Method of regenerating catalyst of processing waste gases and catalyst of processing waste gases, obtained thereof

FIELD: chemistry.

SUBSTANCE: described is method of regenerating catalyst of processing waste gases, which contains ash adhering to its surface, including stages of used catalyst crushing, stage of separation of crushed parts, stage of grinding, stage of formation, stage of annealing, stage of suspension application of coating for application on formed surface of base and stage of coating annealing for annealing of base, which has coating from suspension liquid, at temperature, higher than temperature of annealing in the process of obtaining crushed re-obtained catalyst of processing waste gases, with threshold size S at the stage of separation has value not lower than 0.105 mm.

EFFECT: obtaining regenerated catalyst, possessing high strength and wear resistance.

11 cl, 3 dwg, 3 tbl, 3 ex

 

The technical field

The invention relates to a method for regenerating catalyst for the treatment of exhaust gases containing ash, adhering to its surface, and the catalyst for exhaust gas after treatment obtained in this way. The present invention is extremely effective, particularly when used for catalyst regeneration processing of the exhaust gas, mainly containing titanium dioxide and intended for removal of nitrogen oxide in the exhaust gases from the burned coal.

The level of technology

Line release for exhaust gases from equipment, such as, for example, a boiler with coal furnace and the like, which burn coal, provide a catalyst for exhaust gas after treatment, intended for treatment of nitrogen oxide (NOx) in the exhaust gases. The catalyst for treatment of exhaust gases receive the next following way: titanium dioxide (TiO2) as a main component, and, in addition, tungsten oxide (WO3), vanadium oxide (V2O5) and the like is kneaded together with a binder, molded in the form of honeycomb structures in such a way as to obtain a number of holes, and calcined. In the holes together with the exhaust gases perepuskat reducing agent, such as ammonia (NH3), for the introduction of nitric oxide in the OTP is bothasig gases and the reducing agent into contact with the surfaces of the walls of the hole. This makes possible the decomposition and destruction of nitric oxide.

During use of such a catalyst for treatment of exhaust gases into the holes together with the exhaust gas continuously flows ash (fly ash)generated by burning coal. Thus, components such as calcium (CA) in fly ash, gradually stick (on the thickness of several tens of microns) to the inner surfaces of the walls of the hole. These components inhibit the passage of the contact reaction between nitric oxide and reducing agent on the catalyst surface. In addition to that fly ash is partially deposited within the holes and gradually obstructs the flow of exhaust gases into the holes. Ultimately, fly ash blocks and clog the holes, respectively, worsening performance at denitration.

Based on these assumptions the catalyst for treatment of exhaust gases used during the preliminary period of time, regenerate so, as described, for example, in patent document 1. Specifically, the catalyst for exhaust gas after treatment fracture so that from 70 to 95% (mass.) of total catalyst exhaust gas after treatment would become large chunks having a size that exceeds porogo the initial size S (any value in the range from 0,105 mm to 1.0 mm) (crushing). The fragments thus obtained by crushing of the catalyst for exhaust gas after treatment divided into large pieces having a size that exceeds the threshold size S, and fine particles having a size not greater than the threshold size S (phase separation). Separate large pieces of ground in such a fine powder that it is characterized by an average particle diameter of not larger than 0.1 mm (stage grinding). Fine powder is blended with other materials of raw materials and molded in the form of catalyst for exhaust gas after treatment (phase mixing and phase formation). Molded precursor is dried and calcined (500°C) (stage drying stage and the calcination). Thus, receive the regenerated catalyst exhaust gas after treatment.

The list of citation

Patent literature

[Patent literature 1] Publication of Japanese patent application No. 2009-226388.

[Patent literature 2] Publication of Japanese patent application No. Hei 9-108573.

[Patent literature 3] Publication of Japanese patent application No. Sho 57-180433.

Summary of invention

Technical problem

The regeneration method, described in patent document 1, can provide the catalyst processing otruba ausich gases, in many cases, not causing particular problems. However, as has been established, depending on the state of the poisoning and the like in the catalyst for exhaust gas after treatment, used within a predetermined period of time, in some cases, the operational characteristics of denitration is not sufficiently restored.

As described, for example, in patent document 2, etc. above, in order of countermeasures is possible to develop application on the catalyst exhaust gas after treatment does not demonstrate sufficiently restored performance at denitration coating of the dispersed components, characterized by a distribution of particles having two peaks in the range from 0.1 μm to 50 μm, and also illustrating operational characteristics for denitration, so that the floor could gradually erode from the surface. Thus, sufficient performance characteristics for denitration can be demonstrated over an extended period of time (approximately 15,000 hours). However, recently, it is strongly required continuous use over a longer period of time (in the range from approximately 20,000 to 30,000 hours is in). This measure counter was difficult to satisfy such a need.

Given such circumstances, the objective of the present invention is to propose a method for regenerating catalyst for treatment of exhaust gases and the catalyst for treatment of exhaust gases obtained in this way, the catalyst for treatment of exhaust gases is continuously used for a long period of time (in the range from approximately 20,000 to 30,000 hours), even with regeneration in the first crushing, then re-forming and annealing in the presence of the coating on its surface.

The resolution of the problem

Permit opisyvayuschaya above problems by way of regeneration of the catalyst for exhaust gas after treatment corresponds to the first invention is a method for regenerating catalyst for treatment of exhaust gases containing ash, adhering to its surface, characterized in that the method includes:

stage crushing of used catalyst for crushing catalyst for exhaust gas after treatment that was used;

phase separation to separate the crushed catalyst for treatment of exhaust gases on a rough pieces having a size that exceeds the threshold size S, and fine particles having a size not greater than the threshold size S;

stage grinding of used catalyst for grinding large pieces separated into a fine powder;

stage molding for molding from milled fine powder as a material source of raw materials of the catalyst for exhaust gas after treatment;

stage calcination of the precursor for calcination of the molded catalyst precursor exhaust gas after treatment;

stage crushing newly obtained catalyst for crushing catalyst for exhaust gas after treatment, which was again obtained;

stage suspension for suspension of crushed again obtained catalyst exhaust gas after treatment;

stage suspension coating to be applied on the surface of the base, obtained by calcination at a stage calcination of the precursor, the coating of the liquid suspension; and

stage ignition cover for annealing framework, having a coating of liquid suspension at a temperature greater than the temperature of the annealing while getting crushed again obtained catalyst exhaust gas after treatment and

the threshold size S has a value that is not smaller than 0,105 mm

Way catalyst regeneration processing of the exhaust gas corresponding to the second izaberete the Oia, is a method for regenerating catalyst for treatment of exhaust gases corresponding to the first invention, characterized in that

stage crushing is the stage of annealing at a temperature greater at 25°C or more than the temperature of the annealing while getting crushed again obtained catalyst exhaust gas after treatment.

