CN114682348B - Crushing method of waste denitration catalyst and waste denitration catalyst powder prepared by crushing method - Google Patents

Crushing method of waste denitration catalyst and waste denitration catalyst powder prepared by crushing method Download PDF

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CN114682348B
CN114682348B CN202011625651.1A CN202011625651A CN114682348B CN 114682348 B CN114682348 B CN 114682348B CN 202011625651 A CN202011625651 A CN 202011625651A CN 114682348 B CN114682348 B CN 114682348B
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ball
dispersant
milling
denitration catalyst
powder
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CN114682348A (en
Inventor
周光虎
李柯志
任靖
王博
殷喜平
沈刚
韩帅
张新军
桂建舟
刘丹
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
Sinopec Catalyst Beijing Co Ltd
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
Sinopec Catalyst Beijing Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/20—Disintegrating members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/22—Lining for containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/06—Selection or use of additives to aid disintegrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C2201/00—Codes relating to disintegrating devices adapted for specific materials
    • B02C2201/06—Codes relating to disintegrating devices adapted for specific materials for garbage, waste or sewage

Abstract

The invention relates to the field of recycling of waste denitration catalysts, and discloses a crushing method of waste denitration catalysts and waste denitration catalyst powder prepared by the crushing method. The crushing method of the waste denitration catalyst comprises the following steps: 1) Crushing and screening pretreatment is carried out on the waste denitration catalyst to obtain pretreated powder; 2) Ball milling is carried out on the pretreated powder, ball milling beads and a solution containing a dispersing agent, wherein the dispersing agent is sodium dodecyl sulfate and/or polyoxyethylene lauryl ether, and the weight ratio of the dispersing agent to the pretreated powder is 1:50-100. The method can obviously reduce the particle size of the crushed powder, and can further improve the catalytic performance of the prepared novel denitration catalyst.

Description

Crushing method of waste denitration catalyst and waste denitration catalyst powder prepared by crushing method
Technical Field
The invention relates to the field of recycling of waste denitration catalysts, in particular to a crushing method of waste denitration catalysts and waste denitration catalyst powder prepared by the crushing method.
Background
The selective catalytic reduction method is the most widely used flue gas denitration technology internationally at present, has the advantages of no byproducts, no secondary pollution, simple device structure, safe and reliable operation, simple and convenient maintenance, high denitration efficiency of more than 90 percent and the like, and is basically applied to most power plants in various countries and regions of the world.
However, since the denitration catalyst gradually adheres and accumulates alkali metal, alkaline earth metal, other harmful heavy metal elements and the like in the long-term use process, catalyst poisoning is caused, and soot and the like in the operation process also block the pore channels of the denitration catalyst, the activity of the catalyst is reduced, and the denitration catalyst cannot be continuously applied. Thus, a large amount of spent denitration catalyst is produced each year.
At present, the recovery of the waste denitration catalyst mainly has two ways, namely separation and purification, namely, main components in the waste denitration catalyst such as Ti, W and V react with chemical reagents through chemical reactions to convert the W, V and the like into soluble salts, the soluble salts are leached and separated from the Ti, and then the Ti-containing, W-containing and V-containing compounds or oxides and the like are obtained through respective purification through technologies such as precipitation, enrichment and the like. However, in general, the process route of separation and purification is long, and the input cost is high, so that the industrial utilization value is not high. For example, CN105481007A discloses a method for recycling a waste SCR denitration catalyst, which comprises the steps of reacting the waste denitration catalyst with strong alkali NaOH or KOHCarrying out substitution reaction so as to separate vanadium, tungsten and titanium elements, thereby obtaining solid titanium slag and a solution containing vanadium and tungsten; continuing to add NH to the solution 4 HCO 3 Further separating vanadium element, thereby recovering NH 4 VO 3 Precipitating; in addition, the crystallization method is adopted to finally use Na 2 WO 4 Recovering tungsten element in the form of (a). Although the method realizes separation and purification, the separation and purification process is complex and cumbersome, and a large amount of wastewater is generated in the separation process to pollute the environment.
