Application of polymer-containing solution or water suspension paste for collection of ruthenium in gaseous discharge, and device for its implementation

FIELD: chemistry.

SUBSTANCE: group of inventions concerns application of polymer-containing solution or water suspension paste and a device of ruthenium collection in gaseous discharge. The solution or water suspension paste contains one alkylene glycol polymer and/or one alkylene glycol co-polymer. The alkylene(s) contains 2-6 carbon atoms for ruthenium collection in gaseous discharge. The device includes a ruthenium collection cartridge with a substrate bearing alkylene glycol polymer or co-polymer. The alkylene(s) contains 2-6 carbon atoms.

EFFECT: improved ruthenium collection and chemical recovery of ruthenium oxide.

22 cl, 8 dwg

 

The technical field

The present invention relates to the application of a liquid or aqueous paste containing polymers, and capture device of ruthenium contained in the gas emissions.

It can find application, in particular, for filtering gas emissions resulting from reprocessing of nuclear fuel and containing or likely to contain ruthenium.

Ruthenium is one of the fission product atoms during nuclear reactions. In this capacity, he is present in the irradiated fuel rods. Its share fall to 6 wt.% from a group of fission products, its isotopes103EN and106EN are radioactive.

Methods of processing of nuclear fuel include, first of all, the cutting of fuel rods and their dissolution in nitric acid. Therefore, most of the components of rods, including ruthenium, goes into solution in the form of nitrates. Obtained by dissolving solution then send in the shop liquid-phase extraction. At this stage of the process, the ruthenium contained in the liquid phase, called the solution of fission products. This solution is fed into the plant vitrification, which is his calcination in the furnace, and the resulting elements in the form of oxides then steklovata.

Like other radioactive elements ruthenium subjected to vitrification. Unfortunately, CA is IDNA form RUO Li 4is extremely volatile and, despite the recovery in the processing gas emissions generated during these processes, some, albeit slight, can be released into the environment through possible leaks in the system processing.

Ruthenium in the form of gas RUO Li4can be served in the ventilation system of the building and move through the ventilation channels. He goes through all of seepage barriers ventilation systems. Thus, he comes to chimney stack of the first category and is discharged into the environment.

To date most of the reprocessing of nuclear fuels gas emissions generated in the emitting ruthenium chambers, passed through the complex of the two filters, in which they had been cleared from most of the large particles and which are excluded too fast driving subsequent filtration steps. After that, the emission was passed through the filters of the first and second barriers installed in a lined boxes.

In particular, these filter elements is the present invention creates a highly effective means of abatement of ruthenium.

Prior art

When ruthenium solid RUO Li2it becomes relatively simple its capture by absolutely the filter. Currently it is in the shops vitrification, which use ventilation systems with multiple filtration barriers. Filters very high efficiency of the first, second and third barriers do not pass solids RUO Li2. However, filters, very high efficiency is captured only RUO Li2, which is formed in the front part. If the recovery RUO Li4occurs in the rear part of the filter is very high efficiency, it is obvious that this place may release RUO Li2into the environment.

Indeed, fiberglass filter medium barriers very high efficiency is not able to hold gaseous RUO Li4who can enter the chimney, possibly recovering on the way to RUO Li2. Means for capturing RUO Li4it is, therefore, restore, RUO Li2in front of the filtration barriers with subsequent removal filter very high efficiency.

You can also direct gaseous emissions containing ruthenium, the reducing environment, such as poly(4-vinylpyridine) (PVP), or on wet metal surface serving as a catalyst. However, particulate traps, which is effective at ambient temperature, in particular the standard poly(4-vinylpyridine), cause of the Yan a significant reduction of pressure and therefore, necessitates a significant increase in the power of the fans.

You can also apply the flushing gas emissions aqueous solution containing, if necessary, the reagent, for example, sodium hydroxide. However, the formation of carbonate caustic soda due to sequestration of atmospheric CO2leads to a high consumption of reagent and, consequently, to the formation of a large volume of liquid waste.

As a rule, the effectiveness of these systems is limited. Indeed, the filter elements according to the prior art screen most of the aerosols, but they do not possess the ability to effectively delay RUO Li4.

To solve the obvious environmental issues there is therefore the need to use an effective method of recovery of ruthenium contained, in particular, in the gas emissions of reprocessing irradiated nuclear fuel.

Description of the invention

The inventors have established a method and apparatus for the recovery of ruthenium, which meet the specified need.

In particular, the method of capture is contained in the gas emission of the ruthenium according to the invention differs in that it includes the contacting of the gas emissions with a liquid or aqueous paste containing at least one polymer of the alkyl who glycol and/or, at least one copolymer of alkalophiles in which alkylene or alkylene contain from 2 to 6 carbon atoms.

Also the present invention relates to the use of the specified solution or aqueous paste for capturing contained in the gas emissions of ruthenium.

The method according to the invention can be used either in an apparatus for washing gases, and the polymer or copolymer used in the form added to the wash water reagent, or for the manufacture of the cartridge to trap ruthenium. The cartridge contains, for example, a substrate on which is deposited polymer alkalophilus or copolymer alkalophilus with 2-6 carbon atoms.