Method for regenerating catalyst exhaust gas after treatment, corresponding to a third invention is a method for regenerating catalyst for exhaust gas after treatment corresponds to the second invention, characterized in that

stage calcination of the coating is the stage of calcination at a temperature of 700°C or more.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the fourth invention is a method for regenerating catalyst for treatment of exhaust gases corresponding to any one invention of the first, second and third, characterized in that

crushed and suspended again the catalyst exhaust gas after treatment is characterized by an average particle diameter in the range from 3 to 8 μm.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the fifth invention is a method for regenerating catalyst for treatment of exhaust g the call, corresponding to the invention with first through fourth, characterized in that

the main material source of raw materials of the catalyst for exhaust gas after treatment is a titanium dioxide.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the sixth invention is a method for regenerating catalyst for treatment of exhaust gases corresponding to the fifth invention, characterized in that

the catalyst for treatment of exhaust gases used for treatment of exhaust gases from combustion of coal.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the seventh invention is a method for regenerating catalyst for treatment of exhaust gases corresponding to the sixth invention, characterized in that

the catalyst for treatment of exhaust gases used for treatment of nitrogen oxide in the exhaust gases.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the eighth invention is a method for regenerating catalyst for treatment of exhaust gases corresponding to the invention from the first to the seventh, characterized in that

stage crushing the used catalyst is the stage in which the catalyst for exhaust gas after treatment, which was used, rastall who have thus to from 70 to 95% (mass.) of total catalyst exhaust gas after treatment, which was used, was in large pieces having a size that exceeds a threshold size S.

Method for regenerating catalyst exhaust gas after treatment, corresponding to the ninth invention is a method for regenerating catalyst for treatment of exhaust gases, corresponding to the eighth invention, characterized in that

the threshold size S is set to not more than 1.0 mm

Method for regenerating catalyst exhaust gas after treatment, corresponding to the tenth invention is a method for regenerating catalyst for treatment of exhaust gases corresponding to the invention from the first to the ninth, characterized in that

stage grinding the spent catalyst is the stage in which large pieces grind so that the fine powder was characterized by an average particle diameter of not greater than 0.1 mm

In addition, to resolve the aforementioned problem, a catalyst for exhaust gas after treatment, corresponding to the eleventh invention, is a catalyst for treatment of exhaust gases, characterized in that it is regenerated by the regeneration method of the catalyst for exhaust gas after treatment, corresponding to any one invented the Yu from the first to the tenth.

Advantageous effects of invention

In the method of catalyst regeneration processing of the exhaust gas corresponding to the present invention, on the surface of the base are coated with a liquid suspension of crushed again obtained catalyst exhaust gas after treatment and carry out the annealing at a temperature greater than the temperature at the time of receiving crushed again obtained catalyst exhaust gas after treatment. It can reliably increase the degree of sintering of the surface of the regenerated catalyst for treatment of exhaust gases. Thus, the catalyst for exhaust gas after treatment, corresponding to the present invention has a high strength surface and is able to demonstrate sufficient wear resistance while maintaining sufficient performance characteristics for denitration. Thus, the catalyst for exhaust gas after treatment, corresponding to the present invention, is continuously used for a long period of time (in the range from approximately 20,000 to 30,000 hours).

Brief description of drawings

Figure 1 is a schematic configurational diagram of the catalyst for exhaust gas after treatment, used in the basic version of the method of regenerating the catalyst in the exhaust gas after treatment relevant to the present invention.

Figure 2 is a block diagram showing the methodology of the basic variant of the method of regeneration of the catalyst for exhaust gas after treatment, corresponding to the present invention.

Figure 3 is a graph for obtaining the ratio between the difference in temperature between the annealing and the degree of wear in test example 2 for a method of regeneration of the catalyst for exhaust gas after treatment, corresponding to the present invention.

Description of embodiments

Method for regenerating catalyst for treatment of exhaust gases corresponding to the present invention, and the catalyst for treatment of exhaust gases obtained in this way will be described based on the drawings. However, the present invention is not limited to variants of implementation, vpisivaushiesya below.

The main variant of the implementation

The main variant of the method of regeneration of the catalyst for exhaust gas after treatment, corresponding to the present invention, and the catalyst for treatment of exhaust gases obtained in this way will be described based on Fig 1 and 2.

As shown in figure 1, the catalyst for exhaust gas after treatment 10 corresponding to this variant implementation, the floor is up on the next following way: titanium dioxide (TiO 2) as a main component, and in addition, tungsten oxide (WO3), vanadium oxide (V2O5) and the like is kneaded together with a binder, molded in the form of honeycomb structures in such a way as to obtain a set of holes 10A, and calcined.

Such a catalyst for treatment of exhaust gas 10 is installed in the line release for exhaust gases from equipment such as a boiler with coal furnace for burning coal. The holes 10A together with the exhaust gases perepuskat reducing agent, such as ammonia (NH3), for the introduction of nitrogen oxide (NOx) in the exhaust gases and the reducing agent into contact with the surfaces of the walls of the holes 10A. This makes it possible to decompose and remove nitric oxide.