And secondly, directly recycling without separation, namely directly crushing the waste catalyst without separation of active components and carriers, then removing undesired impurities through washing and other treatments, and recycling the treated materials into preparation of new catalysts. For example, CN109295313a discloses a method for preparing a waste catalyst powder by simple pretreatment of a waste SCR catalyst, and then washing, drying, calcining and other treatments are performed to recover the waste catalyst powder to obtain titanium tungsten powder after removing glass fibers. However, since the conventional method for pulverizing the waste denitration catalyst has a limited pulverizing degree, the particle size of the pulverized waste catalyst powder is still large, and even through subsequent sulfuric acid treatment, activation and the like, it is difficult to efficiently remove impurities, so that the treated material cannot reach the raw material level, and further the catalytic performance of the new denitration catalyst prepared by the method is poor.
Disclosure of Invention
The invention aims to solve the problem that the waste denitration catalyst is difficult to crush and process in the prior art, and provides a crushing method of the waste denitration catalyst and waste denitration catalyst powder prepared by the crushing method. The method can obviously reduce the particle size of the crushed powder, thereby further improving the catalytic performance of the prepared novel denitration catalyst.
The inventors of the present invention have found through extensive studies that, when pulverizing a spent denitration catalyst, the particles of the spent denitration catalyst powder after ball milling can be significantly reduced by ball milling together a spent denitration catalyst powder after crushing and screening pretreatment, ball milling beads, a solution containing a dispersant of sodium dodecyl sulfate and/or polyoxyethylene lauryl ether, and thus completed the present invention.
Accordingly, in a first aspect the present invention provides a method of comminuting a spent denitration catalyst, the method comprising the steps of:
1) Crushing and screening pretreatment is carried out on the waste denitration catalyst to obtain pretreated powder;
2) Ball milling the pretreated powder, ball milling beads and a solution containing a dispersing agent,
wherein the dispersing agent is sodium dodecyl sulfate and/or polyoxyethylene lauryl ether, and the weight ratio of the dispersing agent to the pretreated powder is 1:50-100.
Preferably, in the step 2), the dispersing agent is polyoxyethylene lauryl ether, and the pH of the solution containing the dispersing agent is 3-13; more preferably, in step 2), the dispersant is polyoxyethylene lauryl ether and the pH of the solution containing the dispersant is from 6 to 11.
Preferably, in the step 2), the dispersing agent is sodium dodecyl sulfate, and the pH of the solution containing the dispersing agent is 3-12; more preferably, the dispersant is sodium dodecyl sulfate and the pH of the solution containing the dispersant is 9-11.
Preferably, in step 1), D of the pretreated powder 50 Is less than 50 mm; more preferably, in step 1), D of the pretreated powder 50 Is less than 30 mm.
Preferably, in step 2), the ball-milling beads are one or more of zirconia ball-milling beads, silicon carbide ball-milling beads, agate ball-milling beads and stainless steel ball-milling beads.
Preferably, in step 2), the ball-milling beads have a diameter of 0.5-5.5mm.
Preferably, in step 2), the ball-milling beads include large ball-milling beads having a diameter of 3 to 5.5mm and small ball-milling beads having a diameter of 0.5 to 1mm.
Preferably, in the step 2), the weight ratio of the large ball-milling beads to the small ball-milling beads is 0.1-5:1; more preferably, in step 2), the weight ratio of the large ball-milling beads to the small ball-milling beads is 1-3:1.
Preferably, in the step 2), the weight ratio of the dispersing agent to the pretreated powder is 1:50-90; more preferably, in the step 2), the weight ratio of the dispersing agent to the pretreated powder is 1:55-85.
Preferably, in the step 2), the weight ratio of the ball-milling beads to the pretreated powder is 1-20:1; more preferably, in step 2), the weight ratio of the ball-milling beads to the pretreated powder is 5-15:1.
