阅读说明：本技术 一种废催化剂再生的系统及其应用 (System for regenerating waste catalyst and application thereof ) 是由 熊伟 吕永兴 姜维 佘肖伟 田浩杨 屈茂会 于 2020-12-16 设计创作，主要内容包括：本发明公开一种催化剂再生的系统,涉及催化剂再生技术领域。所述系统包括预处理装置、活化器、过热蒸汽炉、水蒸气冷却装置、烟气冷却净化装置；所述的预处理装置连接活化器；所述的过热蒸汽炉通过烟气管道连接活化器和烟气冷却净化装置,过热蒸汽炉与活化器之间设有烟气混合器,所述的烟气混合器连接烟气冷却净化装置；过热蒸汽炉通过水蒸气管道连接活化器；所述的水蒸气冷却装置连接活化器的出口；所述的活化器还设有氢气入口。本发明的废催化剂再生的系统,对不同的催化剂可以实现不同的再生活化过程,再生过程处理方式灵活,使用范围广,同时,利用多种换热器对各物料充分换热,系统内部协同性能好。(The invention discloses a catalyst regeneration system, and relates to the technical field of catalyst regeneration. The system comprises a pretreatment device, an activator, a superheated steam furnace, a steam cooling device and a flue gas cooling and purifying device; the pretreatment device is connected with the activator; the superheated steam furnace is connected with the activator and the flue gas cooling and purifying device through a flue gas pipeline, a flue gas mixer is arranged between the superheated steam furnace and the activator, and the flue gas mixer is connected with the flue gas cooling and purifying device; the superheated steam furnace is connected with the activator through a steam pipeline; the water vapor cooling device is connected with the outlet of the activator; the activator is also provided with a hydrogen inlet. The system for regenerating the waste catalyst can realize different regeneration and activation processes for different catalysts, has flexible treatment modes in the regeneration process and wide application range, and simultaneously utilizes various heat exchangers to fully exchange heat for various materials, and has good internal synergistic performance.)

1. A system for regenerating a waste catalyst is characterized by comprising a pretreatment device, an activator, a superheated steam furnace, a steam cooling device and a flue gas cooling and purifying device;

the pretreatment device is connected with the activator; the superheated steam furnace is connected with the activator and the flue gas cooling and purifying device through a flue gas pipeline, a flue gas mixer is arranged between the superheated steam furnace and the activator, and the flue gas mixer is connected with the flue gas cooling and purifying device; the superheated steam furnace is connected with the activator through a steam pipeline; the water vapor cooling device is connected with the outlet of the activator; the activator is also provided with a hydrogen inlet.

2. The system for regenerating a spent catalyst according to claim 1, wherein the number of the activators is at least two.

3. The system for regenerating spent catalyst according to claim 2, wherein the water vapor cooling means comprises a condenser, and a gas outlet of the condenser is connected to a gas inlet of the superheated steam boiler.

4. The system for regenerating spent catalyst according to claim 3, wherein the water vapor cooling device further comprises a water-cooled heat exchanger for preheating water in the superheated steam furnace, and the water-cooled heat exchanger is connected with the outlet of the activator and the inlet of the condenser.

5. The system for regenerating the waste catalyst according to claim 4, wherein the flue gas cooling and purifying device comprises a bag-type dust remover and an induced draft fan which are connected in sequence, and the flue gas mixer is connected with an outlet of the bag-type dust remover.

6. The system for regenerating spent catalyst according to claim 5, further comprising an air heat exchanger for preheating air in the superheated steam furnace, the air heat exchanger connecting the flue gas outlet of the superheated steam furnace and the inlet of the bag-type dust collector.

7. The system for regenerating a spent catalyst according to claim 6, wherein a steam heater for steam heating is provided between the superheated steam furnace and the activator.

8. The process of any of claims 1-7, comprising placing the deactivated BDO hydrogenation catalyst in an activator and passing superheated steam at 400 ℃ and 600 ℃ for 3-4 hours.

