CN111495842A - Method for removing tar contained in waste denitration catalyst - Google Patents
Method for removing tar contained in waste denitration catalyst Download PDFInfo
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- CN111495842A CN111495842A CN202010344945.0A CN202010344945A CN111495842A CN 111495842 A CN111495842 A CN 111495842A CN 202010344945 A CN202010344945 A CN 202010344945A CN 111495842 A CN111495842 A CN 111495842A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B5/00—Cleaning by methods involving the use of air flow or gas flow
- B08B5/04—Cleaning by suction, with or without auxiliary action
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/02—Cleaning by the force of jets or sprays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/102—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration with means for agitating the liquid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/007—Heating the liquid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/008—Polymeric surface-active agents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
The invention discloses a method for removing tar contained in a waste denitration catalyst, which relates to the technical field of resource recycling, and comprises the following steps: vacuum dust collection; soaking the catalyst after vacuum dust collection into a diluent of a special cleaning agent for tar cleaning for cleaning; carrying out leaching, spraying and cleaning on the cleaned catalyst; and washing the catalyst after spray washing with water. The method is specially designed for tar in the catalyst, can completely remove the tar on the waste denitration catalyst, has the removal efficiency of more than 98 percent, and has strong penetrability of the cleaning agent, easy water dissolution, normal-temperature use, difficult ignition and no explosion; can directly contact skin, has no harm to human body, and has no damage to cleaned catalyst substrate and TiO2The crystal form of the carrier is not changed, and the carrier can directly enter a regeneration system, so that the resource recycling of the waste SCR catalyst is realized, the environmental protection pressure is solved for the glass industry and the coking industry, and the carrier has better economic and social benefits.
Description
Technical Field
The invention relates to the technical field of resource recycling, in particular to a method for removing tar contained in a waste denitration catalyst, wherein the treated catalyst can enter a regeneration system for regeneration and reuse.
Background
With the increasing strictness of national environmental protection policies, SCR denitration systems are continuously added in the glass industry and the coking industry so as to ensure that the emission limit requirements of NOx are met. However, in the actual operation process, it is found that the denitration catalyst provided in the SCR denitration system is contaminated by tar in the use process. Tar adheres to the catalyst surface, plugging the catalyst pores, leading to catalyst deactivation.
The cause of tar pollution is analyzed, and the relationship between the cause and the arrangement of fuel and a denitration system burnt in a glass plant is realized. The fuel used in glass factories mainly comprises coal, heavy oil, natural gas, petroleum coke and coal tar. In addition to natural gas, when other fuels are not sufficiently combusted, tar is produced, which is in a gaseous state at temperatures above 300 ℃ and in a liquid state at temperatures below 300 ℃. The denitration system of the glass plant is divided into medium-high temperature and low temperature, wherein the operation temperature of the medium-high temperature is 280-410 ℃, and the operation temperature of the low temperature is 150-250 ℃. Denitration systems arranged at low temperature are easy to be polluted by tar, and in severe cases, the catalyst is immediately deactivated, and the catalyst is generally used for 1 year at most.
Similarly, the coking industry uses coal gas as a fuel, which contains a small amount of tar. When the tar is not fully combusted, the tar can enter a denitration system along with the flue gas. The inlet temperature of a denitration system in the coking industry is generally 260-300 ℃, tar in flue gas can be condensed and is adhered to a catalyst to cause rapid inactivation of the catalyst.
Currently, there are some enterprises that try to remove tar from deactivated catalyst by high temperature calcination. The method comprises the following specific steps: the catalyst is calcined by a hot-blast stove, generally tar slowly volatilizes at the temperature of more than 300 ℃, and the catalyst can be combusted when the temperature is continuously increased to more than 350 ℃. High-temperature calcination has an obvious effect on tar removal, but in the heating process, the catalyst inevitably combusts, so that the denitration catalyst is damaged, the catalyst cannot be regenerated and reused, and great danger is caused to production and operation. In addition, although some cleaning agents and cleaning methods for the waste denitration catalyst exist at present, the methods all have strong targeting property and only have effects on ash, heavy metals, alkali metal oxides and the like (especially heavy metals and alkali metal oxides) in the waste denitration catalyst, when the cleaning agents and the cleaning methods are used for removing the substances, part of tar can be taken away to a certain extent, but because the cleaning agents and the cleaning methods are not specially designed for the tar, the residual tar content in the treated catalyst is still too much, the removal rate of the tar is less than 50%, the operation of calcining for removing the tar and the like is still required to be added in the subsequent steps, the residual tar can seriously affect the subsequent catalyst regeneration, the catalyst recovery regeneration rate is greatly reduced, a large amount of resources are wasted, and environmental pollution is caused. Meanwhile, due to the particularity of the catalyst, the method which can be applied to removing tar on the surfaces of steel and the like cannot be applied to removing tar in the catalyst, the used cleaning agent and the matching method can cause the problems that a catalyst substrate is damaged or a crystal form is changed, and the like, and the cleaning agent is usually high in toxicity and can cause serious damage to workers and the environment.
