CN105521831A - Regeneration technology of marine vanadium-titanium catalyst for SCR denitrification - Google Patents
Regeneration technology of marine vanadium-titanium catalyst for SCR denitrification Download PDFInfo
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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Abstract
The invention relates to a regeneration technology of a marine vanadium-titanium catalyst for SCR denitrification. In the main technology, performance of the catalyst is recovered by calcination, oxidation, physical chemical cleaning, active liquid impregnation, drying and activation, etc. In the main technological flow, tail gas generated by calcination and oxidation, acid mist generated by ultrasonic cleaning, chemical cleaning and rinsing, water vapor generated by drying and tail gas generated by drying and activation are collected and then enter a scrubber tower to undergo acid and alkali absorption gas-washing, and discharging is carried out after the processed product reaches the standard. Wastewater generated by physical chemcial treatment in the main technological flow and wastewater generated from the scrubber tower are collected through a wastewater collector and then undergo deep treatment and recycling. Cleaned mud cakes undergo stabilization and solidification to form landfillable solidified blocks. Through the above technological steps, activity of an inactive marine denitrification catalyst can be recovered, zero emission of wastewater can be realized, up-to-standard release of exhaust gas is realized, and the marine catalyst can be recycled.
Description
Technical field
The present invention relates to a kind of SCR denitration vanadium Titanium series catalyst regeneration technology peculiar to vessel.
Background technology
What the active force of large ship generally adopted is large-scale diesel engine, and its fuel is generally as sulfur-bearing, heavy oil that impurity content is high, containing a large amount of NO in the waste gas of therefore boats and ships discharge
x, SO
2, SO
3and PM2.5, the pollution that causes for harbour and coastal air of waste gas of boats and ships discharge is very important, and simultaneously owing to navigating by water in the whole world of foreign-going ship, make it pollute and non local, its toxic emission impacts whole earth atmospheric environment.
Seriously polluted in view of boats and ships discharging waste gas, International Maritime Organization have passed in October, 2008 amendment that supplemental provisions VI " prevents boats and ships from causing atmosphere pollution rule ", has formulated stricter boats and ships SO
2, SO
3, NO
xabgasgesetz.According to supplemental provisions VI amendment, by 2016, low-speed diesel engine NO
xemission limit to be down to 3.4g/ (kWh) from 17.0g/ (kWh), the emission limit of high-speed diesel engine NOx will be down to 1.96g/ (kWh) from 9.8g/ (kWh).In the face of so strict International Emissions regulation, SCR(selective catalytic reduction peculiar to vessel) denitration is used widely.But it should be noted that the vanadium Titanium series catalyst in boats and ships SCR denitration system is very easily losing activity in use, thus denitration cost is increased and produces a large amount of secondary danger to give up.
Be used widely in the SCR denitration that catalyst regeneration techniques uses in power station, technology is ripe, its catalyst blockage caused mainly for flying dust, sulfate, alkali metal are poisoning, arsenic poisoning etc., carry out regeneration recover by blowing, washing with the method for impregnating active.Catalyst peculiar to vessel can be used for reference said method and regenerate, but has a large amount of oil substances in pollutant in SCR catalyst peculiar to vessel, uses common power station denitrating catalyst cleaning and regeneration technology and is not suitable for.No. CN103920540A, the patent of invention " in a kind of diesel exhaust aftertreatment the renovation process of SCR denitration and device " of China's bulletin proposes ozone low temperature coke-burning regeneration method and carries out on-line regeneration, the method tentatively can only solve the impact of carbon distribution on catalyst peculiar to vessel, and the materials such as other grease class, sulfide, alkali metal, arsenic can not be solved to the pollution of catalyst, can not solve catalyst because active material run off and Problem of Failure.Therefore, a kind of technique of the thorough activity recovery of catalyst peculiar to vessel that can make is sought very necessary.