9. The method of using the system as claimed in any one of claims 1 to 7, which comprises immersing the deactivated dimethyl ether catalyst in the active material solution in the pretreatment device, placing the catalyst in an activator, introducing flue gas at 500 ℃ for calcination for 1-3 hours, and then switching to introduce hydrogen for reduction for 0.5-1 hour at the temperature of 150 ℃ and 350 ℃; the active substance solution is specifically prepared by soaking 1-3% of copper nitrate and zinc nitrate solution for 10-14 hours, wherein the weight ratio of CuO: the mass ratio of ZnO is 2:1, and the total mass fraction is 1-3%.

10. The method for applying the system as claimed in any one of claims 1 to 7, comprising the steps of firstly ultrasonically cleaning the deactivated denitration catalyst for 0.5 hour, then immersing the activated material solution in a pretreatment device, placing the activated material solution in an activator, and introducing flue gas at 500-600 ℃ for roasting for 3-5 hours for heat treatment; the active substance solution is specifically impregnated by 0.5-1.5 mass percent of ammonium metavanadate and molybdenum nitrate solution for 20-24 hours, and V₂O₅：MoO₃The total mass fraction is 0.5-1.5 percent and is 3: 1.

Technical Field

The technology relates to the technical field of catalyst regeneration, in particular to a catalyst regeneration system and application thereof.

Background

A substance which can change the chemical reaction rate of other substances in a chemical reaction and has no change in the quality and chemical properties of the substance itself before and after the chemical reaction is called a catalyst. The catalyst has an important role in industrial production because it can change the speed of the chemical reaction, but the catalyst cannot always maintain stable and constant activity, and the catalyst is gradually deactivated with the increase of the service time, so that a large amount of waste catalyst is generated.

It is reported that 50-70 million tons of waste catalyst are produced in the world every year, China is a large industrial country, and the production amount of the waste catalyst is large and is increased year by year. The waste catalyst often contains some toxic components, mainly heavy metals and volatile organic compounds, so that the method has great environmental risk, and is particularly important for harmless treatment and disposal. In addition, the waste catalyst has higher content of noble metal or other valuable metal, some are even far higher than the content of corresponding components in some lean ores, the metal grade is high, and the waste catalyst can be recycled as secondary resources. The comprehensive utilization of the waste catalyst can improve the resource utilization rate, avoid the environmental problems caused by the waste catalyst and realize sustainable development. Therefore, effective disposal and recycling of the spent catalyst has become a very important issue.

The regeneration of the waste catalyst mainly comprises the processes of cleaning, dipping, flue gas roasting, high-temperature steam activation, hydrogen reduction activation and the like. The regeneration method of the waste catalyst is different for the waste catalyst generated by different inactivation reasons, and the regeneration method of the waste catalyst is a single process or a combination of processes. At present, the research on the regeneration of the waste catalyst mainly refers to the regeneration of a single specific waste catalyst, mainly refers to the regeneration of a hydrogenation catalyst, generally adopts methods such as flue gas roasting or high-temperature steam activation, and the like, and a single set of device can only carry out regeneration treatment on one type of waste catalyst. However, a certain factory can simultaneously produce a plurality of waste catalysts, different catalysts have different inactivation reasons, a plurality of different waste catalyst regeneration systems are needed for complete treatment, the cooperativity among the systems is poor, the investment and operation cost is high, and the energy-saving and environment-friendly effects are poor.

Disclosure of Invention

Aiming at the problems, the system and the method for regenerating the catalyst disclosed by the invention have the characteristics of realizing different regeneration and activation processes for different catalysts, strong system flexibility, energy conservation, environmental protection and the like. The technical scheme comprises a material pretreatment system, a regeneration reactor system, a superheated steam and flue gas system, a steam cooling system and a flue gas cooling and purifying system, and the specific scheme is as follows.