Thanks aqueous solution of the above polymer or copolymer of the present invention unexpectedly allows to achieve, for example, in an apparatus for washing gas emissions efficiency that is comparable to the effectiveness of the use of caustic soda, this eliminates the aforementioned problem of the formation of carbonate.

Installation for washing gas emission method according to the invention to a specialist known. For example, we can talk about the Packed column, Venturi scrubber, etc.

In case of use of the cartridge, the flexibility of the method and device according to the invention based on the above polymers and copolymers, effectively creating a trap on the I of ruthenium, compatible with existing installations for the reprocessing of irradiated nuclear fuel. In addition, the number of polymer is very low that allows you to actually override any security problem as well as difficulties for the management of waste resulting from the use of the invention during periodic replacements that may be necessary.

The choice of polymer or copolymer can be produced depending on application conditions, for example, depending on the operating temperature, the kind of other chemicals present in the gas emissions, the applicable substrate, cost, power, fans, etc. According to the invention the selectable properties of the polymers and copolymers used according to the present invention, can be:

- mainly water-solubility of the polymer or copolymer to be applied on the substrate by impregnation with aqueous solutions,

- the composition of the polymer or copolymer should preferably be simple, includes, for example, carbon, oxygen and hydrogen, which reduces the method and the device according to the invention,

the ability of the polymer or copolymer to catch (or catch - these two terms are used in the description of the same value) RUO Li4due to the fact that it contains one or a number of the reducing groups-IT is by analogy with the effect of hydrogen reduction of sodium.

Preferably, the polymer or copolymer contains hydroxyl end. In this case in mind, there are polymers and copolymers of alkalophiles with hydroxyl end groups.

Preferably, according to the invention the polymer alkalophilus was chosen, for example, from the group consisting of polyethylene glycol, polypropyleneglycol, poliatilenglikola or mixtures thereof.

It is preferable that the copolymer alkalophilus was a copolymer consisting of several polymers selected from the group consisting of polyethylene glycol, polypropyleneglycol, poliatilenglikola. For example, a copolymer of alkalophiles may be a copolymer based on at the same time, ethylene glycol, propylene glycol and butyleneglycol.

Preferably, according to the invention is a copolymer of alkalophiles answered the formula

where m and p denote independently from each other integers such as 1≤m≤8 and 3≤p≤12.

The polymer of formula (I) can be, for example, the polymer of polyethylene glycol and polypropylenglycol.

In the method and device according to the invention can be applied in a solution or paste of the above one polymer or copolymer, of a mixture of different of these polymers alkalophilus or of a mixture of different of these copolymers allenglish the I or of a mixture, consisting of one or more of these alkylene glycols and one or more of these copolymers alkalophile. Also, the terms "polymer or copolymer or polymers or copolymers of alkalophile"used in the present description, means, of course, different embodiments of the present invention.

For precipitation of ruthenium using solid substrates, these polymers have additionally the advantage that due to its wetting ability they are easy to apply a thin layer on a substrate, thus providing a higher parameters in relation to the pressure loss and the developed surface than known from the prior art products.

In the case when the implementation of the present invention is applied, the substrate, the aqueous paste of the polymer or copolymer is applied to the substrate. This method allows to effectively reduce the interfacial tension of the substrate depending on the ambient humidity and thus contributes to the capture of water contained in the treated gas emissions on the surface of the substrate, thereby facilitating the absorption of ruthenium and its recovery.

Forms of ruthenium affected by the present invention are mainly RUO Li4and RUO Li2. After contact with the substrate RUO Li4can absorbe is to find a polymer or copolymer, located on the surface and react with them. Indeed, these polymers and copolymers contribute to the absorption RUO Li4and limit its desorption, which, therefore, provides a sufficiently long time RUO Li4on the surface, necessary for its recovery. In addition, the hydroxyl groups of these polymers and copolymers enable recovery of ruthenium in the form of RUO Li2. Thus, the present invention simultaneously contributes to the recovery of ruthenium RUO Li2and chemical recovery.

Also preferably, according to the invention, the substrate was chosen mainly with a large surface contact with the treated gas emissions to reduce the pressure loss. Indeed contained in the emissions of ruthenium is in contact with the surface, as a result of the collision, therefore, it is preferable that the magnitude of the impact was as big as possible, to ensure maximum recovery of ruthenium. Particularly preferably, the substrate had a fragmented view of, for example, the type of fibers, for example, steel fibrous material or clusters of fibers, preferably without seals, to eliminate pressure losses when passing gas emissions through them. In addition, the fibrous substrate has the advantage is that it holds possible solid particles of ruthenium (RUO Li 2). In the case of the use of such a substrate, it is preferable that the contacting gas emissions occurred when the force transmitting these emissions through the fibrous substrate.

According to the invention the substrate can be, for example, metal wool (or steel fibrous material), preferably with a low density and a large developed surface, such as steel fibrous material. In fact, such a substrate allows to achieve very high efficiency with very low pressure loss, there is no need to replace the existing fans. The substrate may be glass wool.

