. 6 – STEL-Compact installation with an anolyte capacity of 10 l/h for use in the field and in transport. 7, 8 – STEL-40 and STEL-20 installations for rural hospitals.

STEL installations with RPE reactors of 2 and 8 PEM-3 elements for the production of AN anolyte on livestock farms.
Manufactured by Hydrofem (Ireland) under license. 2003.

The first experimental model of the BAZEX apparatus for regulating the biocompatibility of a dialysis solution by reactionless changes in its pH and redox potential (ORP).
The use of the BAZEX device normalizes the ORP of the dialysis solution and makes it equal to the ORP of the patient’s internal environment, which reduces the time of hemodialysis by 30-40%, and also contributes to the normalization of patients’ blood pressure, improves their well–being during the hemodialysis procedure, increases the degree of creatinine and urea extraction by increasing the selectivity of hemofiltration. Moscow, VNIIIMT, 1992.

The elements of PEM-3 – MB-11 are combined into a reactor of a given power with the help of stacked collectors formed from identical collector polyvinyl chloride elements EX-1, articulated using sleeve-nipple connections. Reactors of this type have the designation RPE-S. 1996.

In 1997, in order to achieve greater compactness of the RPE-S-36 reactor, the technical specialists of the Battelle Memorial Institute (USA), together with the authors of the FEM-3 elements, developed collector bushings for the FEM-3 elements. The prototype of this development was the collector bushings for FEM-2 elements previously created by Yu.G. Zadorozhny and V.M. Bakhir in 1992 (photo below left).

Further development of the designs of AQUACHLOR installations was carried out in order to determine the optimal conditions for convective circulation of solutions in electrode chambers and the length of hydraulic interchanges of PEM-7 elements. Since it takes a long time for installations to determine these parameters, as a rule, such
studies are carried out on real objects in coordination with competent and thinking specialists who understand the prospects and importance of this work.

Specialists of ceramic production of diaphragms in 1995 – 2008 conducted in-depth studies of their products working in a wide variety of conditions and adjusted the formulation and parameters of firing ceramics in accordance with the results of scientific research.

In–depth study of the structure and properties of ceramics of various compositions operating in extremely aggressive environments made it possible by 2011 to create absolutely reliable ceramic diaphragms used in a new generation of electrochemical systems – AQUACHLOR-M, STEL-ANK-SUPER, EMERALD-REDOX and others

The time of searching for optimal design and technological solutions when creating electrochemical installations with new reactors has always attracted enthusiastic partners with its opportunities to create a new one. They bought reactors and tried to create a working system according to their taste and mood. Sometimes these attempts were successful, but more often they ended in nothing. An example of an installation for obtaining an oxidant solution using ion-selective electrolysis technology with PEM-7 elements refers, rather, to a positive experience. The installation, which can be called AQUACHLOR, has a chlorine capacity of 4.5 kg/ h (160,000 cubic meters/day for disinfected water). It was installed in a chlorination plant in Shymkent (Kazakhstan) in 1999. Structurally modified, she has worked for more than 20 years, which is confirmed by the publications of persons responsible for water supply in the Republic of Kazakhstan in special journals.

Layout and general view of the AQUACHLOR-500 device (model 2005)
Floor area occupied by one device – 0.2 sq. meters; device weight – 60 kg.

AQUACHLOR installations with a capacity of 30, 50 and 100 grams of oxidants per hour are produced not only in the form of separate blocks, but also in the form of systems assembled on a frame and combining a container for saline solution (on the right), a container for an oxidant solution with a level sensor that turns off the installation when the container is filled and turns it on again when it is emptied. Also, a container with a 5% hydrochloric acid solution is placed on the common frame (prefabricated), which is used for flushing electrochemical reactors without shutting down the installation, which is achieved by simply switching the valves (on the panel at the bottom left) on the supply lines to the pump inlet of a salt solution and an acid solution. Usually, for flushing, the installation should be fed with an acid solution for no more than 20 minutes a day with round-the-clock operation.

1 – the very first model of the EMERALD installation, designed and manufactured by V.Bahir and Yu.Zadorozhim in 1990. The first sample of the PEM-2 element was used in the installation. ASPECT Cooperative, Moscow, 1990. 2 – model of 1991. 3 – model of 1993. 4 – model of 1995. Moscow, JV “EMERALD”, 1995. The installations shown in photos 2-4 were mass–produced by the joint Russian-British enterprise EMERALD, among whose founders were the authors.