Preferably, in step 2), the solvent in the solution containing the dispersing agent is water and/or ethanol; more preferably, in step 2), the solvent in the solution containing the dispersant is water.
Preferably, in step 2), the content of the dispersant is 5-25g relative to 1L of the solution containing the dispersant; more preferably, in step 2), the content of the dispersant is 10 to 15g relative to 1L of the solution containing the dispersant.
Preferably, in step 2), the ball milling is performed in a ball mill; more preferably, the ball mill lining material is selected from polytetrafluoroethylene balls and/or stainless steel.
Preferably, the volume of the solution containing the dispersant is 10-80% by volume of the ball mill.
Preferably, in step 2), the ball milling conditions include: the rotating speed is 100-500r/min, and the time is 1-5h; more preferably, in step 2), the ball milling conditions include: the rotating speed is 100-300r/min, and the time is 1-3h.
Preferably, the method further comprises: and (3) filtering, washing and drying the ball-milling slurry obtained after ball-milling in the step (2).
The second aspect of the invention provides a waste denitration catalyst powder prepared by the method according to the first aspect of the invention.
Through the technical scheme, the crushing method of the waste denitration catalyst can obviously reduce the powder particle size of the crushed waste denitration catalyst, and the crushing method is simple and easy to implement and is beneficial to subsequent treatment and recycling.
When the waste denitration catalyst powder treated by the crushing method is used as a raw material and is further prepared into a denitration catalyst, the strength and the catalytic performance of the obtained catalyst are excellent.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the invention, the D 50 The median particle diameter is the particle diameter corresponding to a cumulative distribution percentage of 50%.
The first aspect of the invention provides a method for pulverizing a waste denitration catalyst, which comprises the following steps:
1) Crushing and screening pretreatment is carried out on the waste denitration catalyst to obtain pretreated powder;
2) Ball milling the pretreated powder, ball milling beads and a solution containing a dispersing agent,
wherein the dispersing agent is sodium dodecyl sulfate and/or polyoxyethylene lauryl ether, and the weight ratio of the dispersing agent to the pretreated powder is 1:50-100.
In the present invention, the waste denitration catalyst may be various waste denitration catalysts conventionally used in the art, for example, may be a catalyst containing a carrier TiO 2 Containing the active ingredient WO 3 、V 2 O 5 And other impurities, and the like, without particular limitation.
According to the invention, since the waste denitration catalyst has a large volume and is difficult to directly perform ball milling, the waste denitration catalyst is firstly subjected to crushing and screening pretreatment before ball milling treatment.
In the present invention, the crushing and screening pretreatment may be performed by various methods commonly used in the art for crushing and screening. For example, the crushing may be performed by using various crushing apparatuses commonly used in the art to primarily crush the waste denitration catalyst, and then sieving the primarily crushed waste denitration catalyst to obtain pretreated powder.
As the crushing apparatus, for example, one or more of a jaw crusher, a hammer crusher, and a counterattack crusher may be selected, as long as the waste denitration catalyst having a large volume can be crushed into particles having a small volume. For example, the particles of the waste denitration catalyst may be crushed to particles having a particle diameter of 100mm or less by preliminary crushing, and preferably, the particles of the waste denitration catalyst may be crushed to particles having a particle diameter of 50mm or less by preliminary crushing.
In addition, in order to make the particle size of the crushed powder more uniform, the subsequent ball milling operation is better carried out, the crushed powder is screened, and the D of the powder obtained after screening is realized 50 Is 50mm or less, preferably such that D of the powder obtained after sieving 50 Is less than 30 mm.
In the present invention, the sieving may be performed using various methods conventionally used in the art for performing powder sieving, for example, one or more of a vibrating screen, a rotary screen, a fixed screen, and a shaking screen may be used, without particular limitation, and preferably, the powder sieving is performed using a vibrating screen.