The polymer or copolymer can be applied to the substrate by any suitable method known to the expert. It is preferable that, for example, when using a fibrous substrate, damage to the tool didn't score a substrate in order to permit the passage through it of gas emissions, limiting, if necessary, the pressure loss. Preferably used in the present invention, the polymers and copolymers were soluble in water and, therefore, allowed to get practical aqueous solutions, called impregnating solutions for the application of polymers and copolymers on a substrate, for example, by simple immersion in the name of the e impregnating solutions. The concentration of the solution can be determined, in particular, taking into account the amount of polymer or copolymer to be applied on the substrate. The preparation of such a solution and impregnation are described in the following examples. Preferably, after treatment on a substrate, such as forming its fiber was applied a thin layer or film of an aqueous paste of the selected polymer or copolymer on the whole area, i.e. in the case of fibers, all forming the substrate fiber.

According to the invention the contacting of the gas emissions with a solution or paste of the polymer or copolymer, applied, if necessary, on a substrate, can be carried out at a temperature at which the applied substances (polymers, the substrate) are not destroyed. Typically, the contacting is conducted at a temperature of from 20 to 50°C.

In the device according to the invention, the cartridge may further comprise the design, the carrier substrate coated with a polymer or copolymer of alkalophiles. According to the invention this design, in addition to his appointment to serve as a support for the substrate, can be used for insertion of the cartridge into the pipeline for gas emissions, which was previously installed. It may take the form of, for example, baskets. This design is made mostly of material suitable to primeneniyu conditions of the present invention, for example, stainless steel. Typically, this design gives the bullet its geometric shape.

According to the invention the geometry of the removable element is mainly conformed to the order, mainly, removable to place it in the pipeline for gas containing ruthenium involuntary passing of gas emissions through the cartridge. Indeed, in the result, it becomes possible pre-production modules of the substrate and carrier, the installation of which does not require modifying any equipment or technology. In addition, the cartridge may be provided on the periphery of the hermetic seals for forcing a gas containing ruthenium emissions take place, preferably without leakage through the cartridge. This is important for the direction of gas emission through the substrate impregnated with the polymer or copolymer, and to prevent any leakage from the cartridge to fully grasp the ruthenium contained in the gas emissions.

According to a preferred variant implementation cartridge according to the present invention can contain:

a substrate coated with a polymer or copolymer of alkalophilus, and the surface is formed of glass wool or steel fibrous material

- structure or frame, a supporting substrate coated with polim the rum or copolymer alkalophilus, moreover, this design is mostly a view of the basket, preferably lattice

- sealing means located on the periphery of the cartridge, for example, seal, such as Viton (trademark) or silicone, providing authoritative direction of gas emission through the substrate.

According to the invention can be applied one or more cartridges, situated if necessary, for example, sequentially, to sequentially pass through them gas emissions.

The ventilation system provided by the invention and related to the recovery of ruthenium, should, in particular, to ensure that the extraction and processing of cameras vitrification, and camera cleaning equipment for reprocessing irradiated nuclear fuel. Ventilation systems for equipment reprocessing of nuclear fuels contain, as a rule, several filter barriers:

- pre-prefilters average cleaning and prefilters high purification directly in the camera

filters very high efficiency in the first and second barriers inside lined boxes,

filters very high efficiency in the third barrier, located in boxes sealed gateways

- highly effective traps at the base of the chimney.

To capture RUO Li4at least one cartridge agreement is but the invention can be introduced, for example, in one or more of the above filter elements. An embodiment of the present invention is described below with examples.

Replaceable element according to the invention can be located either in the first barrier or the second. Filter elements of the first barrier will be mostly replaced at least every two years. Their replacement is made, in particular, after too intense radiation caused by radioactive particles that have been captured and which may have caused clogging. Filter elements of the second barrier are replaced, usually, rarely, as there are no high degree of exposure and significant clogging.

Placement of system of catching of ruthenium according to the invention in the first barrier provides the advantage that in the case of a decrease in the efficiency facilitates the periodic replacement of the first barrier. But after such placement, the substrate or medium for the recovery of ruthenium subjected to a more intense radiation that can cause aging.

Other characteristics and advantages of the present invention are explained using the following illustrative examples with reference to the attached drawings.

Brief description of drawings

Figure 1 shows the test stand for testing of this image is to be placed. It consists of a glass tube, inside of which are disks of steel fibrous material (S)impregnated with polymer or copolymer according to the invention, and a control disk. Through this tube, pass gas emissions containing ruthenium;

figure 2 is a graph showing the amount of ruthenium captured from the gas emission disks of steel fibrous material impregnated with a polymer or copolymer according to the invention, as well as the control, not the former use, the disk of steel fibrous material;

figure 3 - chart showing the collection efficiency of ruthenium (% monolayer) at ambient temperature using a layer of substrate WB 12 (trade mark), saturated polymers with different molecular weight, the extent of impregnation of about 100 wt.%;

figure 4 is a chart where you can see the captured amount of ruthenium in mass percent for each disk D1, D2 and D3 of the test bench in figure 1 using different polymers and copolymers according to the invention;

figure 5 - schematic illustration of the construction for placing the substrate impregnated with the polymer or copolymer according to the invention. The design consists of two concentric cylinders of the grid;

figure 6 is a schematic illustrating the location of the mean is the LCD (in this case, the collapsed), impregnated polymer or copolymer according to the invention, around the Central cylinder as the design depicted in figure 5;

7 is a schematic representation illustrating the installation of the outer cylinder as a design figure 5 around the substrate, coiled around a Central cylinder 6, for forming cartridge according to the invention;

on Fig - schematic representation of the filter is very high efficiency, which comprises a cartridge according to the invention, depicted in Fig.7.