Household installations IZUMRUD manufactured by the company “Laboratory of Electrotechnology” (LLC “LET” in the period from 1996 to 2011. During this period, 15 different technological schemes of water purification and conditioning were tested. Technological schemes of water purification differed in the sequence of stages of water treatment, their number, depth of treatment (current strength, load weight of auxiliary reactors (electrokinetic sedimentation, catalytic, flotation).

The layout of the elements inside the EMERALD installation housing with the technological scheme of AMETHYST cleaning. The installation was intended for use in offices. The capacity is 100 liters per hour. Auxiliary reactors of increased volume are made of quartz glass. Moscow, 2000.

EMERALD installations for food industry enterprises. The 1998 model. The capacity is 1000 liters per hour, the power of the current source is 1200 watts. Mixing reactors, flotation, destructive purification by microbubbles, catalytic), are made of standard cartridge filter housings.

Installation of the EMERALD “FOUNTAIN” for installation in places of collective use. The capacity is 40 liters per hour, the electric power consumption is 100 watts. Moscow, 2000.

The EMERALD plant with a capacity of 5000 liters per hour is designed to supply the small village of Samofalovka with purified water. The source water comes from the well, contains a large amount of hydrogen sulfide.
The installation uses five electrochemical reactors with a capacity of 1000 liters per hour. The photo shows two reactors. Yeisk, 2001.

1 – 3 EMERALD installations with a capacity of 500 liters per hour, electric power consumption of 900 – 1200 watts. Designed to remove iron, manganese, microbes and microbial toxins, organic compounds (phenols, petroleum products, surfactants) from water. Moscow, 2000 – 2006. The frequency of cleaning is from one to two times a month. Indication of the need for cleaning by the pressure sensor before the electrokinetic sedimentation reactor.

Installations for water purification in the field EMERALD-300C.
The hydraulic scheme of the installations corresponds to the technological process of water purification TOPAZ.
Hydroperoxide oxidants are introduced into the purified water at a concentration of 0.1 mg / l. The plant capacity is 300 l/h. Moscow, 2001.

Fundamental structural and technological changes in the elements of the MB-11 series made it possible in 2011 to create a number of new designs with significantly improved parameters: MB-11 elements with a cooled cathode (left), MB-11 element with a porous anode (center), MB-11 element with improved hydrodynamics of gas-liquid flows

Flow element electrochemical modular MB-11-03-01 . Moscow, Dolphin Aqua, 2011.

The need for a deep electrochemical transformation of liquids with high temperature, which was revealed during the inversion of sugar syrup (90 ° C) in the MB-11 elements mounted with silicone bushings on titanium collectors (photo bottom left), forced the development of the MB element-11-03-01 , which can work for a long time at temperatures up to 150 ° C.

STEL-UNIVERSAL devices with a capacity of 500 l/h for anolyte and catholyte. Right – 2008 model, left – 2011 model.STEL-UNIVERSAL devices with a capacity of 500 l/h for anolyte and catholyte. Right – 2008 model, left – 2011 model.

Electrochemical reactors of the STEL-UNIVERSAL units of the 2011 (1 and 2) and 2008 (3 and 4) models. The reactor of the STEL-UNIVERSAL installation of the 2011 model is assembled from 16 flow-through electrochemical elements.-26-09-01 unlike the reactor of the STEL-UNIVERSAL installation of the 2008 model, the reactor of which consists of 60 MB-11 elements. The design of the MB element-26-09-01 it allows for increased reliability of the installation when working in the field and during the electrochemical conversion of viscous liquids, for example, glycerin

The reactor of 8 MB-26 elements developed in 2009 (left) in 2011, two MB elements were replaced-26-01-01 (right). Advantages: one diaphragm instead of four; self-cleaning from cathode deposits; an order of magnitude longer service life. On the way between one and the other reactors, there were many experimental models of reactor elements of various designs, many variants of ceramic diaphragms, many variants of anode coatings (below). New design principles have opened up the possibility to significantly expand the range of operation of electrochemical modular systems.