During use of the catalyst for exhaust gas after treatment 10 in the hole 10A together with the exhaust gas continuously flows ash (fly ash)generated by burning coal. Thus, components such as calcium (CA) in fly ash, gradually stick (on the thickness of several tens of microns) to the inner surfaces of the walls of the holes 10A. Components inhibit the passage of the contact reaction between nitric oxide and reducing agent on the surfaces of the holes 10A. In addition, she fly ash is partially deposited within the holes 10A and Ostapenko impedes the flow of exhaust gases into the holes. Ultimately, fly ash blocks and clog the holes, respectively, worsening performance at denitration. For this reason, after a predetermined period of use, the catalyst is extracted from the exhaust gas line and transferred to the installation of the recovery processing.

After this we used the catalyst for exhaust gas after treatment 11, translated in the plant regeneration processing, is introduced into the crushing machine, for example, crusher, without holding stage leaching processing when using a washing liquid, such as water. The catalyst fracture so that from 70 to 95% (mass.) of total catalyst exhaust gas after treatment 11 was large pieces 12 having a size that exceeds the threshold size S (any value in the range from 0,105 mm to 1.0 mm), (figure 2 crushing the used catalyst S1).

The fragments resulting from crushing of the catalyst for exhaust gas after treatment 11, served on a sieve having a mesh equal to the threshold size S. then the fragments are divided into large pieces 12 having a size that exceeds the threshold size S, and the fine particles 13 having a size not greater than the threshold size S (figure 2 separation stage S2).

Small frequent the hospitals 13, passed through the sieve mesh, exposed to salvage treatment. Meanwhile, large pieces 12 remaining on the sieve cells, injected into the grinding machine, for example, a hammer mill, and grind into a fine powder, which is characterized by an average particle diameter of not larger than 0.1 mm (preferably 70 μm), (figure 2 stage grinding the spent catalyst S3).

After this fine powder as material feedstock together with other ingredients such as a binder and water, served in a kneader machine, for example, kneading machine, and uniformly kneaded (figure 2 stage mixing S4). The kneaded product is fed into the extruder and molded in the form of honeycomb structures (figure 2 stage molding S5). This molded precursor is dried in natural conditions, and then dried under the action of hot air (100°C), and the like (figure 2 stage drying predecessor S6). After that, the dried precursor calcined in the calcining furnaces were (approximately 500°C) (figure 2 stage calcination of the precursor S7). Thus, get the base 14 of the regenerated catalyst for treatment of exhaust gases.

On the other hand, receive and enter into the crushing machine, for example, the crusher, and the fracture using again the catalyst treatment the exhaust gas 15, such catalyst for exhaust gas after treatment 10, (figure 2 crushing newly obtained catalyst S8). The fragments resulting from crushing the newly obtained catalyst exhaust gas after treatment 15, is introduced into a ball mill together with water and suspended in concurrent secondary crushing (to obtain the average diameter of the particles is approximately equal to the value in the range of from about 3 to 8 μm) (figure 2 phase suspension S9).

After that, the base 14 is dipped in the above liquid suspension 16 and on the surface of the base 14 are coated with a liquid suspension of 16 (figure 2 stage application of slurry coatings S10). After that, the resulting product is dried under the action of hot air (100°C), and the like (figure 2 stage drying coating S11) and injected into the kiln and calcined at a temperature (in the range from 525 to 700°C), greater than the temperature of calcination (500°C) during the preparation of the catalyst of the exhaust gas after treatment 15, (figure 2 stage ignition cover S12). Thus, receive the regenerated catalyst exhaust gas after treatment 17.

In other words, in the present embodiment, on the surface of the base 14 are coated with the liquid suspension 16 crushed again the floor is built of catalyst for exhaust gas after treatment 15 and carry out the calcination at a temperature greater than the temperature during preparation of the catalyst of the exhaust gas after treatment 15. Thereby, receive the regenerated catalyst for treatment of exhaust gases 17 and reliably increased the degree of sintering of the surface.

Therefore, in accordance with the present embodiment, the catalyst for exhaust gas after treatment 17 has a high-strength surface even when regeneration in the first crushing, then re-forming and annealing in the presence of the surface. The catalyst for treatment of exhaust gases 17 are able to demonstrate sufficient wear resistance while maintaining sufficient performance characteristics for denitration. Thus, the catalyst for exhaust gas after treatment 17 is continuously used for a long period of time (in the range from approximately 20,000 to 30,000 hours).

You should pay attention to the fact that in case of differences of temperature of calcination on the stage of calcination of the coating S12 temperature annealing during retrieval of newly acquired catalyst for exhaust gas after treatment 15, which must be allocated for coating the base 14, at 25°C and more than this can more reliably to increase the degree of sintering of the surface that is exclusively prefer enim. Meanwhile, in case of excess temperature annealing on the stage of calcination of the coating S12 700°C the crystal structure of the main component of titanium dioxide (TiO2will change, going from the anatase form to rutile form. This leads to shrinkage of the catalyst for exhaust gas after treatment 17 and can degrade performance at denitration, which is not preferable.

In addition, in the case of the crushed and suspended again obtained catalyst exhaust gas after treatment 15 average particle diameter in the range from 3 to 8, it is more likely to improve the wear resistance, which is extremely preferred.

In addition, the aforementioned crushing the used catalyst S1 used the catalyst for exhaust gas after treatment 11 preferably fracture so that from 70 to 95% (mass.) of total catalyst exhaust gas after treatment 11 would become large chunks 12. This is due to the fact that in the case of a large number of pieces 12, obtained by crushing, less than 70% (mass.) of the total spent catalyst processing of the exhaust gas 11, together with the ash and dust and the like is to be disposed of excessive amounts of catalyst processing OTP is bothasig gases. It is, accordingly, reduces the regeneration efficiency and increases the cost of regeneration. Meanwhile, in case of exceeding the number of large pieces 12, obtained by crushing, 95% (mass.) of the total spent catalyst exhaust gas after treatment 11 fly ash and the like can be in large quantities included in the base 14.

Other embodiments of the

You should pay attention to the fact that in the aforementioned embodiment was the description of a case in which the catalyst for exhaust gas after treatment 10 is formed in the form of honeycomb structures. However, the present invention is not limited with this. The present invention can also be used according to the method similar to that of the aforementioned variants of implementation, in other embodiments in the case of forming the catalyst for exhaust gas after treatment, for example, in the form of granules, in the form of pipes or in another form.