Therefore, at present, there is no feasible technology to effectively remove tar on the waste denitration catalyst, so that no denitration catalyst recovery enterprise is willing to receive the waste catalyst containing tar, and the waste denitration catalyst is managed as hazardous waste, and is not allowed to be stored in a waste production enterprise for a long time, and the temporary storage condition is harsh and needs to meet the management system of hazardous waste, which becomes a difficult problem in glass factories and coking industries.
Disclosure of Invention
In order to solve the problem that no feasible technology is available for effectively removing tar in the waste denitration catalyst in the regeneration process of the waste denitration catalyst, the invention provides a method for removing tar contained in the waste denitration catalyst, and the technical scheme is as follows:
a method for removing tar contained in a waste denitration catalyst comprises the following steps:
(1) vacuum dust collection is carried out on the waste denitration catalyst module;
(2) soaking the catalyst module after vacuum dust collection into a diluent of a special cleaning agent for tar cleaning for cleaning;
(3) leaching, spraying and cleaning the catalyst module cleaned in the step (2) from top to bottom;
(4) and washing the catalyst module after spray cleaning with water.
And (2) removing the dust blocked in the catalyst pore channel by vacuum dust collection in the step (1). And (2) separating tar and other toxic substances from the catalyst by using a special cleaning agent. And (3) mixed liquid of the special cleaning agent for cleaning tar and tar remained on the catalyst module can be cleaned.
Preferably, in the step (1), the vacuum dust collection is carried out, wherein the vacuum pressure is 200-235 mbar, and the air volume is 200-265 m3H; the dust collection time is 20-40 min.
The special cleaning agent for cleaning tar in the step (2) comprises fatty alcohol-polyoxyethylene ether (AEO-20), secondary alkyl sodium sulfonate (SAS-60), ethanol, sodium hydroxide, triethanolamine, sodium tripolyphosphate, carbazone and water.
Preferably, in the special cleaning agent for tar cleaning in the step (2), the components in percentage by mass of the cleaning agent are as follows: 6 to 14 percent of fatty alcohol-polyoxyethylene ether (AEO-20), 1 to 11 percent of secondary alkyl sodium sulfonate (SAS-60), 2 to 13 percent of ethanol, 1 to 3 percent of sodium hydroxide, 1 to 5 percent of triethanolamine, 0.1 to 0.7 percent of sodium tripolyphosphate, 0.1 to 0.5 percent of carbazone and the balance of water.
Preferably, in the step (2), the liquid in the container is kept flowing by bubbling upwards from the lower part of the cleaning container.
Preferably, the mass/volume ratio of the catalyst module in the step (2) to the diluent of the special cleaning agent for cleaning tar is 1g, (80-120) m L.
Preferably, in the dilution of the tar cleaning special cleaning agent in the step (2), the tar cleaning special cleaning agent accounts for 20-60 vol%; the solvent for dilution is water.
Preferably, the cleaning in the step (2) is carried out at the temperature of 20-60 ℃ for 30-75 min.
Preferably, the spraying and cleaning time in the step (3) is 20-45 min; the spray cleaning liquid is water.
Preferably, the ratio of the catalyst module to water in the step (4) is 1g, (80-120) m L, and the water washing time is 30-75 min.