EXAMPLES

Example 1. The use of polymers and copolymers according to the invention

The following table 1 are grouped different polymers, copolymers and mixtures used according to the present invention.

They are commercially available and are offered in particular, firms:

- LAMBERT RIVIÈRE (manufactured by ICI),

- ALBRIGHT&WILSON,

- ROTH SOCHTIEL.

Table 1
DesignationFull nameMelting point, °
PEGThe polyethylene glycol-
PEG 300-35000Polyethylene glycol with molecular weight 300-35000 g/mol-
COPO 1A block copolymer of polyethylene glycol and the floor is propylene glycol <0
COPO 2Copolymer of ethylene, propylene and butyleneglycol27
COPO 7The polyethylene glycol 2000 + polyethylene glycol 300, a weight ratio of 50/5025
COPO 9The polyethylene glycol 2000 + polyethylene glycol 300+ block copolymer of polyethylene glycol and polypropylenglycol, a weight ratio of 70/20/1034
SORO 10The polyethylene glycol 2000 + polyethylene glycol 300 + block copolymer of polyethylene glycol and polypropylenglycol, a weight ratio of 45/45/1023
COPO 11The polyethylene glycol 2000 + is a copolymer of ethylene, propylene and butyleneglycol, the weight ratio 50/5038
SORO 14The copolymer based on ethylene, propylene and butyleneglycol37

Example 2. Recovery of ruthenium copolymer according to the invention

Samples of steel fibrous material (diameter fibers 12 μm), denoted by WB 12 (trade mark), the substrate was soaked with a solution of a copolymer according to the invention, when the degree of impregnation of 5 wt.%. The copolymer used in this case and possessing surfactant properties, served as a copolymer of polyethylene glycol-polypropylenglycol remaining liquid at the temperature of the he environment and identified in table 1 as COPO1. He was delivered by the company Albright&Wilson under the trade name AMPLICAN.

The test conditions were as follows:

- T:18,5°C

- hygrometry: 42%,

- [O3]: 1.8 mg·l-1,

- consumption: 2,24 m·h-1,

- duration of test: 5 hours,

is one not used disk + three disks WB 12 impregnated CAR when the degree of saturation of 100%.

Figure 1 shows the test stand (1)used in this example. It consists of a glass tube (2), inside which there are three drive WB 12 (S), soaked in 100% COPO1, and control, not the former in the use of the disk (6) of the steel fiber material. Arrow (8) shows the direction of flow of gas emissions with the content of ruthenium in the pipe.

Three CDs and one control disk at the beginning of the traps were analyzed, the number of captured disks ruthenium (QRu) is shown in table 2 below. The percentage of entrapped ruthenium corresponds to the number of ruthenium, caught one disc relative to the total amount of the formed ruthenium. The percentage of ruthenium received into the trap corresponded to the number of ruthenium, caught one disc relative to the amount of ruthenium coming to the disk.

A control device mounted in the end of the stand, has allowed to determine the amount of ruthenium, which was not str is established with representation from disk.

Table 2
Not used the disk from WB 12Disk # 1 from WB12+COPO 1Disk # 2 from WB12+COPO 1Disk # 3 from WB12+COPO 1The control device
QRu mg0,0560,8180,2120,014<0,01
Caught ruthenium,%574191-
% ruthenium collected from entrants into the trap of ruthenium57894--

The results are presented in the graph in figure 2. This figure Dv means not used disk of steel fibrous material, D1, D2 and D3 are different, mentioned earlier drives, installed during the passage of gas emissions (from D1 to D3). The results are very satisfying, as almost all the amount of ruthenium was caught three, successively installed disks.

Example 3. The effect of increasing the melting temperature of the polymer or copolymer according to the invention

To study the impact of changes in the melting temperature of the polymer on the effectiveness of the inventors tested a series of polymer is the same number, differing only in molecular weight and hydroxyl number.

These polymers are the polyethylene glycols, whose properties are listed in table 3.

Table 3
State t° environmentMolecular mass, g/molThe melting point °Hydroxyl number, I(OH)
Polyethylene glycol 600Liquid60015-25178-197
Polyethylene glycol 1500Solid150042-4870-80
The polyethylene glycol 35000Solid3500060-653-4

On the graph of figure 3 shows the efficiency of the trapping layer of the substrate from WB12-impregnated polymer in an amount of about 100 wt.% (the weight of the polymer is equal to the mass of steel fibrous material), when the ambient temperature.