In addition, in the aforementioned embodiment was the description of a case in which the catalyst for exhaust gas after treatment 10 is installed in the line release for exhaust gases from equipment such as a boiler with coal furnace for burning coal. However, the present invention is not limited with this. The present invention can be is used by the method, similar to that of the aforementioned variants of implementation, if only ash in the exhaust gases will stick to the catalyst surface treatment of exhaust gases and deposited on it.

EXAMPLES

In the remainder of this document describes the tests for compliance with the technical conditions to confirm the effects of the regeneration method of the catalyst for exhaust gas after treatment, corresponding to the present invention, and the catalyst for exhaust gas after treatment obtained in this way. However, the present invention is not limited vpisivaushiesya following test for compliance with specifications.

The test example 1

Obtaining samples for testing

The sample for testing And

A catalyst for exhaust gas after treatment And (TiO2=77.3 per cent, WO3=9,00%, V2O5=0,55%, other=13,15%) for denitration has the form of honeycomb structures (height: 150 mm width: 150 mm, length: 800 mm, wall thickness: 1.15 mm pitch (distance between centers of adjacent walls): 7.4 mm, number of cells (n): 20×20), used in-line exhaust gas boiler with coal furnace for approximately 70000 hours. The catalyst was crushed using a crusher to obtain the fragments.

After that, the fragments as obtained by crushing, sieving them on the ITA (having a mesh of 0.5 mm (nominal dimensions in accordance with Japanese industrial standards (JIS)). Large pieces remaining on the sieve, grind into powder (mean particle diameter of approximately 20 μm) using a hammer mill. The thus obtained fine powder (15 kg), organic binder (0.7 kg), fiberglass (1.5 kg (diameter: 11 μm, length: 3 mm)and water (good number) was mixed when using a kneading machine and uniformly mixed. The obtained kneaded product was applied in the extruder to obtain a catalyst precursor processing exhaust gases having a kind of cellular structures (height: 69 mm, width: 69 mm, length: 800 mm, step-cells: 7.4 mm, hole size cells: 6.25 mm, number of cells (n): 9×9). Predecessor sufficiently dried in natural conditions, and then dried under the action of hot air (100°C.×5 hours). Thereafter, the precursor was subjected to exposure prikalivalsa treatment (500°C.×3 hours) in the kiln. Thus, given a sample for testing And the regenerated catalyst exhaust gas after treatment (basic).

The sample for testing

A catalyst for exhaust gas after treatment In (TiO2=77.3 per cent, WO3=9,00%, V2O5=0,55%, other=13,15%) for denitration has the form of honeycomb structures (height: 150 mm width: 150 mm, length: 800 mm, wall thickness: 1.15 mm pitch (distance between centers of the adjacent walls): 7.4 mm, the number of cells (n): 20×20), used in-line exhaust gas boiler with coal furnace for approximately 65000 hours. The catalyst was crushed using a crusher to obtain fragments b.

After that, the fragments of b, obtained by crushing were subjected to exposure processing by the method similar to that of the splintered fragments and sample for testing A. Thus, given a sample for testing for the regenerated catalyst exhaust gas after treatment (basic).

Sample test

A catalyst for exhaust gas after treatment With (TiO2=77.3 per cent, WO3=9,00%, V2O5=0,55%, other=13,15%) for denitration has the form of honeycomb structures (height: 150 mm width: 150 mm, length: 800 mm, wall thickness: 1.15 mm pitch (distance between centers of adjacent walls): 7.4 mm, number of cells (n): 20×20), used in-line exhaust gas boiler with coal furnace for about 60,000 hours. The catalyst was crushed using a crusher to obtain fragments of C.

After that, the fragments resulting from crushing, was subjected to processing by the method similar to that of the splintered fragments and sample for testing A. Thus, given a sample to test for the regenerated catalyst processing atrebates the x gases (basic).

Test method

The degree of denitration

Each of the samples for testing from a to C was cut into pieces (number of cells: 6×7, length: 800 mm). One piece was placed in the reactor. The degree of denitration was obtained for each sample for testing at opissyvayusya following conditions. You should pay attention to the fact that mapping also received the degree of denitration for newly acquired catalyst for exhaust gas after treatment (comparative sample).

* Test conditions
The composition of exhaust gases -NOx:150 hours/million
NH3:150 hours/million
SO2:800 hours/million
About2:4%
CO2:12,5%
H2About:approximately 11.5%of
N2:the carrying amount

Exhaust gas temperature: 380°C

The amount of exhaust gas: 19,56 nm3per hour

Ugs: 2,3 nm/sec

AV: 23,26 nm3/m2·hours

The degree of denitration (%)={1-(concentration of NOxat the outlet of the catalyst/concentration of NOxat the entrance of catalyst)}×100

Test results

The following table 1 shows the test results for samples for testing from a to C and comparative sample.

Table 1
The degree of denitration (%)
The sample for testing And79,5
The sample for testing75,8
Sample test78,0
Comparative sample82,1

As you can see from the above table 1, the degree of denitration samples for testing from a to C, according to the government, obtained from materials of raw materials of catalysts for the treatment of exhaust gases from a to C and used in the aforementioned conditions, were lower than the degree of denitration in comparative sample (newly acquired product) about the approximate value in the range from 3 to 6%. Despite the uncertainty of the exact reasons you can imagine that used coal contained a relatively large number of components, poisoning the catalyst, and poisoned a relatively large amount of catalyst components.

The test example 2

Obtaining samples for testing

Liquid suspensions α

Again the catalyst exhaust gas after treatment (TiO2=77.3 per cent, WO3=9,00%, V2O5=0,55%, other=13,15%, temperature of ignition: 500°C) for denitration has the form of honeycomb structures used in the boiler with coal furnace was crushed using a crusher. Fragments and resulting from crushing, (1.5 kg) and water (5 liters) was introduced in a ball mill (capacity: 7.2 liter) together with balls of aluminum oxide (having a diameter of 25 mm and 15 mm, each 2.1 kg) and split (to an average particle diameter 4,94 μm). After that regulated their concentration (21%). Thus was obtained a liquid suspension of α.