Advantageous effects
The invention has the beneficial effects that:
after the treatment by the method provided by the invention, tar on the waste denitration catalyst can be completely removed, and the removal efficiency reaches more than 98%. The cleaning agent has strong permeability, is easy to dissolve in water, can be used at normal temperature, is not easy to ignite and cannot explode; can be directly contacted with skin, and has no harm to human body. In addition, the ash content, partial water-soluble metal oxide and other toxic substances in the waste catalyst are removed simultaneously through treatment, the cleaned catalyst substrate is not damaged, and TiO2The crystal form of the carrier is not changed, and the carrier can directly enter a regeneration system for regeneration and reuse, thereby realizing the purpose ofThe resource recycling of the waste SCR catalyst solves the environmental protection pressure for the glass industry and the coking industry, and has better economic and social benefits.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples and comparative examples are parallel runs, with the same processing steps and parameters, unless otherwise indicated.
Preparation example 1 preparation of cleaning agent for cleaning Tar
The composition comprises fatty alcohol-polyoxyethylene ether (AEO-20), secondary alkyl sodium sulfonate (SAS-60), ethanol, sodium hydroxide, triethanolamine, sodium tripolyphosphate, carbazone and water. The components account for the mass percent of the cleaning agent as follows: 6% of fatty alcohol-polyoxyethylene ether (AEO-20), 1% of secondary alkyl sodium sulfonate (SAS-60), 2% of ethanol, 1% of sodium hydroxide, 1% of triethanolamine, 0.1% of sodium tripolyphosphate, 0.1% of carbazone and the balance of water. The reagent is taken according to the components and the proportion and is mixed evenly.
Preparation example 2 cleaning agent for cleaning tar
The composition comprises fatty alcohol-polyoxyethylene ether (AEO-20), secondary alkyl sodium sulfonate (SAS-60), ethanol, sodium hydroxide, triethanolamine, sodium tripolyphosphate, carbazone and water. The components account for the mass percent of the cleaning agent as follows: 14% of fatty alcohol-polyoxyethylene ether (AEO-20), 11% of secondary alkyl sodium sulfonate (SAS-60), 13% of ethanol, 3% of sodium hydroxide, 5% of triethanolamine, 0.7% of sodium tripolyphosphate, 0.5% of carbazone and the balance of water. The reagent is taken according to the components and the proportion and is mixed evenly.
Preparation example 3 preparation of cleaning agent for cleaning Tar
The composition comprises fatty alcohol-polyoxyethylene ether (AEO-20), secondary alkyl sodium sulfonate (SAS-60), ethanol, sodium hydroxide, triethanolamine, sodium tripolyphosphate, carbazone and water. The components account for the mass percent of the cleaning agent as follows: 8% of fatty alcohol-polyoxyethylene ether (AEO-20), 8% of secondary alkyl sodium sulfonate (SAS-60), 8% of ethanol, 2% of sodium hydroxide, 2% of triethanolamine, 0.5% of sodium tripolyphosphate, 0.2% of carbazone and the balance of water. The reagent is taken according to the components and the proportion and is mixed evenly.
Example 1A method for removing tar contained in a spent denitration catalyst
The special cleaning agent for cleaning tar prepared in preparation example 3 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 220m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 30 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:80m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 30 vol.%, the cleaning temperature is 40 ℃, and the cleaning time is 40 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; spraying for 30 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 80m L, the cleaning time is 40min, the tar removal rate of the catalyst module subjected to water cleaning reaches 98.2%, and the catalyst module does not contain other toxic substances and can be directly treated in a subsequent catalyst regeneration system.
Example 2 method for removing tar contained in waste denitration catalyst
The special cleaning agent for cleaning tar prepared in preparation example 3 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions that the vacuum pressure is 220mbar and the air volume is 230m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 30 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:100m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 40 vol.%, the cleaning temperature is 40 ℃, and the cleaning time is 40 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; the spraying time is 35 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 100m L, the cleaning time is 40min, the tar removal rate of the catalyst module subjected to water cleaning reaches 98.6%, and the catalyst module does not contain other toxic substances and can be directly treated in a subsequent catalyst regeneration system.
Example 3A method for removing tar contained in a spent denitration catalyst
The special cleaning agent for cleaning tar prepared in preparation example 3 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 240m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:120m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 40 vol%, the cleaning temperature is 35 ℃, and the cleaning time is 55 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; spraying for 40 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, the cleaning time is 55min, the removal rate of tar of the catalyst module subjected to water cleaning reaches 99.5%, and the catalyst module does not contain other toxic substances and can directly enter a subsequent catalyst regeneration system for treatment.