The collection efficiency decreases dramatically with increasing molecular weight and decreasing hydroxyl number of I(OH). These two properties vary oppositely to each other, a hydroxyl number as a measure of the number of ends of primarygames (HE - chain ether - oxide - HE). If you divide the polymer chain, the number of ends of the chain (HE) will increase, but will decrease the molecular weight. These parameters are linked by the way, is summarized in table 4

Table 4
Molecular weightHydroxyl number
Polyethylene glycol 1500Divided by 2.5Multiplied by 2.5
Polyethylene glycol 600

The higher you raise the melting point of the polymer to increase its mechanical strength, the less efficient it is. Therefore, there is a compromise between mechanical strength and effectiveness, which can easily be found on the basis of the present description.

For the following examples, the inventors chose the polymers, the melting point of which lies in the selected application range of about 40°C.

At this temperature the polymer is in the form of wax, i.e. it is not liquid, and a soft body.

Example 4. Mixtures of polymers

Simultaneously with the search for a polymer with a melting point of 40°With the inventors prepared a mixture of polymers, which allowed for ucati the melting point of the mixture 40° C. In the basis should be the ability to combine the polymer with a high molecular weight and high melting point of the polymer with low molecular weight, giving the surface-active properties and hydroxyl number.

Were obtained mixture: SORO 7, SORO 11, SORO 2, SORO 9 and SORO 10 above in table 1.

Steel fibrous material WB 12 has infiltrated in the amount of 100% of each of these mixtures before the start of the test on the above-mentioned test bench. The tests were conducted at 20°C and 40% relative humidity.

The results are presented in the graph on figure 4, showing the amount of entrapped ruthenium wt.% for each of the disks D1, D2 and D3.

The fact that the effectiveness of the layer 3 exceeds the efficiency located in front of the layers can be explained by the saturation of these layers of ruthenium. All tested products had a high efficiency. For this reason, the selection was performed according to the sole criterion of delivery and, consequently, the availability of reagents on the market.

As PEG 2000 and SORO 2 was available in sufficient quantity for impregnation on an industrial scale, the authors of the invention in this example used SORO 11 as the reference product.

Sometimes the mix can detect defects, such as delamination, which may cause changes in properties the polymer over time. It is preferable to use according to the invention copolymers, in particular those of them, which has all the properties SORO 11, namely the melting point and efficiency. Polymer with optimal properties is, for example, SORO 14, which is derived from ethylene, propylene and butyleneglycol offered on the market, for example, the firm Lambert Rivière (manufactured by ICI) under the commercial name SYMPEPERONIC A20.

Example 5. Substrate treatment

The application of the copolymer to the substrate represents an important stage in the manufacturing process cartridge trap according to the invention. If it is not made qualitatively, in particular, if the copolymer will not cover the substrate completely, for example, steel fibrous material, as is the case in this example, the cartridge will skip RUO Li4and its efficiency will drop dramatically. You also need to impregnation occurred evenly and prevent the preferred way of penetration.

These experiments were aimed at determining the amount of polymer or copolymer to be applied on the substrate during impregnation.

The first experiments consisted of changing the concentration of the impregnating polymer. The substrate consisted of steel fibrous material WB 12 (trade mark). Samples of this material WB 12 in this example had dimensions of 70×10 mm They were immersed in the polymer solution, and then put on a metal grid (stainless steel) for drying overnight at 40°C. the results of the impregnation are shown in table 5.

Table 5
SORO 14, g·l-1WB12, gWB 12 + SORO 14 (g)The degree of impregnation, %
1001,88023,8863107
501,87292,701144
251,83882,250122
101,94692,11909
52,12222,21354

Therefore, the number of applied polymer modified quasi-linear depending on the concentration of the impregnating solution.

This practical choice, the inventors have identified a solution with a concentration of 10 g·l-1for the manufacture of industrial traps using the specified fibrous material.

In the same way, we performed experiments with steel fiber material WB 22 (trade mark). This material differs from the material WB 12 diameter fibers (12 μm - WB 12 and 22 μm - WB 22). The specific gravity of the layer remains constant for both of these m the materials (300 g· m-2). For this steel fibrous material, the inventors have identified an impregnating solution with a concentration of 25 g·l-1.

The results of the impregnation are shown in table 6.

Table 6
SORO 14, g·l-1The degree of impregnation, %
4027
3018
2510
207,5
156

Therefore, the amount of deposited polymer is also changing quasilinear depending on the concentration of the impregnating solution. In this case, the applied concentration of 25 g/L.

To control the homogeneity of the polymer coating on the substrate surface of the steel fiber material (WB 12) the authors of this invention have placed the disk from WB 12 impregnated SORO 14, in a stream of air containing ruthenium.

The sample is examined under an electron microscope. Then they compared the x-ray, special lines of ruthenium on the same sample. They clearly established that both images are combined and are quasiidentity, which confirms the fact that ruthenium is evenly distributed over the surface of the steel fiber material and that the investigator is about, the polymer qualitatively covered fiber of the above-mentioned material.

Example 6. The resistance of the polymer to NOx and ozone

Taking into account the possible presence of nitrogen oxides or nitrous fumes (NOx) and ozone in industrial gas emissions, the inventors conducted tests on the behavior of the substrate, impregnated SORO 14, in the presence of NOx and ozone.