Thus, the pretreated powder is obtained by crushing and sieving. Then, the pretreated powder, ball-milled beads and a solution containing a dispersing agent are subjected to ball milling together.
In the present invention, the ball-milling beads may employ various ball-milling beads commonly used in the art for ball-milling waste denitration catalysts, and are not particularly limited, and for example, the ball-milling beads may be one or more of zirconia ball-milling beads, silicon carbide ball-milling beads, agate ball-milling beads, and stainless steel ball-milling beads. Preferably, the ball-milling beads are zirconia ball-milling beads.
According to the present invention, the ball-milling beads may have a diameter of 0.5 to 5.5mm, and preferably, the ball-milling beads have a diameter of 0.8 to 5.2mm.
In addition, in order to further improve the ball milling effect, the ball milling beads can comprise large ball milling beads and small ball milling beads, the large ball milling beads can produce larger kinetic energy in the ball milling process, so that waste denitration catalyst powder is rapidly crushed, the small ball milling beads can further reduce the size of the powder, and the uniformity of products obtained by ball milling is improved. The diameter of the large ball-milling beads can be 3-5.5mm, and the diameter of the small ball-milling beads can be 0.5-1mm; preferably, the diameter of the large ball-milling beads is 3-5.2mm, and the diameter of the small ball-milling beads is 0.7-1mm.
According to the present invention, the weight ratio of the large ball-milling beads to the small ball-milling beads may be 0.1 to 5:1, and preferably, the weight ratio of the large ball-milling beads to the small ball-milling beads is 1 to 3:1. By controlling the weight ratio of the large ball-milling beads to the small ball-milling beads within the above range, the effect of ball milling can be further improved.
In the present invention, the solution containing the dispersant may be obtained by mixing the dispersant with a solvent, which may be water and/or ethanol, preferably, water.
In the present invention, the content of the dispersant in the dispersant-containing solution may vary within a wide range, and is not particularly limited as long as the weight ratio of the dispersant to the pretreated powder is within the range defined in the present invention. For example, the dispersant may be present in an amount of 5 to 25g relative to 1L of the dispersant-containing solution; preferably, the content of the dispersant is 8-15g relative to 1L of the solution containing the dispersant; more preferably, the content of the dispersant is 10 to 15g relative to 1L of the solution containing the dispersant.
The inventors of the present invention have also found that by adjusting the pH of the solution containing the dispersant, the effect of ball milling can be significantly further improved, and the particle size after the pulverization treatment can be greatly reduced.
Specifically, when the dispersant is polyoxyethylene lauryl ether, it is preferable to adjust the pH of the solution containing the dispersant to 3 to 13; more preferably, the pH of the dispersant-containing solution is adjusted to 6-11.
When the dispersing agent is sodium dodecyl sulfate, the pH value of the solution containing the dispersing agent can be adjusted to 3-12; preferably, the pH of the dispersant-containing solution is adjusted to 9-11.
In addition, when the dispersant is sodium dodecyl sulfate and polyoxyethylene lauryl ether, the pH of the dispersant-containing solution may be adjusted to 3 to 12; preferably, when the dispersant is sodium dodecyl sulfate and polyoxyethylene lauryl ether, the pH value of the solution containing the dispersant is adjusted to 7-12; more preferably, when the dispersant is sodium dodecyl sulfate and polyoxyethylene lauryl ether, the pH of the dispersant-containing solution is adjusted to 9 to 11.
In the present invention, the pH of the solution containing the dispersant may be adjusted by various methods commonly used in the art for adjusting the pH of a solution, for example, an acid solution, a base, an alkali solution, etc. may be added to the solution to adjust the pH of the solution, and the description thereof will be omitted.
The inventor of the invention discovers that when the dispersant sodium dodecyl sulfate and/or polyoxyethylene lauryl ether disclosed by the invention is adopted for ball milling, the weight ratio of the dispersant to the pretreated powder needs to be controlled within the range of 1:50-100 so as to obviously improve the ball milling and crushing effects.