Example 4A method for removing tar contained in a spent denitration catalyst
The special cleaning agent for cleaning tar prepared in preparation example 3 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions that the vacuum pressure is 235mbar and the air volume is 250m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:120m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 20 vol.%, the cleaning temperature is 50 ℃, and the cleaning time is 55 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; spraying for 45 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, the cleaning time is 55min, the removal rate of tar of the catalyst module subjected to water cleaning reaches 99.1%, and the catalyst module does not contain other toxic substances and can directly enter a subsequent catalyst regeneration system for treatment.
Example 5A method for removing tar contained in a spent denitration catalyst
On the basis of embodiment 3, the cleaning agent for cleaning tar prepared in preparation example 1 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 240m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:120m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 40 vol%, the cleaning temperature is 35 ℃, and the cleaning time is 55 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; spraying for 40 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, the cleaning time is 55min, the removal rate of tar of the catalyst module subjected to water cleaning reaches 99.3%, and the catalyst module does not contain other toxic substances and can directly enter a subsequent catalyst regeneration system for treatment.
Example 6A method for removing tar contained in a spent denitration catalyst
On the basis of embodiment 3, the cleaning agent for cleaning tar prepared in preparation example 1 in this embodiment includes the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 240m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) cleaning the catalyst module subjected to vacuum dust collection in a diluent of a tar cleaning special cleaning agent, wherein a bubbling device is arranged in a cleaning tank (at the bottom) of a cleaning container to enable liquid in the tank to flow up and down, the ratio of the catalyst module in the cleaning tank to the diluent of the tar cleaning special cleaning agent is 1g:120m L, the volume ratio of the tar cleaning special cleaning agent in the diluent of the tar cleaning special cleaning agent is 40 vol%, the cleaning temperature is 35 ℃, and the cleaning time is 55 min;
(3) putting the catalyst module cleaned by the special cleaning agent for cleaning tar into an empty cleaning tank, and spraying and cleaning the module from top to bottom to clean the mixed liquid of the tar cleaning agent and the tar remained on the module, wherein the spraying liquid is tap water; spraying for 40 min;
(4) and (2) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, the cleaning time is 55min, the removal rate of tar of the catalyst module subjected to water cleaning reaches 99.6%, and the catalyst module does not contain other toxic substances and can directly enter a subsequent catalyst regeneration system for treatment.
Comparative examples 1-3 verification of effect of removing tar contained in waste denitration catalyst by adopting traditional waste denitration catalyst cleaning method
Preparing a cleaning agent: the components are uniformly mixed according to the following mass percent:
cleaning agent a: 0.5% of lauryl trimethyl ammonium bromide, 0.5% of fatty alcohol-polyoxyethylene ether, 5% of nitric acid and the balance of water;
and (b) cleaning agent b: 1% of lauryl trimethyl ammonium bromide, 1% of fatty alcohol-polyoxyethylene ether, 8% of nitric acid and the balance of water;
and (3) cleaning agent c: 0.8% of lauryl trimethyl ammonium bromide, 0.8% of fatty alcohol-polyoxyethylene ether, 6.5% of nitric acid and the balance of water.
Respectively adopting the cleaning agents a, b and c to clean the catalyst by the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 240m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) putting the catalyst module after vacuum dust collection into (completely immersed into) a cleaning agent for cleaning, wherein a bubbling device is arranged in a cleaning tank (the bottom) of a cleaning container, so that liquid in the tank can flow up and down; the cleaning temperature is 35 ℃ and the cleaning time is 55 min;
(3) putting the cleaned catalyst module into an empty cleaning tank, and spraying and cleaning the module from top to bottom to remove mixed liquid remained on the module, wherein the spraying liquid is tap water; spraying for 40 min;
(4) and (3) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, and the cleaning time is 55 min.
The tar removal rates of the catalyst modules cleaned by the cleaning agents a, b and c are respectively 30%, 33% and 18%.