Summary of the invention
For problems of the prior art, the object of the present invention is to provide a kind of technical scheme of SCR denitration vanadium Titanium series catalyst regeneration technology peculiar to vessel.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that comprising following processing step:
A. utilize calcining furnace to calcine decaying catalyst, temperature controls at 300-600 DEG C, and time controling, at 10-30 minute, heating rate 2-10 DEG C/min, makes the carbonization of grease pollutant;
B. the catalyst after calcining enters oxidation furnace and carries out oxidation processes, ozone-air gas mixture that concentration is 20-300mg/l is passed in oxidation furnace, the temperature of ozone-air gas mixture controls at 50-300 DEG C, oxidation furnace oxidization time controls at 10-120min, ozone in oxidation furnace-air gas mixture flow control, at 0.5-15m/min, makes carbon distribution and the pollutant that is carbonized be removed by oxidation reaction;
C. pass through the near 30-50 DEG C of temperature after air blast cooling through the redox catalyst of oxidation furnace, rate of temperature fall controls at 2-10 DEG C/min;
D. the catalyst after cooling is put into ultrasonic cleaning pond and is carried out ultrasonic cleaning, and clean the fine particulates remained in catalyst microcellular structure, scavenging period controls at 10-30 minute;
E. the catalyst after ultrasonic cleaning is put into Chemical cleaning pond and is carried out soda acid Chemical cleaning, cleaning agent is added in cleaning, catalyst after Chemical cleaning realizes removing the harmful substance that attachment affects catalyst activity on a catalyst, and Chemical cleaning time controling is at 10-30 minute;
F. rinsing bath put into by the catalyst through Chemical cleaning, utilizes pure water to carry out abundant rinsing to the catalyst in rinsing bath, and wash away chemical agent residual in catalyst, rinsing time controls at 10-30 minute;
G. the catalyst of rinsed clean is put into drying box and is carried out drying, and remove catalyst surface moisture, baking temperature controls at 50-100 DEG C;
H. the catalyst that drying is complete is put into active liquid impregnating bath and is flooded, and pass into active liquid in impregnating bath, dip time controls at 10-30 minute, and active liquid Main Ingredients and Appearance is ammonium metavanadate, ammonium paratungstate, pure water;
I. after the catalyst taking-up of active liquid dipping drains, dry activation stove is put into, carry out drying to catalyst to activate, controlling heating rate is 2-10 DEG C/min, maximum temperature controls within 450 DEG C, the ammonium metavanadate flooded in the catalyst, ammonium paratungstate is carried out being decomposed to form active material vanadic anhydride and tungstic acid is attached on matrix;
J. the catalyst completed after activation forms product through packing and binding.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that: during the dry activation of the dry and step I of step a calcining, step b oxidation, step g, can tail gas be produced, can acid mist be produced when steps d ultrasonic cleaning, step e Chemical cleaning, when step g is dry, also can produce water vapour; Waste gas collection device is utilized to collect to the tail gas produced, acid mist, water vapour, waste gas after collection enters aeration tower and carries out soda acid absorption, and produce a small amount of waste water, after the tail gas of soda acid absorption reaches discharge standard, enter air-introduced machine, air-introduced machine is discharged by aiutage after being attracted by qualified tail gas.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that: the waste water produced after steps d ultrasonic cleaning, step e Chemical cleaning, step f rinsing is collected by waste water collection device, waste water through collecting enters dosing, stirring, precipitation three header process, add inorganic polymer chelating agent, fully remove the heavy metal in waste water and other harmful substances; The supernatant collection of dosing, stirring, precipitation three header enters the recycling of technique water tank, the sewage of dosing, stirring, precipitation three header enters micropore fine filtration machine and filters, filtrate water enters the recycling of technique water tank, carries out collection stand-by to the mud cake produced.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that the waste water that described aeration tower produces is collected by waste water collection device, waste water through collecting enters dosing, stirring, precipitation three header process, add inorganic polymer chelating agent, fully remove the heavy metal in waste water and other harmful substances; The supernatant collection of dosing, stirring, precipitation three header enters the recycling of technique water tank, the sewage of dosing, stirring, precipitation three header enters micropore fine filtration machine and filters, filtrate water enters the recycling of technique water tank, carries out collection stand-by to the mud cake produced.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that described micropore fine filtration machine mud cake out enters mixed stirring device, add cement in mixed stirring device, sandstone, stabilizing agent, water is fully uniformly mixed, slurry through being fully uniformly mixed enters compacting calciner plant, slurry is pressed and calcines, can be transferred to landfill yard and carry out landfill by landfill cured block after calcining.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the cleaning agent in described step e comprises the component of following weight portion: oxalic acid 1-3, surfactant PO-1040-47, penetration enhancer JFC40-47, pure water 6-17.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the weight portion of each component in the active liquid in described step h is: ammonium metavanadate 5-10, ammonium paratungstate 1-5, pure water 85-90.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the Main Ingredients and Appearance of described inorganic polymer chelating agent is sodium carbonate.