Family SORO is sensitive to NOx, and the reaction proceeds with the formation of decomposition products, which are unstable and decompose with evolution of heat, however, this reaction to the explosion or ignition does not.

Similarly, as with NOx, steel fibrous material impregnated with from SORO 14 when the degree of impregnation of 30% was subjected to the flow of ozone, using the above described test bench. Conditions were determined on the basis of hypotheses about the formation of ozone in the radiolysis of air. The samples were placed in a stream of ozonized air 2.5 m·h-1when ozone 0.7 g·m-3in the humid air.

It seems that for NOx and ozone properties SORO 14 were similar. However, the phenomenon of disintegration under the action of ozone was significantly less pronounced: lower heat, an exothermic peak of thermogram was at 85°C.

Example 7. The capture device ruthenium according to which obreteniyu

The solution used in this example allows the use of existing equipment without modification. It consists in placing traps for ruthenium according to the invention in the Central part of the cylindrical filter very high efficiency of the second barrier. This is achieved by cutting the upper terminals of the filter and injection baskets with wool WB 12 impregnated SORO 14.

The copolymer

For this example was selected copolymer SORO 14 (see table 1).

Substrate

As the substrate chose steel fibrous material, as it has a large surface area contact with the gas emissions with a slight decrease in pressure. Steel fibrous material WB 12 consists of fibers with a diameter of 12 μm. Its specific surface area is 13 m2/m2when the thickness of the coat of 7 mm, which is about 1857 m2/m2not compacted material. Its specific gravity is equal to 300 g/m2i.e. about 43 kg/m2(still without seal).

Impregnation

It was tested several methods of impregnation to achieve complete impregnation traps: baskets with 2 kg of steel fibrous material. After numerous tests it was decided to impregnate steel fibrous material as separate layers and then to collect the trap. Given the degree of impregnation was 5%, propety is whether dipping layers of specified material.

This experience was the criterion of quality, which consisted in the rejection of any reservoir, the degree of impregnation which was less than 2% or more 10%.Thus, for a trap with a content of about 2 kg of material the maximum number SORO 14 was 200, Used impregnating solution contained 10 g of copolymer per liter of water (see example above). The impregnated material was dried in factored form at 40°C.

Chuck

Metal design type of basket used in bullet-trap, as shown in figure 5, had the form of a double cylinder: inner cylinder (Ci) and the outer cylinder (CE). The inner cylinder (Ci) made of perforated sheet stainless steel C10U12, i.e. with holes in the form of squares with a side of 10 mm and a center distance of 12 mm (mesh). The cylinder is welded to the circular base (Su) stainless steel with large diameter, containing in the center a hole for the passage axis, retaining the filter element (if necessary in such a cylinder, of course, Pets design without holes in the center).

It is on the first cylinder (Ci) is made of eight layers of steel fibrous material impregnated with the copolymer forming the substrate (S), as shown in Fig.6. Then on top added two more, not impregnated with the copolymer layer of the specified material. The outer cylinder (CE) for rivet steel fibrous material, it uses stainless steel mesh sizes of 12.7×12.7mm. The base of the structure is a flat bottom stainless steel, provided with a hole for the passage axis to maintain the filter element with very high efficiency. Chuck-trap contains 10 layers of steel fibrous material. Two wound last layer were not used, i.e. did not contain copolymer: they need to prevent possible movement of the copolymer in the outer direction of the element.

The cartridge (CA), made according to the invention, depicted in Fig.7. The total weight of the formed basket+steel fibrous material+the copolymer is about 8 kg and is distributed approximately as follows:

- design in the form of a basket: about 5.5 kg,

steel fibrous material is from 2 to 2.5 kg,

- a coating of copolymer: not more than 200 g,

- seal Viton (trade mark)+silicone (also with very high efficiency): from 300 to 400 g

The placement of the cartridge according to the invention in an existing installation

In conclusion, the cartridge-trap made in accordance with the invention, is introduced into the filter element (very high efficiency), consisting of optical fibers on a perforated sheet (Tr). The complex is depicted in Fig.

From Phi is Trouser item (F) remove the supporting axle (s), then insert inside the cartridge trap (SA). The ends of the cartridge traps have silicone seals (J) to provide adhesion and sealing between the cartridge-trap and a filter element (F). Then maintain the axis again establish into place. Filter element and its patron-trap can now be placed in lined ducts of the ventilation Department.

Measurement of pressure loss

Measuring the pressure loss was conducted on this system at different flow rates of the processed gas. The results are presented in table 7.

Values were measured in several experiments at ±25%.

In this case, the impregnation of the steel fiber material copolymer did not cause a significant loss of pressure.