In addition, in the present invention, preferably, the weight ratio of the dispersant to the pretreated powder is 1:50-90; more preferably, the weight ratio of the dispersing agent to the pretreated powder is 1:55-85. By controlling the weight ratio of the dispersant to the pretreated powder within the above range, the dispersant can be made to function more effectively, and the ball milling effect can be further improved.
According to the invention, during ball milling, the amount of the ball milling beads and the pretreated powder can be changed in a large range, for example, the weight ratio of the ball milling beads to the pretreated powder can be 1-20:1; preferably, the weight ratio of the ball-milling beads to the pretreated powder is 5-15:1. The ball milling effect can be ensured by controlling the weight ratio of the ball milling beads to the pretreated powder within the above range.
In the present invention, the ball milling may be performed by various apparatuses commonly used in the art for performing ball milling, so long as the pretreated powder, ball milling beads and a solution containing a dispersant may be ball-milled together, without particular limitation. Preferably, the ball milling is performed in a ball mill.
In the present invention, the ball mill may be a conventional choice in the art, and is not particularly limited as long as it can perform ball milling. Preferably, the ball mill lining material is selected from polytetrafluoroethylene and/or stainless steel.
In the invention, when the ball mill is adopted for ball milling, the ball milling efficiency can be improved by increasing the feeding amount in the ball mill, but if the feeding amount in the ball mill is too large, the treatment effect can be reduced, and the waste denitration catalyst is not easy to crush. The volume of the solution containing the dispersing agent is 10-80% of the volume of the ball mill; preferably, the volume of the solution containing dispersant is 10-50% by volume of the ball mill volume; more preferably, the volume of the solution containing the dispersant is 10-20% by volume of the ball mill.
According to the present invention, the conditions for the ball milling may include: the rotating speed is 100-500r/min, and the time is 1-5h; preferably, the ball milling conditions include: the rotating speed is 100-300r/min, and the time is 1-3h. The ball milling effect can be further ensured by controlling the rotating speed and the time during ball milling in the range, and the waste denitration catalyst powder with high crushing degree can be obtained.
In addition, according to the invention, after the ball milling is finished, the ball milling slurry obtained by the ball milling can be filtered to remove ball milling beads; further washing may be performed to remove the added dispersant. Of course, the washing may be followed by drying to remove the washing liquid used for the washing. In addition, since the waste denitration catalyst powder may be aggregated and agglomerated during the drying process, further grinding treatment may be performed, so that the aggregated powder is dispersed.
The above-mentioned filtration, washing, drying, grinding, etc. may be carried out by various methods conventional in the art, without particular limitation, and will not be described in detail herein.
In a particularly preferred embodiment of the present invention, the washing is performed using an ethanol solution (ethanol concentration of 90-100 wt%), and when the washing is performed using the ethanol solution, not only the dispersant can be removed more efficiently, but also the washing can be naturally dried by merely standing at room temperature (15-30 ℃) for 0.1-2 hours without performing a subsequent drying treatment. And the washed materials are not easy to agglomerate, and the subsequent treatments such as dispersing and grinding are not needed, so that the treatment flow can be further reduced, and the treatment efficiency is improved.
The second aspect of the invention provides a waste denitration catalyst powder prepared by the method of the first aspect of the invention.
According to the invention, D of the waste denitration catalyst powder obtained after ball milling treatment is obtained by the crushing method according to the first aspect of the invention 50 Can be as low as 5 μm or less, preferably, D of the waste denitration catalyst powder obtained after the ball milling treatment 50 Is less than 2.5 μm.
The present invention will be described in detail by examples.
In the following examples and comparative examples, the waste denitration catalyst was a waste denitration catalyst produced after 2 years of denitration catalytic reaction from petrochemical Co., ltd.
In the following examples and comparative examples, ball mills were used, commercially available from Changsha Tianchuang powder technology Co., ltd., model number VBP-0.2A, and the ball mill tank was a polytetrafluoroethylene liner with a volume of 20mL.