Samples for testing from A11 to A16

After this is th each of the test specimens And, obtained in the above test example 1, was immersed in the liquid suspension of α to be applied on the surface of the sample for testing And coating of liquid suspensions of α. Then, the resulting samples for testing And was dried under the action of hot air (100°C.×5 hours) and was subjected to prikalivalsa treatment (5 hours) at different temperatures (500°C, 550°C, 600°C, 650°C, 700°C, 750°C) in the kiln. Thus, the received samples for testing from A11 to A16 catalyst for treatment of exhaust gases with the surface of the coating amount of the coating on the area of the outer surface: 100 g/m2).

Test method

The degree of denitration

The degree of denitration for samples for testing from A11 to A16 received by the method similar to that in the above test example 1.

Wear

One piece each of the samples for testing from A11 to A16 placed in a vertical reactor. Gas containing quartz sand (average particle diameter: 50 μm) (at a concentration of 300 g/m3), was perepustili through it from top to bottom in opissyvayusya following conditions. Thus, received the degree of wear. It should be noted that the used sample for testing And had cell (n): 20×20, and a length of 100 mm, and for comparison also received the degree of wear and newly acquired cat who lyst exhaust gas after treatment (comparative sample).

* Test conditions

Temperature: 20°C

Pressure: atmospheric pressure

The flow rate through the cross-section of the catalyst): 10 m/s

The period of the course: 1 hour

The degree of depreciation (%)={(W0-W)/W0}×100,

where W0represents the weight of catalyst before the test and W is the weight of the catalyst after the test.

Test results

The following table 2 shows the results of tests on the degree of denitration and wear. In addition, figure 3 shows a graph for obtaining the correlation between the degree of wear and the difference of temperature of annealing in relation to the temperature of the annealing while getting crushed and suspended again obtained catalyst exhaust gas after treatment.

Table 2
The temperature of calcination of the coating (°C)The difference of temperature of calcination (°C)The degree of denitration (%)The degree of depreciation (%)
The sample for testing A11500082,11,30
The sample for testing A125505082,10,72
The sample for testing A1360010081,70,67
The sample for testing A1465015081,30,64
The sample for testing A1570020080,90,60
The sample for testing A16750250*1*1
Comparative sample------82,10,51
*Vsledstvii shrinkage of the sample and the apparent impossibility of its use as a catalyst, the measurement is not performed.

As you can see from the above table 2, the temperature of annealing the specimen is to A16 test was excessively high (750°C), and crystal structure of the main component of titanium dioxide (TiO2changed, moving from the anatase form to rutile form. It's too excessively increased the degree of sintering, and, accordingly, the sample for testing A16 has undergone shrinkage, so that the sample for testing A16 was not able to demonstrate the function of the catalyst.

Meanwhile, samples for testing from A11 to A15 (temperature annealing coverage: from 500 to 700°C) according to the observations were able to demonstrate sufficient operational characteristics according to the degree of denitration.

In addition, as can be seen from the context of figure 3, samples for testing from A12 to A15 (the temperature difference of ignition: ≥25°C) according to the observations were able to demonstrate sufficient operational characteristics according to the degree of deterioration (not more than 1%; the possibility of continuous use for a period of from 20000 to 30000 hours).

The TEST EXAMPLE 3

Obtaining samples for testing

Liquid suspensions from α1 to α5

Liquid suspensions from α1 to α5, characterized by the average diameters of the particles and demonstrated in the following table 3 were obtained by the method similar to that of the liquid suspension of α in the above test example 2.

Samples for testing from A21 to A25

After that bratzilla tests And, obtained in the above test example 1, was immersed, respectively, in fluid suspensions from α1 to α5 to be applied on the surface of samples for testing And coatings from liquid suspensions from α1 to α5. Then, the resulting samples for testing And was dried under the action of hot air (100°C.×5 hours) and was subjected to prikalivalsa treatment (550°C.×5 hours) in the kiln. Thus, the received samples for testing from A21 to A25 catalyst for treatment of exhaust gases with the surface of the coating amount of the coating on the area of the outer surface: 100 g/m2).

Test method

The degree of denitration

The degree of denitration for samples for testing from A21 to A25 received by the method similar to that in the above test example 1.

Wear

The degree of denitration for samples for testing from A21 to A25 received by the method similar to that in the above test example 2.

Test results

The following table 3 shows the results of tests on the degree of denitration and wear.

Table 3
Liquid suspensionThe degree of depreciation (%)
The sample for testing A21α12,501,97
The sample for testing A22α23,120,78
The sample for testing A23α35,160,70
The sample for testing A24α47,410,80
The sample for testing A25α59,201,30

As you can see from the above table 3, the samples for testing from A22 to A24, resulting from the use of liquids suspensions from α2 to α4, characterized by average particle diameters in the range from 3 to 8 μm, as observed were able to demonstrate sufficient performance characteristics for wear (not more than 1%; the possibility of continuous use for a period of from 20000 to 30000 hours).

Applicability in industry.

The regeneration process of catalysis is the torus exhaust gas after treatment the corresponding present invention, and the catalyst for treatment of exhaust gases obtained in this way are extremely useful and beneficial in various industries.

The reference list of items

10 the Catalyst for treatment of exhaust gases

10A Hole.