A system for regenerating a waste catalyst comprises a pretreatment device, an activator, a superheated steam furnace, a steam cooling device and a flue gas cooling and purifying device;

the pretreatment device is connected with the activator; the superheated steam furnace is connected with the activator and the flue gas cooling and purifying device through a flue gas pipeline, a flue gas mixer is arranged between the superheated steam furnace and the activator, and the flue gas mixer is connected with the flue gas cooling and purifying device; the superheated steam furnace is connected with the activator through a steam pipeline; the water vapor cooling device is connected with the outlet of the activator; the activator is also provided with a hydrogen inlet.

Preferably, the number of the activators is at least two.

Specifically, the water vapor cooling device comprises a condenser, and a gas outlet of the condenser is connected with a fuel gas inlet of the superheated steam furnace.

Preferably, the water vapor cooling device further comprises a water-cooling heat exchanger for preheating water in the superheated steam furnace, and the water-cooling heat exchanger is connected with the outlet of the activator and the inlet of the condenser.

Preferably, the flue gas cooling and purifying device comprises a bag-type dust remover and an induced draft fan which are connected in sequence, and the flue gas mixer is connected with an outlet of the bag-type dust remover.

Further, the system also comprises an air heat exchanger for preheating air in the superheated steam furnace, wherein the air heat exchanger is connected with a smoke outlet of the superheated steam furnace and an inlet of the bag-type dust collector.

Preferably, a steam heater for heating water vapor is arranged between the superheated steam furnace and the activator.

Preferably, the air inlet of the superheated steam furnace is provided with a combustion fan.

Preferably, the outlet of the flue gas mixer is provided with a flue gas fan.

Preferably, a gas fan is arranged at a gas outlet of the condenser.

The pretreatment device can carry out pretreatment of the waste catalyst material, including cleaning of the deactivated catalyst and impregnation of the active substance solution. Different pretreatment processes may be used depending on the catalyst. After the materials are pretreated, the waste catalyst is loaded into an activation reactor. The active substance solution is impregnated by 0.5-5% by mass of copper nitrate, cobalt nitrate, nickel nitrate, bismuth nitrate, aluminum nitrate, molybdenum nitrate, zinc nitrate, ferric nitrate, manganese nitrate, ammonium metavanadate, palladium chloride or chloroplatinic acid for 6-24 hours.

The reactor is preferably a fixed bed type activation regeneration device, two activators are arranged, and the two activators alternately operate at intervals to realize continuous operation of the system. Different catalysts need different activation processes, including high-temperature steam activation, flue gas roasting activation and hydrogen reduction activation, and different regeneration activation processes can be realized for different catalysts by the reactor of the system. After the waste catalyst is loaded into an activator, introducing corresponding activated gas, wherein the specific processes are as follows:

(1) water vapor activation: the high-temperature water vapor comes from a superheated steam furnace, the temperature of the water vapor is 600-900 ℃, the temperature can be adjusted, the activation time of the water vapor is 2-4 hours, the high-temperature water vapor reacts with the carbon deposition of the catalyst to generate carbon monoxide and hydrogen, the carbon deposition is eliminated, the activity of the waste catalyst is recovered, and meanwhile, the water vapor can remove dust impurities deposited on the surface of the catalyst.

(2) Flue gas activation: the flue gas also comes from a superheated steam furnace, the temperature of the flue gas is 300-800 ℃, the activation time of the flue gas is 1-3 hours, carbon deposition in the catalyst can be removed through flue gas roasting, the catalyst can be regenerated, and meanwhile, the waste catalyst after being impregnated with the active substance solution can be roasted through the flue gas.

(3) Hydrogen reduction and activation: after the waste catalyst is roasted by dipping in an active substance solution, further reduction is needed, hydrogen is introduced at the temperature of 150-350 ℃ to reduce the catalyst, the reduction time is 0.5-2 hours, metal active sites are added, and the reduced hydrogen enters a superheated steam furnace for combustion.