Table 7
Consumptionm3/h100020003000
The pressure loss in the filter element very high efficiencyPA90180270
The pressure loss in the design of the cartridge trapsPA40100200
The pressure loss in 10 layers of wool stainless steelPA110 200360
Total:PA240480830

Example 8. Active test

Was experimental circuit, containing one or two experienced serial cartridge (experiments 1, 2) according to the invention, zero or 1 cartridge of poly(4-vinylpyridine) - derivatives), filter paper and two serial patron of poly(4-vinylpyridine) - derivatives) (PVP1 and PVP2), volumetric meter and the pump. Gas emission was passed through this circuit in sequence. The diameter of the cartridges was 5 see the Number of selected samples were allowed to provide a speed of 0.5-1 m·-1that is the representative speed for filters with a very high efficiency of the second barrier installations for the reprocessing of used nuclear fuel.

The unit was installed in the rear part of the filters in the ventilation Department.

The first series of tests was carried out using glass wool impregnated SORO 1 when the degree of saturation of 100%. The results are presented in table 8, in which106EN. Rh (Bq) means the quantity of ruthenium (and its decay product of rhodium), measured by the radiometer.

Table 8
106Ru.Rh (Bq)Volume, m3
Experience No. 1Poly(4-vinylpyridine)Paper filterPoly(4-vinylpyridine 1)Poly(4-vinylpyridine 2)
1 week3206,2<5,7<8,6<7620
2 weeks, a new cartridge410a 4.94,2<7,7<6,7>200

The results obtained within one week of use, turned out to be optimistic, poly(4-vinylpyridine), located in the very rear end of the pilot cartridge, was at the detection limit, indicating the absence of leaks.

The second series of experiments were conducted with the use of steel fiber material WB 12 impregnated SORO 1 when the degree of saturation of 100%. The cartridge consisted of 8 layers WB 12. Left it in place for the dough to life.

The results are shown in table.

Table 9
106Ru.Rh (Bq)Volume, m3
Experience No. 1Poly(4-vinylpyridine)Paper filterPoly(4-vinylpyridine 1)Poly(4-vinylpyridine 2)
7 daysnp<a 6.3of 5.45,5<7,8533
14 daysnp<7,86,25,8<6,1309
21 daysnp189,216<a 6.3359
31 days65006001601100401226
38 days59002500<6,8<8,217396
(np: no sampling was performed)
106Ru.Rh (Bq) - the number of ruthenium (and the product of its decay rhodium)measured by the radiometer.

After 21 days of the test, the inventors suspect a leak, after 7 days drew cartridge. The results of the research located at the rear of poly(4-vinylpyridine) - derivatives), as well as reuse of the cartridge in the next 7 days confirmed the leak, caused by a slow migration COPO 1, in which the conditions of the experiment (40° (C) proved to be too liquid.

Third series of experiments were conducted to evaluate the effectiveness of steel fibrous material WB 22 soaked SORO 2, TRAI is my market, for example, the firm Lambert Rivière (manufacturer ICI), under the commercial name SYMPERONIC A11. Used for impregnation with the level of 22%. The cartridge consisted of a single layer WB22. The results are shown in table 10.

Table 10
106Ru.Rh (Bq)Volume, m3
Experience No. 1Empty cartridgePaper filterPoly(4-vinylpyridine 1)Poly(4-vinylpyridine 2)
7 days400011074927,51054

Already a single layer proved to be very effective, despite the fact that the rate of passage of gas emissions at 2-3 times the rate during the previous experiments.

The fourth experiment was the experiment for the determination of service life with a configuration similar to the configuration of other traps of the second barrier, namely 8 layers WB 12 impregnated 5.7% SORO 14 (these 8 layers distributed between the two cartridges (experiment No. 1 and experience No. 2) and have a thickness of 8 cm). The results are shown in table.

Table 11
106Ru.Rh (Bq) Volume, m3
Experience No. 1Experience No. 2Paper filterPoly(4-vinylpyridine 1)Poly(4-vinylpyridine 2)
9 days *8600280577125858
20 daysnpnp3,7np5970
25 daysnpnp4,1<7,4<a 7.1369
32 daysnpnp<a 5.4<a 8.4<a 4.9621
39 daysnpnp<7<a 9.6<8,2596
49 daysnpnp<a 7.2<4,2<8,8723
56 daysnpnp<a 4.7<3,1<4,4528
63 daysnpnp<5<6,5<7/
70 daysnpnp6,7<7<6,9586
79 days npnp<6<a 7.2<7759
86 daysnpnp<6,2<4,2<6,8504
93 daysnpnp<5,2<7,4<8,7539
100 daysnpnp<a 4.7<5,9<7561
109 daysnpnp178<8830
118 daysnpnp26<7,9<7,4563
124 daysnpnp22<a 9.2<6,5443
133 daysnpnp18<8,7<6,8619
140 daysnpnp10<7,4<7,4585
144 days34000430<8,1<7,4<7,5320
np: without sampling
After 144 the bottom of the experiment, which corresponds to the processing 11790 m3experimental cartridges have been removed, thus reducing their effectiveness has not been noticed.
(*): discovered the violation of integrity, which led to a slight activity of poly(4-vinylpyridine) - derivatives). The cartridges were extracted for installation of seals and after counts were installed in its place.