In the following examples and comparative examples, the pH of the dispersant-containing solution was adjusted with a sulfuric acid solution in which the concentration of sulfuric acid was 20% by weight and a sodium hydroxide solution in which the concentration of sodium hydroxide was 1mol/L.
Example 1
1) Crushing the waste denitration catalyst by using a crusher, and sieving to obtain D 50 A pretreated powder of 30mm or less;
2) 2.5g of the pretreated powder obtained in the step 1) is put into a polytetrafluoroethylene ball milling tank, 25g of zirconia ball milling beads are added, wherein the zirconia ball milling beads comprise 15g of large ball milling beads with the diameter of 3-5.2mm and 10g of small ball milling beads with the diameter of 0.87mm, and then 3mL of polyoxyethylene lauryl ether aqueous solution with the pH of 6.7 and the polyoxyethylene lauryl ether content of 10g/L is added;
3) Ball milling for 2h under the condition of 200r/min rotating speed;
4) Filtering the ball-milling slurry obtained in the step 3), removing ball-milling beads, washing the ball-milling slurry obtained after filtering by using ethanol solution with the concentration of 99.5 weight percent, wherein the content of the ethanol solution is 5 times of the volume of the ball-milling slurry, and standing for 0.5h at the temperature of 25 ℃ after washing to obtain waste denitration catalyst powder, wherein D is 50 As shown in table 1.
Examples 2 to 18 and comparative examples 1 to 12
The procedure of example 1 was followed, except that:
the pH of the polyethylene lauryl ether solutions in examples 2-9 and the amount of polyoxyethylene lauryl ether used were varied;
in examples 10-18, the dispersant was sodium dodecyl sulfate, and the pH of the sodium dodecyl sulfate solution, the amount of sodium dodecyl sulfate used, and the ball milling time were different;
in comparative examples 1 to 3, the dispersant was sodium dodecyl sulfate, and the amounts thereof were different;
in comparative examples 4 to 6, the dispersant was polyoxyethylene lauryl ether, and the amounts thereof were different;
in comparative example 7, 3mL of deionized water was used instead of the aqueous polyoxyethylene lauryl ether solution of example 1 without using a dispersant;
comparative examples 8-12 polyoxyethylene lauryl ether was replaced with a different dispersant (tween 20 or polyethylene glycol 1000) and the pH of the solutions containing the dispersants was different;
the results of examples 1 to 18 and comparative examples 1 to 12 are shown in Table 1.
TABLE 1
Figure BDA0002879202500000111
As can be seen from the results of Table 1, when ball milling is performed using the dispersant polyoxyethylene lauryl ether provided by the present invention, the polyoxyethylene lauryl ether is in phase with the polyoxyethylene lauryl ether when no dispersant is added and other conventional dispersants are addedUnder the same ball milling condition, the ball milling effect is obviously improved within the dosage range of the dispersing agent defined by the invention, and the D of the powder obtained by ball milling 50 Significantly reduced, below 3 μm, especially when the pH of the dispersant-containing solution is 6-11, D of the powder obtained by ball milling 50 Can be reduced to below 2.5 μm.
In addition, when the sodium dodecyl sulfate provided by the invention is used as the dispersing agent, D of the powder obtained by ball milling can be obtained by adjusting the weight ratio of the dispersing agent to the pretreated powder within the range limited by the invention 50 Reducing the particle diameter to below 5 mu m, particularly under the condition of pH value of 9-11, and ball milling the obtained powder D 50 Can be reduced to below 2.5 mu m, and the ball milling effect is obviously better compared with the comparative example without adding dispersing agent and the comparative example with adding other conventional dispersing agents.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (27)

1. A method for crushing a waste denitration catalyst, which is characterized by comprising the following steps:
1) Crushing and screening pretreatment is carried out on the waste denitration catalyst to obtain pretreated powder;
2) Ball milling the pretreated powder, ball milling beads and a solution containing a dispersing agent,
wherein the dispersing agent is sodium dodecyl sulfate and/or polyoxyethylene lauryl ether, and the weight ratio of the dispersing agent to the pretreated powder is 1:50-100.