The superheated steam furnace is used for generating high-temperature steam and flue gas for activating and regenerating a catalyst by an activator and mainly comprises the superheated steam furnace and a steam heater. The main fuel of the superheated steam furnace is natural gas, and a small amount of fuel gas generated by the activator is cooled and then sent into the superheated steam furnace for combustion, so that the natural gas is saved. Combustion-supporting air and softened water are respectively sent into the superheated steam furnace after heat exchange through the heat exchanger, sufficient heat exchange is realized, energy is saved, emission is reduced, generated superheated steam is further heated through the steam heater to reach the temperature required by reaction, the temperature is introduced into the activator, generated flue gas enters the flue gas cooling and purifying system, and when the flue gas is required to be activated and heated, the flue gas can enter the activator in advance.

The water vapor from the activator firstly passes through the water-cooling heat exchanger to add the water needed by the superheated steam furnaceHeating, passing through condenser, collecting condensed water in collecting tank, and delivering to owner sewage treatment system, wherein the non-condensable fuel gas (mainly comprising CO and H) is obtained₂) And the waste catalyst is sent into an overheated steam furnace by a fan for combustion treatment, the whole process fully utilizes energy for heat exchange and combustible gas generated by organic matters in the waste catalyst, and the waste catalyst is energy-saving and environment-friendly.

The flue gas purification mainly adopts a 'cloth bag dust removal' process technology. The main fuel is natural gas and a small amount of fuel gas (CO, H) generated by activation₂) Are clean fuel gas, and the main pollutant in the flue gas is a small amount of dust which may exist. The flue gas that the superheated steam stove came out, give combustion-supporting air through air heat exchanger and preheat earlier, simultaneously flue gas self cooling, the exhaust gas temperature control is about 150 ℃, then passes through the sack cleaner dust removal and carries out purification treatment, and flue gas up to standard is finally led the chimney by the draught fan and is discharged.

A method for applying the system comprises the steps of placing the deactivated BDO hydrogenation catalyst in an activator, and introducing overheated steam with the temperature of 400 ℃ and 600 ℃ for 3-4 hours.

The other method applying the system comprises the steps of dipping the inactivated dimethyl ether catalyst in an active substance solution in a pretreatment device, placing the dipped inactivated dimethyl ether catalyst in an activator, introducing flue gas at the temperature of 300-350 ℃ for roasting for 1-3 hours, and then switching and introducing hydrogen at the temperature of 150-350 ℃ for reduction for 0.5-1 hour; the active substance solution is specifically prepared by soaking 1-3% of copper nitrate and zinc nitrate solution for 10-14 hours, wherein the weight ratio of CuO: the mass ratio of ZnO is 2:1, and the total mass fraction is 1-3%.

The other method for applying the system comprises the steps of firstly ultrasonically cleaning the inactivated denitration catalyst for 0.5 hour, then dipping the inactivated denitration catalyst in an active substance solution in a pretreatment device, placing the activated denitration catalyst in an activator, and introducing flue gas at the temperature of 500-; the active substance solution is specifically impregnated by 0.5-1.5 mass percent of ammonium metavanadate and molybdenum nitrate solution for 20-24 hours, and V₂O₅：MoO₃The total mass fraction is 0.5-1.5 percent and is 3: 1.

The system for regenerating the waste catalyst can realize different regeneration and activation processes for different catalysts, including high-temperature steam activation, flue gas roasting activation and hydrogen reduction activation, has flexible treatment modes and wide application range in the regeneration process of the waste catalyst, simultaneously utilizes various heat exchangers to fully exchange heat for various materials, has good synergistic performance in the system, and utilizes combustible gas generated in the regeneration process of the waste catalyst, thereby saving energy and protecting environment of the whole system.

Drawings

FIG. 1 is a schematic diagram of a system for regenerating spent catalyst according to the present invention;

FIG. 2 is a process flow diagram of a system for regenerating a spent catalyst according to the present invention.