Comparative examples 4-6 verification of effect of removing tar contained in waste denitration catalyst by adopting traditional waste denitration catalyst cleaning method
Respectively adopting the cleaning agents a, b and c prepared in comparative examples 1-3 to clean the catalyst by the following steps:
(1) the waste denitration catalyst module is processed under the conditions of vacuum pressure of 200mbar and air volume of 240m3Vacuum dust collection is carried out under the condition of/h to remove the dust blocked in the catalyst pore channel, and the dust collection time is 40 min;
(2) putting the catalyst module subjected to vacuum dust collection into (completely immersed into) a cleaning agent for ultrasonic cleaning, wherein an ultrasonic oscillation device is arranged in a cleaning tank of a cleaning container; the cleaning temperature is 35 ℃, and the ultrasonic cleaning time is 55 min;
(3) putting the cleaned catalyst module into an empty cleaning tank, and spraying and cleaning the module from top to bottom to remove mixed liquid remained on the module, wherein the spraying liquid is tap water; spraying for 40 min;
(4) and (3) putting the catalyst module subjected to spray cleaning into a tap water cleaning tank, and finally washing with water, wherein the ratio of the catalyst module to the water is 1g to 120m L, and the cleaning time is 55 min.
The tar removal rates of the catalyst modules cleaned by the cleaning agents a, b and c are 39%, 45% and 21%, respectively.
It can be seen that, although the traditional method for cleaning the waste denitration catalyst can remove other toxic substances in the catalyst, such as heavy metals, alkaline metal oxides and the like, the tar removal effect is not ideal, the method provided by the invention is specially designed for the tar removal requirement, the tar in the waste denitration catalyst can be removed in a targeted manner, the removal rate can reach 96%, the test verifies that other toxic substances in the catalyst, such as ash, water-soluble alkaline metal oxides and the like, are also removed, the treated catalyst can be directly regenerated, the regenerated catalyst is verified, the problem that the catalyst substrate is damaged or the crystal form is changed does not occur, and the method can be used for industrial production of regeneration of the waste denitration catalyst.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. A method for removing tar contained in a waste denitration catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) vacuum dust collection is carried out on the waste denitration catalyst module;
(2) soaking the catalyst module after vacuum dust collection into a diluent of a special cleaning agent for tar cleaning for cleaning;
(3) leaching, spraying and cleaning the catalyst module cleaned in the step (2) from top to bottom;
(4) and washing the catalyst module after spray cleaning with water.
2. The method for removing tar contained in a spent denitration catalyst according to claim 1The method is characterized in that: in the step (1), vacuum dust collection is carried out, wherein the vacuum pressure is 200-235 mbar, and the air volume is 200-265 m3H; the dust collection time is 20-40 min.
3. The method for removing tar in the waste denitration catalyst as set forth in claim 1, wherein the mass/volume ratio of the catalyst module in the step (2) to the diluent of the cleaning agent for cleaning tar is 1g (80-120) m L.
4. The method for removing tar contained in a spent denitration catalyst according to claim 1, characterized in that: in the diluent of the special cleaning agent for cleaning tar in the step (2), the special cleaning agent for cleaning tar accounts for 20-60 vol%; the solvent for dilution is water.
5. The method for removing tar contained in a spent denitration catalyst according to claim 1, characterized in that: the special cleaning agent for cleaning tar in the step (2) comprises fatty alcohol-polyoxyethylene ether, sodium secondary alkyl sulfonate, ethanol, sodium hydroxide, triethanolamine, sodium tripolyphosphate, carbazone and water.
6. The method of removing tar contained in a spent denitration catalyst according to claim 5, characterized in that: in the special cleaning agent for cleaning tar, the components in percentage by mass of the cleaning agent are as follows: 6 to 14 percent of fatty alcohol-polyoxyethylene ether, 1 to 11 percent of secondary alkyl sodium sulfonate, 2 to 13 percent of ethanol, 1 to 3 percent of sodium hydroxide, 1 to 5 percent of triethanolamine, 0.1 to 0.7 percent of sodium tripolyphosphate, 0.1 to 0.5 percent of carbazone and the balance of water.
7. The method for removing tar contained in a spent denitration catalyst according to claim 1, characterized in that: and (3) cleaning at the temperature of 20-60 ℃ for 30-75 min.
8. The method for removing tar contained in a spent denitration catalyst according to claim 1, characterized in that: the spraying and cleaning time in the step (3) is 20-45 min; the spray cleaning liquid is water.
9. The method for removing tar contained in the waste denitration catalyst according to claim 1, wherein the ratio of the catalyst module to water in the step (4) is 1g (80-120) m L, and the water washing time is 30-75 min.
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