Example 9. Recovery of ruthenium aqueous solution of copolymer

According to the invention, the polymers and copolymers of ethylene glycol, propylene glycol and butyleneglycol can be used as reagents to be added to the wash water for cleaning systems for gas (Packed column, Venturi scrubber etc).

Indeed, benchmarking experiments using different reagents, during which the surface of the liquid blew air containing RUO Li4. Physical parameters (geometry, velocity) applied the same for all experiments, changing only the chemical composition of the solution.

Shown in table results show, for example, that a copolymer of ethylene glycol - propylene glycol, indicated in this case COPO1 is very effective for absorption RUO Li4.

Table 12
Formed RUO Li4, 10-6molesAbsorbed RUO Li4, 10-6molesAbsorption, %Measured or calculated pH
Experiments using pure water
Clean water: the experience And19,046,0231,6the 5.7
Clean water: the experience In9,803,2132,85,7*
Experiments in the presence of reagents
Na2CO3(0,4M)+NaHCO3(0,2M)19,73as 4.0220,4the 10.1
Na2CO3(0,4M)+NaHCO3(0,2M)9,432,00of 21.29,5
Buffer solution, pH 73,831,0427,26,9
Na2SO49,482,6427,87,5
HNO35,311,7633,11,6
Caustic soda 0.01 M21,697,1332,9
Sodium hydroxide 0.1 M: experience And11,926,6655,9
Sodium hydroxide 0.1 M: the experience In 23,6113,3756,6
Sodium hydroxide 1 M: experience Andof 11.6911,1795,6
Sodium hydroxide 1 M: the experience In12,11the 10.1of 83.4
NHA 0.5 M3,793,0680,7
NHA 0,0475 M7,156,2587,5
SORE 5%13,2813,198,6

1. The use of a solution or aqueous paste containing at least one polymer alkalophiles and/or at least one copolymer alkalophilus in which alkylene or alkylene contain 2-6 carbon atoms, for recovery of ruthenium contained in the gas emissions.

2. The use according to claim 1, wherein the polymer alkalophilus is selected from the group consisting of polyethylene glycol, polypropyleneglycol, poliatilenglikola or mixtures thereof.

3. The use according to claim 1, wherein the copolymer alkalophilus is a copolymer formed by polymers selected from the group consisting of polyethylene glycol, polypropyleneglycol, poliatilenglikola or mixtures thereof.

4. The use according to claim 1, wherein the copolymer alkalophilus is a copolymer based on ethylene, polyethylene and butyleneglycol.

5. The use according to claim 1 or 3, to the m a copolymer of alkalophiles corresponds to the formula (I):

where m and p denote independently from each other integers such as 1≤m≤8 and 3≤p≤12.

6. The use according to claim 1 or 5, wherein the copolymer alkalophilus is a copolymer of ethylene glycol and propylene glycol.

7. The use according to claim 1, wherein the solution or aqueous paste is applied to the fibrous substrate.

8. The use according to claim 7, wherein the substrate consists of glass wool or steel fibrous material.

9. The use according to claim 7, wherein the polymer alkalophilus or copolymer alkalophilus is applied to the above substrate by immersing it in an aqueous solution of the polymer or copolymer.

10. The use according to claim 1, wherein the polymer alkalophilus or copolymer alkalophilus contains hydroxyl end.

11. Cartridge for trapping a ruthenium-containing substrate with a deposited polymer alkalophilus or copolymer alkalophilus in which alkylene or alkylene contain 2-6 carbon atoms.

12. The cartridge according to claim 11, in which the polymer alkalophilus is selected from the group consisting of polyethylene glycol, polypropyleneglycol or poliatilenglikola.

13. The cartridge according to claim 11, in which the copolymer alkalophilus is a copolymer formed by polymers selected from the group formed by polyethylene glycol, polypropyleneglycol is m, poliatilenglikole.

14. The cartridge according to claim 11, in which the copolymer alkalophilus is a copolymer based on ethylene, propylene and butyleneglycol.

15. The cartridge according to claim 11 or 12, in which the copolymer alkalophilus corresponds to the formula (I):

where m and p denote independently from each other integers such as 1≤m≤8 and 3≤p≤12.

16. The cartridge according to claim 11 or 15, in which the copolymer alkalophilus is a copolymer of ethylene glycol and propylene glycol copolymer.

17. The cartridge according to claim 11, in which the substrate is formed of fibers.

18. The cartridge according to claim 11, in which the substrate is formed of glass wool or steel fibrous material.

19. The cartridge according to § § 11, 17 or 18 in which the polymer or copolymer of alkalophiles is applied to the surface by immersing the substrate in an aqueous solution of the polymer or copolymer.

20. The cartridge according to claim 11, containing advanced design for placement of a substrate on which is coated with the polymer or copolymer of alkalophiles.

21. The cartridge according to claim 11, containing:

a substrate to which is applied a polymer or copolymer of alkalophilus, and this surface is formed of glass wool or steel fibrous material

the design for the location of the substrate to which is applied a polymer or copolymer of alkalophilus,

means for GE the cross on the periphery of the cartridge to force the direction of gas emission through the substrate.

22. The use according to claim 1, wherein the aqueous solution is added to the wash water cleaning systems for gas.



 

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