Detailed Description

In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to specific embodiments.

Examples

The system for regenerating the waste catalyst shown in fig. 1 comprises a pretreatment device, an activator, a superheated steam furnace, a water vapor cooling device and a flue gas cooling and purifying device.

The pretreatment device is connected with the activator; the pretreatment device can carry out pretreatment of the waste catalyst material, including cleaning of the deactivated catalyst and impregnation of the active substance solution. Different pretreatment processes may be used depending on the catalyst. After the materials are pretreated, the waste catalyst is loaded into an activation reactor. The active substance solution is impregnated by 0.5-5% by mass of copper nitrate, cobalt nitrate, nickel nitrate, bismuth nitrate, aluminum nitrate, molybdenum nitrate, zinc nitrate, ferric nitrate, manganese nitrate, ammonium metavanadate, palladium chloride or chloroplatinic acid for 6-24 hours.

The two activators are arranged side by side, and each activator is provided with a hydrogen inlet, a gas inlet and a gas outlet. The reactor is preferably a fixed bed type activation regeneration device, two activators are arranged, and the two activators alternately operate at intervals to realize continuous operation of the system.

The superheated steam furnace is provided with a water inlet, an air inlet, a natural gas inlet, a fuel gas inlet, a water vapor outlet and a flue gas outlet. A flue gas mixer is arranged between the superheated steam furnace and the activator, a flue gas outlet of the superheated steam furnace is connected with the flue gas mixer through a flue gas pipeline, the flue gas mixer is connected with a gas inlet of the activator through a flue gas pipeline, and a flue gas fan is arranged at an outlet of the flue gas mixer. A steam heater for heating the steam is arranged between the superheated steam furnace and the activator, a steam outlet of the superheated steam furnace is connected with the steam heater through a steam pipeline, and the steam heater is connected with a gas inlet of the activator.

The superheated steam furnace is used for generating high-temperature steam and flue gas for activating and regenerating a catalyst by an activator and mainly comprises the superheated steam furnace and a steam heater. The main fuel of the superheated steam furnace is natural gas, and a small amount of fuel gas generated by the activator is cooled and then sent into the superheated steam furnace for combustion, so that the natural gas is saved. Combustion-supporting air and softened water are respectively sent into the superheated steam furnace after heat exchange through the heat exchanger, sufficient heat exchange is realized, energy is saved, emission is reduced, generated superheated steam is further heated through the steam heater to reach the temperature required by reaction, the temperature is introduced into the activator, generated flue gas enters the flue gas cooling and purifying system, and when the flue gas is required to be activated and heated, the flue gas can enter the activator in advance.

The flue gas cooling and purifying device comprises a bag-type dust remover, an induced draft fan and a chimney which are connected in sequence.

The system for regenerating the waste catalyst further comprises an air heat exchanger for preheating air in the superheated steam furnace, a smoke inlet of the air heat exchanger is connected with a smoke outlet of the superheated steam furnace, a smoke outlet of the air heat exchanger is connected with an inlet of the bag-type dust collector, and an air outlet of the air heat exchanger is connected with an air inlet of the superheated steam furnace. The air inlet of the superheated steam furnace is provided with a combustion fan.

The outlet of the bag-type dust collector is also provided with a pipeline connected with a flue gas mixer. The flue gas purification mainly adopts a 'cloth bag dust removal' process technology. The main fuel is natural gas and a small amount of fuel gas (CO, H) generated by activation₂) Are clean fuel gas, and the main pollutant in the flue gas is a small amount of dust which may exist. The flue gas coming out of the superheated steam furnace is preheated for combustion air through an air heat exchanger, simultaneously the flue gas is cooled, the temperature of the discharged flue gas is controlled to be about 150 ℃, then the flue gas is subjected to dust removal through a bag-type dust remover to be purified, and the flue gas reaching the standardAnd finally, leading the waste gas to a chimney by an induced draft fan for discharging.