1. Method for regenerating catalyst for treatment of exhaust gases containing ash, adhering to its surface, characterized in that the method includes:
stage crushing of used catalyst for crushing catalyst for exhaust gas after treatment that was used;
phase separation to separate the crushed catalyst for treatment of exhaust gases on a rough pieces having a size that exceeds the threshold size S, and fine particles having a size not greater than the threshold size S;
stage grinding of used catalyst for grinding large pieces separated into a fine powder;
stage molding for molding the catalyst for treatment of exhaust gases from milled fine powder as the source material;
stage calcination of the precursor for calcination of the molded catalyst precursor exhaust gas after treatment;
stage crushing newly obtained catalyst for crushing catalyst processing amrabat is our gases, which was again obtained;
stage suspension for suspension of crushed again obtained catalyst exhaust gas after treatment;
stage suspension coating to be applied on the surface of the base, obtained by calcination at a stage calcination of the precursor, the coating of the liquid suspension; and
stage ignition cover for annealing framework, having a coating of liquid suspension at a temperature higher than the temperature of the annealing while getting crushed again obtained catalyst exhaust gas after treatment, and
the threshold size S has a value that is not smaller than 0,105 mm

2. Method for regenerating catalyst for treatment of exhaust gases according to claim 1, characterized in that
stage calcination of the coating is a stage of annealing at a temperature greater at 25°C or more than the temperature of the annealing while getting crushed again obtained catalyst exhaust gas after treatment.

3. Method for regenerating catalyst for treatment of exhaust gases according to claim 2, characterized in that
stage calcination of the coating is a stage of annealing at a temperature of 700°C or more.

4. Method for regenerating catalyst for treatment of exhaust gases according to any one of claims 1 to 3, otlichalis the same time, what
crushed and suspended again the catalyst exhaust gas after treatment is characterized by an average particle diameter in the range from 3 to 8 μm.

5. Method for regenerating catalyst for treatment of exhaust gases according to any one of claims 1 to 3, characterized in that
the main source material of the catalyst for exhaust gas after treatment is a titanium dioxide.

6. Method for regenerating catalyst for treatment of exhaust gases according to claim 5, characterized in that
the catalyst for treatment of exhaust gases used for treatment of exhaust gases from combustion of coal.

7. Method for regenerating catalyst for treatment of exhaust gases according to claim 6, characterized in that
the catalyst for treatment of exhaust gases used for treatment of nitrogen oxide in the exhaust gases.

8. Method for regenerating catalyst for treatment of exhaust gases according to any one of claims 1 to 3, characterized in that
crushing the used catalyst is a stage in which the catalyst for exhaust gas after treatment, which was used crushed so that from 70 to 95 wt.% of total catalyst exhaust gas after treatment, which was used, was in large pieces having a size that exceeds a threshold size S.

9. Method for regenerating catalyst is the processing of exhaust gases according to claim 8, characterized in that
the threshold size S is set to not more than 1.0 mm

10. Method for regenerating catalyst for treatment of exhaust gases according to any one of claims 1 to 3, characterized in that
stage grinding the spent catalyst is a stage in which large pieces grind so that the fine powder was characterized by an average particle diameter of not greater than 0.1 mm

11. The catalyst for treatment of exhaust gases, characterized in that it is regenerated by the regeneration method of the catalyst for exhaust gas after treatment, corresponding to any one of claims 1 to 3.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: inventions can be used to decompose pollutants in waste water and process streams of public and industrial pollution sources. To realise the method, an aqueous mixture containing an undesirable component is brought into contact with a soluble copper catalyst and an oxidant at temperature from 240°C to critical temperature and pressure from 30 atm to 275 atm to form an oxidised aqueous mixture, a portion of the catalyst is deposited by adjusting pH of the oxidised aqueous mixture from 6 to 12 in the presence of oxygen at temperature of about 80°C in form of solid copper oxide particles. When recycling the catalyst, pH is controlled in the range from 6 to 12 to dissolve solid copper oxide particles. The apparatus has a wet oxidation unit (206), an aqueous mixture source (202), a copper catalyst source dissolved in the aqueous mixture (224) lying between the aqueous suspension source and the wet oxidation unit, a pH sensor, an oxidised aqueous mixture pH control unit (212), a separator (220) configured to deposit part of the copper catalyst in form of copper oxide and lying on the outlet side of the wet oxidation unit (206) and a line for recirculating the recycled catalyst (224).

EFFECT: inventions provide 95% efficiency of purifying aqueous mixtures from different pollutants which can be decomposed by oxidation and reduce power consumption of the apparatus.

31 cl, 6 dwg, 6 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of regenerating catalytic activity of a spent hydrogen processing catalyst which does not contain an additive. A method is described for regenerating catalytic activity of a spent hydrogen processing catalyst which does not contain an additive (versions), which involves: bringing a spent non-additive containing hydrogen processing catalyst which contains a metal component and carrier material, which has low catalytic activity with respect to the catalyst in fresh state before its use, which results in the catalyst being spent, with a solution, where the said solution contains a chelating agent chosen from a group of compounds consisting of amino carboxylic acids, and a solvent, and where said contacting takes place in a period of time longer than 10 hours, with provision for regenerated catalytic activity, obtaining old catalyst containing said chelating agent and said solvent, where said spent hydrogen processing catalyst contains amount of said chelating agent in the interval from 0.005 mole of chelating agent per mole of active metal to 1 mole of chelating agent per mole of active metal; keeping said old catalyst in conditions which include drying temperature so as to remove part of said solvent from said old catalyst with removal of not less than 50 wt % of said chelating agent from said old catalyst, obtaining dried old catalyst as a result; and treatment of said dried old catalyst with sulphur, obtaining regenerated catalyst. Also described is a catalyst produced using methods described above and hydrogen processing method, involving bringing hydrocarbon starting material in hydrogen processing conditions with a catalyst produced using methods described above.

EFFECT: higher degree of regenerated catalytic activity of spent hydrogen processing catalyst.

19 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of regenerating catalytic activity of spent catalyst. A method is described for regenerating catalytic activity of spent water treatment catalyst (versions), where the said method involves: provision for said spent water treatment catalyst with first carbon concentration of over 3 wt %; reduction of carbon concentration on the said spent water treatment catalyst, obtaining catalyst with low carbon concentration as a result, with second carbon concentration ranging from 0.5 wt % to 2.5 wt %, with bringing the said spent water treatment catalyst into contact with oxygen-containing gas in carbon burning conditions and regulation of amount of carbon removed from the said spent water treatment catalyst so as to obtain the said catalyst with low carbon concentration, with the said second carbon concentration; and bringing the said catalyst with low carbon concentration into contact with a solution which contains a chelating agent and a solvent so as to introduce the said chelating agent into the said catalyst with low carbon content; ageing of the said catalyst with low carbon content, containing the said solution during ageing time, obtaining aged catalyst as a result, where the said ageing time is sufficient for regenerating catalytic activity of said catalyst with low carbon content; and drying the said aged catalyst with removal of part of the said solvent from the said aged catalyst, obtaining dried aged catalyst as a result; and sulphur treatment of the said dried aged catalyst, that way obtaining the said regenerated catalyst.