Significant design improvements of the MB-26 elements made it possible to create new, highly reliable, MB elements with a number of additional features-26-09-1 (photo on the right), which can be successfully used to replace outdated models of elements (PEM-7, PEM-9, MB-26 – photo at the bottom left) in installations AQUACHLOR and STEL-ANK-PRO.
MB Elements-26-09-01 they have a number of additional features, which allows them to be used in installations of the STEL-UNIVERSAL type with a direct (without a gas separation chamber) duct through the anode assembly.

With the advent of a new generation of reactors, since the beginning of 2011, expensive and time-consuming technological processes for manufacturing anodes for elements PEM-7, PEM-9, MB-26 have become a thing of the past.

The electrochemical reactor of the AQUACHLOR-500M installation (1, 2) has the ability to self-clean from cathode deposits of hardness salts, unlike the reactor of the AQUACHLOR-500 installation (3, 4). This is due to differences in the intensity and direction of the electromigration transfer of mass and energy through the diaphragms of the MB-26 elements in the AQUACHLOR-500 installation and the MB elements-26-01-01 in the AQUACHLOR-500M installation.

AQUACHLOR and ECOCHLOR installations with one MB reactor-26-02-02 they provide a chlorine capacity of 1.5 kg/hour when operating in nominal mode and 2.0 kg/hour when operating with a maximum load for 24 hours.

Troitsk, Moscow, 2013. AQUACHLOR-500M device disinfects up to 6000 – 7000 m3 per day of drinking water.

Ugut, Khanty-Mansiysky autonomous region, 2013. One AQUACHLOR-250M device (the second one is reserve) disinfects up to 500 m3 of sewage water of village.

USA. ROYAL CHEMICAL, 2013. 2 AQUACHLOR-500M devices produce disinfectants.

USA. CHEMSTAR, 2014. 3 AQUACHLOR-500M devices produce disinfectants.

Needle valves VIT-4 (1) and VP-4 (2,3) with titanium and polypropylene shut-off elements, Up to 4. Membrane valves VM-5 (4,5,6) Up to 5 and VM-8 (7) Up to 8. Housing material – polypropylene, membrane – rubber IRP-1314.

Fittings made of titanium VT1-00. The diameters of the through sections (DN) are from 4 to 8 mm. Designed for the articulation of flexible hoses made of PVC or fluoroplast F 4MB.

1, 5, 8 – fittings-f Du 4 to 5 mm; 3, 4 – быстроразъемное compound, Du 4, and 5 mm; 2, 6, 7 – водоструйные насосы Du 4 производительностью from 20 to 80 l/h. Vacuum OT -0.5 to -0.9 kgs/cm2 when entering 2 to 3 kgs / cm2.

1 – level sensor of chlorine–saturated anolyte; 2 – 5 – pressure stabilizers “up to themselves” of gas-liquid, gas (chlorine) or liquid medium. The adjustable pressure range is from 0.1 to 3.0 kgf/cm2. The liquid throughput is up to 150 l / h. 6 is a separator for the pressure gauge, protecting it from an aggressive environment. Pressure range from 0 to 6 kgf/cm2. 7- water jet pump VN-200 for mixing chlorine with water, 200 l/h.

1,2 – quick-release couplings, DN 2 mm; 3-8 – DN4 fittings; 9 – fluid flow sensor. Response threshold – 30 l/h, fluid flow range – from 0 to 150 l/h; fluid pressure from 0 to 6 kgf/cm2; 10 – end filter (stainless steel mesh, mesh 0.3 mm), DN5 mm; 11, 12 – straight-through mesh filter, DN5 mm.

The uniqueness of the Delfin Aqua company was based on the direct participation of the author of electrochemical activation and the team of scientists and specialists he had been heading for many years in the development and production of electrochemical systems, which allowed Delfin Aqua in the period from 2011 to 2015 to occupy a leading position in the world in the creation and practical use of electrochemical Green technologies.In 2015, the Institute ceased its exclusive partnership with Delfin Aqua. This allowed the staff of the Institute to begin a new stage of scientific and technical activities in the field of design and production, as well as to resume work on joint scientific and technical projects with various companies – R&D partners of the Institute.

4th period, 1989 – 2015: development of flow-through electrochemical diaphragm reactors with coaxial electrodes with consideration of optimal size and materials