2. The method according to claim 1, wherein in step 2), the dispersant is polyoxyethylene lauryl ether, and the pH of the solution containing the dispersant is 3 to 13.
3. The method according to claim 2, wherein in step 2), the dispersant is polyoxyethylene lauryl ether, and the pH of the solution containing the dispersant is 6 to 11.
4. The method of claim 1, wherein in step 2), the dispersant is sodium dodecyl sulfate and the pH of the dispersant-containing solution is 3-12.
5. The method of claim 4, wherein the dispersant is sodium dodecyl sulfate and the pH of the dispersant-containing solution is 9-11.
6. The method according to any one of claims 1 to 5, wherein in step 1), D of the pretreated powder 50 Is 50mm or less.
7. The method according to claim 6, wherein in step 1), D is the pretreated powder 50 Is less than 30 mm.
8. The method of any one of claims 1-5, wherein in step 2) the ball-milling beads are one or more of zirconia ball-milling beads, silicon carbide ball-milling beads, agate ball-milling beads, and stainless steel ball-milling beads.
9. The method according to any one of claims 1 to 5, wherein in step 2), the ball-milling beads have a diameter of 0.5 to 5.5mm.
10. The method according to any one of claims 1 to 5, wherein in step 2), the ball-milling beads include large ball-milling beads having a diameter of 3 to 5.5mm and small ball-milling beads having a diameter of 0.5 to 1mm.
11. The method of claim 10, wherein in step 2), the weight ratio of the large ball-milling beads to the small ball-milling beads is 0.1-5:1.
12. The method of claim 11, wherein in step 2), the weight ratio of the large ball-milling beads to the small ball-milling beads is 1-3:1.
13. The method according to any one of claims 1 to 5, wherein in step 2), the weight ratio of the dispersant to the pretreated powder is 1:50-90.
14. The method of claim 13, wherein in step 2), the weight ratio of the dispersant to the pretreated powder is 1:55-85.
15. The method of any one of claims 1-5, wherein in step 2), the weight ratio of the ball-milled beads to the pretreated powder is 1-20:1.
16. The method of claim 15, wherein in step 2), the weight ratio of the ball-milling beads to the pretreated powder is 5-15:1.
17. The method according to any one of claims 1 to 5, wherein in step 2) the solvent in the solution containing the dispersant is water and/or ethanol.
18. The method of claim 17, wherein in step 2), the solvent in the solution containing the dispersant is water.
19. The method according to any one of claims 1 to 5, wherein in step 2), the content of the dispersant is 5 to 25g relative to 1L of the dispersant-containing solution.
20. The method according to claim 19, wherein in step 2), the content of the dispersant is 10 to 15g with respect to 1L of the solution containing the dispersant.
21. The method according to any one of claims 1-5, wherein in step 2), the ball milling is performed in a ball mill.
22. A method according to claim 21, wherein the ball mill lining material is selected from polytetrafluoroethylene balls and/or stainless steel.
23. A method according to claim 21, wherein the volume of the solution containing dispersant is 10-80% by volume of the ball mill volume.
24. The method according to any one of claims 1 to 5, wherein in step 2), the ball milling conditions include: the rotating speed is 100-500r/min, and the time is 1-5h.
25. The method of claim 24, wherein in step 2), the ball milling conditions include: the rotating speed is 100-300r/min, and the time is 1-3h.
26. The method of any of claims 1-5, wherein the method further comprises: and (3) filtering, washing and drying the ball-milling slurry obtained after ball-milling in the step (2).
27. Waste denitration catalyst powder prepared by the method according to any one of claims 1 to 26.
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CN105709861B (en) * 2014-12-05 2018-07-03 中国石油化工股份有限公司 A kind of regeneration method of SCR denitration
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