EFFECT: design of a method of regenerating activity of catalysts, obtaining regenerated catalyst with higher level of regenerated catalytic activity.

22 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of reactivating silicoaluminophosphate molecular sieve catalyst, subjected to hydrothermal deactivation. The catalyst is reactivated by putting it into contact with warm water, aluminium salts, dilute acids or water vapour at low pressure until the level of catalytic activity does not increase by at least 25%.

EFFECT: reactivation of catalytic activity of silicoaluminophosphates through simple processing.

10 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: cleaning of liquid and solid sediments from porous matrix is performed by matrix heating to (1-1.2)Tcr, where Tcr is critical temperature of the extraction agent used, in a device including throttle device 1, separator 2, compressor or pump 3, separation valve 4, adsorbing extractor 5, with further processing by extraction agent at pressure of (1-10)Pcr, where Pcr is critical pressure of the extraction agent used. Valves 6-9 are installed additionally between adsorbing extractor and throttle device and between compressor or pump and adsorbing extractor, if Tcr is equal to melting point of solid sediments in matrix. Extraction agent flow is directed downflow at Re≤20 and upflow at Re>20.

EFFECT: reduced time of cleaning liquid and solid sediments from matrix at lower power consumption and matrix cleaning in fine dispersion form.

2 cl, 1 dwg

The invention relates to a method of modifying thermoelectrode zeolite catalyst and the use of the modified catalyst in the processes formatselection conversion of hydrocarbons such as the disproportionation of toluene

FIELD: process engineering.

SUBSTANCE: invention relates to treatment of high-pressure hydrocarbon gas flow with high concentration of carbon dioxide to be removed therefrom to form treated gas flow and gas flow enriched with carbon dioxide. Proposed method comprises bringing hydrocarbon gas flow in contact with lean solvent bearing aqueous solution of ammonia and product of NH3-CO2-H2O system reaction to facilitate reaction of the portion of carbon dioxide with lean solvent. This brings about a compound containing carbon dioxide. It comprises also releasing treated flow of hydrocarbon gas and used solvent suspension containing settles solid particles and fluid from contact device. It includes feeding portion of used solvent suspension into regenerator for recovery in conditions facilitating decomposition of the portion of settled solid materials to release carbon dioxide. Finally, it includes releasing concentrated flow of carbon dioxide and lean solvent from said regenerator.

EFFECT: high-efficiency treatment.

15 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to recovery of amino solutions used in gas or hydrocarbon fluid cleaning of acid components by amino solutions. Saturated amino solution is fed via recuperative heat exchanger into stripper. Acid gases together with water vapors are fed from stripper top into vapor-gas mix cooler for separation into acid gases and fluid. Amino solution to be recovered is fed via heat exchanger into stripper stilling section wherefrom recovered amino solution is fed to inlet of pump that develops pressure of 0.1-1.5 MPa. Then, said solution is divided into two flows. First flow is fed to heater inlet to maintain solution fluid state. Then, heated flow is directed into pressure regulator to convert heated amino solution into two-phase vapor-liquid state while formed two-phase mix is fed into stripper stilling section. Produced vapor is fed therefrom into stripper mass exchange section. Second flow is fed into recuperative heat exchanger. Note here that equal flow rates of amino portions fed to saturate amino solution unit and those escaping from liquid recovered amino solution unit.

EFFECT: decreased erosion of structural elements and amine losses.

4 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for cleaning exhaust gases, a method of regenerating such a catalyst, as well as a device and a method of cleaning exhaust gases using the said catalyst. The invention describes a catalyst for cleaning exhaust gases where a noble metal is attached to a metal oxide support. In an oxidative atmosphere, the noble metal on the surface of the support is in a high oxidation state and the noble metal is bonded to the cation of the support though an oxygen atom on the surface of the support with formation of a surface oxide layer. In a reductive atmosphere, the noble metal on the surface of the support is metallic state and the amount of noble metal open on the surface of the support, measured through CO chemisorption, is equal to or greater than 10 at % of the total amount of noble metal attached to the support. Described is a method of regenerating a catalyst for cleaning exhaust gases in which the above described catalyst for cleaning exhaust gases undergoes oxidative treatment by heating in an oxidative atmosphere which contains oxygen, and reduction treatment. Described also are devices for cleaning exhaust gases (versions) and a method of cleaning exhaust gases, involving cleaning exhaust gases by bringing the exhaust gases into contact with the above described catalyst.

EFFECT: prevention of reduction of catalyst activity.

18 cl, 11 tbl, 46 ex, 10 dwg

FIELD: process engineering.

SUBSTANCE: invention relates can be used in metallurgy, electronics and in production of pigments and welding electrodes. Wastes of production of ferrous alloys containing, mainly, manganese represent slimes of fume gases washing from furnaces producing ferromanganese and silicon manganese. Said wastes are directed for thermal sulphating 1 that comprises furnace processing of material fed from mixer wherein said wastes have been subjected to treatment by acid with flow rate approximating to stoichiometric. Teflon chutes are used inside the furnace to produce SO2. Then hydrometallurgical phase is performed consisting of vatting stage 2, primary 3 and secondary 4 washing stages and that of conditioning. Vatting is carried out at intensive mixing in reactor with coating that regulates acidity using anolyte of electolyser or synthetic anolyte. Primary washing stage 3 is carried out in the same reactor till pH increases to values approximating to neutral one by removing, mainly, iron and aluminium. Produced fine pulp is filtered in pressure filter, flushed by water, preferably, in the same pressure filter, to produce inert wastes. Fine pulp flushing water is added into the mixer or used again to concentrate manganese therein. At secondary flushing stage 4, zinc impurity is removed by settling ZnS. Solution obtained after conditioning 5, is directed to electrolysis 6 to produce electrolytic manganese.