Described one SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the proportionate relationship of described cement, sandstone, stabilizing agent, water is 30:40:5:25.
Beneficial effect of the present invention:
1. remove by physics, chemical method the harmful substance that denitrating catalyst was lost efficacy;
2. supplement active material by dipping and recover monolith performance;
3. the waste gas produced in pair regeneration process, waste water, refuse carry out advanced treating, realize waste gas qualified discharge, wastewater zero discharge;
4. this technique can be divided into Base environment to produce and mobile production;
5. described in this technique, mobile production adopts the theory of mobile regeneration ship to realize;
6. utilize mobile regeneration ship can realize regenerating with ship.
Accompanying drawing explanation
Fig. 1 is main process chart of the present invention;
Fig. 2 is exhaust-gas treatment flow process figure of the present invention;
Fig. 3 is wastewater treatment process figure of the present invention;
Fig. 4 is Treatment of Sludge flow chart of the present invention.
Detailed description of the invention
Below in conjunction with Figure of description, the invention will be further described:
A kind of SCR denitration vanadium Titanium series catalyst regeneration technology peculiar to vessel, comprise main technological process, exhaust-gas treatment flow process, wastewater treatment process and the several part of Treatment of Sludge flow process, its main technological process processing step is as follows:
A. utilize calcining furnace to calcine decaying catalyst (deactivated catalyst), temperature controls at 300-600 DEG C, and time controling, at 10-30 minute, heating rate 2-10 DEG C/min, makes the carbonization of grease pollutant;
B. the catalyst after calcining enters oxidation furnace and carries out oxidation processes, ozone-air gas mixture that concentration is 20-300mg/l is passed in oxidation furnace, the temperature of ozone-air gas mixture controls at 50-300 DEG C, oxidation furnace oxidization time controls at 10-120min, ozone in oxidation furnace-air gas mixture flow control, at 0.5-15m/min, makes carbon distribution and the pollutant that is carbonized be removed by oxidation reaction;
C. pass through the near 30-50 DEG C of temperature after air blast cooling through the redox catalyst of oxidation furnace, rate of temperature fall controls at 2-10 DEG C/min;
D. the catalyst after cooling is put into ultrasonic cleaning pond and is carried out ultrasonic cleaning, and clean the fine particulates remained in catalyst microcellular structure, scavenging period controls at 10-30 minute;
E. the catalyst after ultrasonic cleaning is put into Chemical cleaning pond and is carried out soda acid Chemical cleaning, cleaning agent is added in cleaning, cleaning agent comprises the component of following percentage by weight: oxalic acid 1-3, surfactant PO-1040-47, penetration enhancer JFC40-47, pure water 6-17, can carry out separate configurations according to different batches; Catalyst after Chemical cleaning realizes removing the harmful substance that attachment affects catalyst activity on a catalyst, and Chemical cleaning time controling is at 10-30 minute;
F. rinsing bath put into by the catalyst through Chemical cleaning, utilizes pure water to carry out abundant rinsing to the catalyst in rinsing bath, and wash away chemical agent residual in catalyst, rinsing time controls at 10-30 minute;
G. the catalyst of rinsed clean is put into drying box and is carried out drying, and remove catalyst surface moisture, baking temperature controls at 50-100 DEG C;
H. the catalyst that drying is complete is put into active liquid impregnating bath and is flooded, active liquid is passed in impregnating bath, dip time controls at 10-30 minute, active liquid Main Ingredients and Appearance is ammonium metavanadate, ammonium paratungstate, pure water, and in active liquid, the weight portion of each component is: ammonium metavanadate 5-10, ammonium paratungstate 1-5, pure water 85-90;
I. after the catalyst taking-up of active liquid dipping drains, dry activation stove is put into, carry out drying to catalyst to activate, controlling heating rate is 2-10 DEG C/min, maximum temperature controls within 450 DEG C, the ammonium metavanadate flooded in the catalyst, ammonium paratungstate is carried out being decomposed to form active material vanadic anhydride and tungstic acid is attached on matrix;
J. the catalyst completed after activation forms product through packing and binding.
Exhaust-gas treatment flow process:
Can tail gas be produced during dry activations of the dry and step I of above-mentioned steps a calcining, step b oxidation, step g, can acid mist be produced when steps d ultrasonic cleaning, step e Chemical cleaning, during step g drying, also can produce water vapour; Waste gas collection device is utilized to collect to the tail gas produced, acid mist, water vapour, waste gas after collection enters aeration tower and carries out soda acid absorption, and produce a small amount of waste water, after the tail gas of soda acid absorption reaches discharge standard, enter air-introduced machine, air-introduced machine is discharged by aiutage after being attracted by qualified tail gas.