The water vapor cooling device comprises a condenser and a water-cooled heat exchanger. The water-cooled heat exchanger is connected with the outlet of the activator and the inlet of the condenser and is used for preheating water in the superheated steam furnace. The gas outlet of the condenser is connected with the gas inlet of the superheated steam furnace, and the gas outlet of the condenser is provided with a gas fan.

The water vapor from the activator firstly passes through the water-cooling heat exchanger to heat the water required by the superheated steam furnace, then passes through the condenser, the condensed water enters the collecting tank and then is sent into the owner sewage treatment system, and the fuel gas (the main components are CO and H) which can not be condensed₂) And the waste catalyst is sent into an overheated steam furnace by a fan for combustion treatment, the whole process fully utilizes energy for heat exchange and combustible gas generated by organic matters in the waste catalyst, and the waste catalyst is energy-saving and environment-friendly.

The system can realize different regeneration and activation processes for different catalysts according to the system process flow of catalyst regeneration shown in FIG. 2. After the waste catalyst is loaded into the activator, according to the requirement, the required activating gas is introduced, and the optional activating process is as follows:

(1) water vapor activation: the high-temperature water vapor comes from a superheated steam furnace, the temperature of the water vapor is 400-900 ℃, the temperature can be adjusted, the activation time of the water vapor is 2-4 hours, the high-temperature water vapor reacts with the carbon deposition of the catalyst to generate carbon monoxide and hydrogen, the carbon deposition is eliminated, the activity of the waste catalyst is recovered, and meanwhile, the water vapor can remove dust impurities deposited on the surface of the catalyst.

(2) Flue gas activation: the flue gas also comes from a superheated steam furnace, the temperature of the flue gas is 300-800 ℃, the activation time of the flue gas is 1-3 hours, carbon deposition in the catalyst can be removed through flue gas roasting, the catalyst can be regenerated, and meanwhile, the waste catalyst after being impregnated with the active substance solution can be roasted through the flue gas.

(3) Hydrogen reduction and activation: after the waste catalyst is roasted by dipping in an active substance solution, further reduction is needed, hydrogen is introduced at the temperature of 150-350 ℃ to reduce the catalyst, the reduction time is 0.5-2 hours, metal active sites are added, and the reduced hydrogen enters a superheated steam furnace for combustion.

For different catalyst types, the corresponding activation method can be selected, as follows.

1) Activation of BDO hydrogenation catalyst

And (3) water vapor activation, namely putting the inactivated BDO hydrogenation catalyst into an activator, and introducing overheated water vapor at the temperature of 500 ℃ for 4 hours.

2) Activation of dimethyl ether catalyst

Pretreatment, flue gas activation and hydrogen reduction activation: the inactivated dimethyl ether catalyst is soaked in an active substance solution in a pretreatment device, then is placed in an activator, is introduced with flue gas at 400 ℃ for roasting for 2 hours, and then is switched to be introduced with hydrogen for reduction for 0.5 hour. The active substance solution impregnation is specifically that copper nitrate and zinc nitrate solution with the mass fraction of 2% is impregnated for 12 hours, and the ratio of CuO: the ZnO mass ratio is 2:1, and the total mass fraction is 2%.

3) Activation of denitration catalyst

Pretreatment and flue gas activation: the method comprises the following steps of firstly ultrasonically cleaning an inactivated denitration catalyst for 0.5 hour to remove dust impurities and the like, then soaking the inactivated denitration catalyst in an active substance solution in a pretreatment device, placing the impregnated denitration catalyst in an activator, and introducing flue gas at 550 ℃ for roasting for 4 hours for heat treatment to recover the activity of the regenerated catalyst. The active substance solution is impregnated by 1 percent of ammonium metavanadate and molybdenum nitrate solution for 24 hours, and V is₂O₅：MoO₃The ratio is 3:1, and the total mass fraction is 2%.

The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.