EFFECT: possibility to recover wastes to produce 99,9%-pure manganese.

5 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: purification of amine solution generated in the process of gases purification from hydrogen sulphide and carbon dioxide is carried out by extraction of foam-forming substances with polyphenyl ether with volume ratio "polyphenyl ether-amine solution" equal 1:50-300. The used polyphenyl ether is regenerated by mixing with methyl ethyl ketone in volume ratio equal respectively 1:1-3 with following deposition of foam-forming substances. Then the obtained mixture is separated in steam-stripping column for reuse in the purification process.

EFFECT: supporting of the admissible level of the foam-forming substances in the circulating amine solution, recovery of extraction properties of the polyphenyl ether and reuse of the latter in the process of amine solution purification.

1 dwg, 2 tbl

FIELD: production of hydrogen-containing gas suitable for supply of low-temperature fuel cells in self-contained small-sized electric generators.

SUBSTANCE: hydrogen-containing gas is produced on fixed layer containing the mixture of catalyst of steam conversion of hydrocarbons and regenerated carbon dioxide absorbent including the following stages performed in cyclic succession: A) reaction of steam conversion by passing the gaseous mixture of hydrocarbons and steam through said layer; B) regeneration of carbon dioxide absorbent by passing the regenerating agent through the said layer in direction opposite to direction of delivery of reagents at stage (A). At stage (A), said layer has area at temperature above 700C and area at temperature from 550C to 700C which are so located that reagent are first brought in contact with hotter area of layer and then which area of lower temperature. Regeneration of carbon dioxide absorbent used in production of hydrogen-containing gas is performed by passing the gaseous regenerating agent at content of oxygen no less than 5 vol-% through the said layer. Simultaneously, hydrogen-containing gas at content of hydrogen no less than 40 vol-% is introduced into various areas of the said layer; hydrogen-containing gas goes into exothermic reaction with oxygen of regenerating agent, thus generating the heat for regeneration of absorbent. Proposed method makes it possible to produce hydrogen from hydrocarbon fuel of purity of 98% at content of CO and CO2 lesser than 100 ppm.

EFFECT: facilitated procedure; enhanced efficiency.

8 dwg, 1 ex

The invention relates to processes of absorption and cleaning of gases from sulfur-containing impurities and can be used in the purification of gases of different composition

The invention relates to the field of gas industry, cryogenics

The invention relates to the field of adsorptive purification of hydrocarbon gases from mercaptans and hydrogen sulfide and can be used in gas, oil and petrochemical industries in the regeneration of zeolites used for these purposes

The invention relates to cryogenic technique and can be widely used for creating blocks for removal of moisture from in helium liquefaction and refrigeration plants

FIELD: production of hydrogen-containing gas suitable for supply of low-temperature fuel cells in self-contained small-sized electric generators.

SUBSTANCE: hydrogen-containing gas is produced on fixed layer containing the mixture of catalyst of steam conversion of hydrocarbons and regenerated carbon dioxide absorbent including the following stages performed in cyclic succession: A) reaction of steam conversion by passing the gaseous mixture of hydrocarbons and steam through said layer; B) regeneration of carbon dioxide absorbent by passing the regenerating agent through the said layer in direction opposite to direction of delivery of reagents at stage (A). At stage (A), said layer has area at temperature above 700C and area at temperature from 550C to 700C which are so located that reagent are first brought in contact with hotter area of layer and then which area of lower temperature. Regeneration of carbon dioxide absorbent used in production of hydrogen-containing gas is performed by passing the gaseous regenerating agent at content of oxygen no less than 5 vol-% through the said layer. Simultaneously, hydrogen-containing gas at content of hydrogen no less than 40 vol-% is introduced into various areas of the said layer; hydrogen-containing gas goes into exothermic reaction with oxygen of regenerating agent, thus generating the heat for regeneration of absorbent. Proposed method makes it possible to produce hydrogen from hydrocarbon fuel of purity of 98% at content of CO and CO2 lesser than 100 ppm.

EFFECT: facilitated procedure; enhanced efficiency.

8 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: purification of amine solution generated in the process of gases purification from hydrogen sulphide and carbon dioxide is carried out by extraction of foam-forming substances with polyphenyl ether with volume ratio "polyphenyl ether-amine solution" equal 1:50-300. The used polyphenyl ether is regenerated by mixing with methyl ethyl ketone in volume ratio equal respectively 1:1-3 with following deposition of foam-forming substances. Then the obtained mixture is separated in steam-stripping column for reuse in the purification process.

EFFECT: supporting of the admissible level of the foam-forming substances in the circulating amine solution, recovery of extraction properties of the polyphenyl ether and reuse of the latter in the process of amine solution purification.

1 dwg, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates can be used in metallurgy, electronics and in production of pigments and welding electrodes. Wastes of production of ferrous alloys containing, mainly, manganese represent slimes of fume gases washing from furnaces producing ferromanganese and silicon manganese. Said wastes are directed for thermal sulphating 1 that comprises furnace processing of material fed from mixer wherein said wastes have been subjected to treatment by acid with flow rate approximating to stoichiometric. Teflon chutes are used inside the furnace to produce SO2. Then hydrometallurgical phase is performed consisting of vatting stage 2, primary 3 and secondary 4 washing stages and that of conditioning. Vatting is carried out at intensive mixing in reactor with coating that regulates acidity using anolyte of electolyser or synthetic anolyte. Primary washing stage 3 is carried out in the same reactor till pH increases to values approximating to neutral one by removing, mainly, iron and aluminium. Produced fine pulp is filtered in pressure filter, flushed by water, preferably, in the same pressure filter, to produce inert wastes. Fine pulp flushing water is added into the mixer or used again to concentrate manganese therein. At secondary flushing stage 4, zinc impurity is removed by settling ZnS. Solution obtained after conditioning 5, is directed to electrolysis 6 to produce electrolytic manganese.

EFFECT: possibility to recover wastes to produce 99,9%-pure manganese.

5 cl, 6 dwg

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