Waste water cleaning process:
The waste water that the waste water produced after above-mentioned steps d ultrasonic cleaning, step e Chemical cleaning, step f rinsing and aeration tower produce is collected by waste water collection device, waste water through collecting enters dosing, stirring, precipitation three header process, add inorganic polymer chelating agent (Main Ingredients and Appearance is sodium carbonate), fully remove the heavy metal in waste water and other harmful substances; The supernatant collection of dosing, stirring, precipitation three header enters the recycling of technique water tank, the sewage of dosing, stirring, precipitation three header enters micropore fine filtration machine and filters, filtrate water enters the recycling of technique water tank, carries out collection stand-by to the mud cake produced.
Treatment of Sludge flow process:
Above-mentioned micropore fine filtration machine mud cake out enters mixed stirring device, add cement in mixed stirring device, sandstone, stabilizing agent, water (proportion relation 30:40:5:25) is fully uniformly mixed, slurry through being fully uniformly mixed enters compacting calciner plant, slurry is pressed and calcines, can be transferred to landfill yard and carry out landfill by landfill cured block after calcining.
By deactivated denitrating catalyst activity recovery peculiar to vessel, and wastewater zero discharge, waste gas qualified discharge can be realized through above-mentioned processing step, make catalyst peculiar to vessel can regeneration.
The calcining furnace that the present invention uses, oxidation furnace enter, ultrasonic cleaning pond, Chemical cleaning pond, rinsing bath, drying box, impregnating bath, dry stove, waste gas collection device, aeration tower, air-introduced machine, waste water collection device, (dosing, stirring, precipitation) three headers, technique water tank, micropore fine filtration machine, mixed stirring device, the compacting calciner plant etc. of activating are conventional equipment, do not repeat them here its concrete outcome.
The present invention proposes the new technology of a kind of reproducible utilization SCR denitration peculiar to vessel, and system is simple, complete, and environmental friendliness is without secondary pollution; Every technology maturation of the present invention is reliable, easily realizes; Base environment can be realized produce, also can realize mobile and produce.
Claims (9)
1. a SCR denitration vanadium Titanium series catalyst regeneration technology peculiar to vessel, is characterized in that comprising following processing step:
A. utilize calcining furnace to calcine decaying catalyst, temperature controls at 300-600 DEG C, and time controling, at 10-30 minute, heating rate 2-10 DEG C/min, makes the carbonization of grease pollutant;
B. the catalyst after calcining enters oxidation furnace and carries out oxidation processes, ozone-air gas mixture that concentration is 20-300mg/l is passed in oxidation furnace, the temperature of ozone-air gas mixture controls at 50-300 DEG C, oxidation furnace oxidization time controls at 10-120min, ozone in oxidation furnace-air gas mixture flow control, at 0.5-15m/min, makes carbon distribution and the pollutant that is carbonized be removed by oxidation reaction;
C. pass through the near 30-50 DEG C of temperature after air blast cooling through the redox catalyst of oxidation furnace, rate of temperature fall controls at 2-10 DEG C/min;
D. the catalyst after cooling is put into ultrasonic cleaning pond and is carried out ultrasonic cleaning, and clean the fine particulates remained in catalyst microcellular structure, scavenging period controls at 10-30 minute;
E. the catalyst after ultrasonic cleaning is put into Chemical cleaning pond and is carried out soda acid Chemical cleaning, cleaning agent is added in cleaning, catalyst after Chemical cleaning realizes removing the harmful substance that attachment affects catalyst activity on a catalyst, and Chemical cleaning time controling is at 10-30 minute;
F. rinsing bath put into by the catalyst through Chemical cleaning, utilizes pure water to carry out abundant rinsing to the catalyst in rinsing bath, and wash away chemical agent residual in catalyst, rinsing time controls at 10-30 minute;
G. the catalyst of rinsed clean is put into drying box and is carried out drying, and remove catalyst surface moisture, baking temperature controls at 50-100 DEG C;
H. the catalyst that drying is complete is put into active liquid impregnating bath and is flooded, and pass into active liquid in impregnating bath, dip time controls at 10-30 minute, and active liquid Main Ingredients and Appearance is ammonium metavanadate, ammonium paratungstate, pure water;
I. after the catalyst taking-up of active liquid dipping drains, dry activation stove is put into, carry out drying to catalyst to activate, controlling heating rate is 2-10 DEG C/min, maximum temperature controls within 450 DEG C, the ammonium metavanadate flooded in the catalyst, ammonium paratungstate is carried out being decomposed to form active material vanadic anhydride and tungstic acid is attached on matrix;
J. the catalyst completed after activation forms product through packing and binding.
2. one according to claim 1 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that: during the dry activation of the dry and step I of step a calcining, step b oxidation, step g, can tail gas be produced, can acid mist be produced when steps d ultrasonic cleaning, step e Chemical cleaning, when step g is dry, also can produce water vapour; Waste gas collection device is utilized to collect to the tail gas produced, acid mist, water vapour, waste gas after collection enters aeration tower and carries out soda acid absorption, and produce a small amount of waste water, after the tail gas of soda acid absorption reaches discharge standard, enter air-introduced machine, air-introduced machine is discharged by aiutage after being attracted by qualified tail gas.
3. one according to claim 1 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that: the waste water produced after steps d ultrasonic cleaning, step e Chemical cleaning, step f rinsing is collected by waste water collection device, waste water through collecting enters dosing, stirring, precipitation three header process, add inorganic polymer chelating agent, fully remove the heavy metal in waste water and other harmful substances; The supernatant collection of dosing, stirring, precipitation three header enters the recycling of technique water tank, the sewage of dosing, stirring, precipitation three header enters micropore fine filtration machine and filters, filtrate water enters the recycling of technique water tank, carries out collection stand-by to the mud cake produced.
4. one according to claim 2 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, it is characterized in that the waste water that described aeration tower produces is collected by waste water collection device, waste water through collecting enters dosing, stirring, precipitation three header process, add inorganic polymer chelating agent, fully remove the heavy metal in waste water and other harmful substances; The supernatant collection of dosing, stirring, precipitation three header enters the recycling of technique water tank, the sewage of dosing, stirring, precipitation three header enters micropore fine filtration machine and filters, filtrate water enters the recycling of technique water tank, carries out collection stand-by to the mud cake produced.
5. the SCR denitration vanadium peculiar to vessel of the one according to claim 3 or 4 Titanium series catalyst regeneration technology, it is characterized in that described micropore fine filtration machine mud cake out enters mixed stirring device, add cement in mixed stirring device, sandstone, stabilizing agent, water is fully uniformly mixed, slurry through being fully uniformly mixed enters compacting calciner plant, slurry is pressed and calcines, can be transferred to landfill yard and carry out landfill by landfill cured block after calcining.
6. one according to claim 1 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the cleaning agent in described step e comprises the component of following weight portion: oxalic acid 1-3, surfactant PO-1040-47, penetration enhancer JFC40-47, pure water 6-17.
7. one according to claim 1 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the weight portion of each component in the active liquid in described step h is: ammonium metavanadate 5-10, ammonium paratungstate 1-5, pure water 85-90.
8. the SCR denitration vanadium peculiar to vessel of the one according to claim 3 or 4 Titanium series catalyst regeneration technology, is characterized in that the Main Ingredients and Appearance of described inorganic polymer chelating agent is sodium carbonate.
9. one according to claim 5 SCR denitration vanadium peculiar to vessel Titanium series catalyst regeneration technology, is characterized in that the proportionate relationship of described cement, sandstone, stabilizing agent, water is 30:40:5:25.
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| CN106870081A (en) * | 2017-02-09 | 2017-06-20 | 江苏万路达环保科技有限公司 | Automobile exhaust system is diagnosed and restorative procedure |
| CN106914281A (en) * | 2017-02-24 | 2017-07-04 | 南京智道环境材料有限公司 | A kind of V of arsenic poisoning2O5‑WO3/TiO2The renovation process of catalyst |
| CN109251762A (en) * | 2018-10-10 | 2019-01-22 | 天津大学 | A kind of coke cleaning method using ozone mixed gas |
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| CN113477083A (en) * | 2021-07-05 | 2021-10-08 | 国家电投集团远达环保催化剂有限公司 | Regeneration method of inactivated denitration dedusting ceramic tube |
| CN114534798A (en) * | 2022-02-21 | 2022-05-27 | 华电青岛环保技术有限公司 | Regeneration preparation method of carbon deposition SCR denitration catalyst |
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