CN107837681B - System and method for recovering desulfurizer in gas after catalytic cracking regeneration waste gas desulfurization - Google Patents
System and method for recovering desulfurizer in gas after catalytic cracking regeneration waste gas desulfurization Download PDFInfo
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- CN107837681B CN107837681B CN201711191728.7A CN201711191728A CN107837681B CN 107837681 B CN107837681 B CN 107837681B CN 201711191728 A CN201711191728 A CN 201711191728A CN 107837681 B CN107837681 B CN 107837681B
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 50
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 32
- 239000002912 waste gas Substances 0.000 title claims abstract description 30
- 230000008929 regeneration Effects 0.000 title claims abstract description 19
- 238000011069 regeneration method Methods 0.000 title claims abstract description 19
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 238000011084 recovery Methods 0.000 claims abstract description 8
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 8
- 229910001039 duplex stainless steel Inorganic materials 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
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- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
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- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
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- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 33
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 239000000112 cooling gas Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910000856 hastalloy Inorganic materials 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000009270 solid waste treatment Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a recovery system and a method of a desulfurizer in gas after catalytic cracking regeneration waste gas desulfurization, wherein the recovery system comprises a desulfurizing tower, a condensing heat exchanger, a mechanical separation purifier, a heating heat exchanger and a filter, wherein a gas outlet of the desulfurizing tower is communicated with a gas inlet of the mechanical separation purifier through a first pipeline, and the condensing heat exchanger is arranged in the first pipeline; the heating heat exchanger is arranged in an exhaust pipeline of the mechanical separation purifier; the condensing heat exchanger and the mechanical separation purifier are respectively communicated with the filter through a second pipeline. The invention can effectively reduce the dew point of the gas at the outlet of the desulfurizing tower, reduce the water vapor content in the gas at the outlet and the concentration of the carried desulfurizing agent and catalyst particles, recover most of the desulfurizing agent, reduce the discharging loss of the desulfurizing agent, reduce the operation cost and reduce the environmental pollution; through setting up heating heat exchanger, can prevent that the exhaust gas from getting into the temperature and still can condense out the liquid drop at once less than gas temperature environment, avoid forming the white fog.
Description
Technical Field
The invention relates to the technical field of environmental protection processes, in particular to a system and a method for recovering a desulfurizing agent in gas after catalytic cracking regeneration waste gas desulfurization.
Background
Catalytic cracking is an important process in the production of oil refining. The catalyst for catalytic cracking needs to be periodically regenerated, and the waste gas generated in the regeneration process contains pollutants such as sulfur dioxide and the like, and can be discharged after being purified by a desulfurization process. The desulfurization is generally carried out by a wet desulfurization process, wherein the desulfurizing agent is alkali liquor, and is contacted with gas to react with sulfur dioxide to remove the sulfur dioxide in the gas. The alkali liquor can be lime, sodium hydroxide or sodium carbonate, ammonia, etc., and the corresponding desulfurization processes are respectively called calcium method, sodium-alkali method and ammonia method desulfurization processes. The desulfurized gas contains saturated water vapor, entrained desulfurizer and residual catalyst particles. Because the waste gas generated by catalytic cracking regeneration is large in quantity, the total quantity of entrained water vapor, catalyst particles, a desulfurizing agent and the like is large, and if the waste gas is not treated, the environmental pollution is caused. Besides pollution, the entrained desulfurizer also causes desulfurizer loss, additional desulfurizer has to be supplemented, and the operation cost is increased.
The main components of the catalytic cracking catalyst are alumina and silicate, the main components are insoluble in water, have small particle size, generally have particle size of 40-80 mu m, are easily entrained by gas, have high hardness and have obvious erosion effect on the wall of equipment. This is a clear difference between the desulfurized gas from the catalytic cracking regenerated flue gas and the desulfurized gas from other flue gases. Therefore, the erosion effect of the high-hardness catalyst particles needs to be considered, and the equipment needs to be specially modified or designed.
Flue gas-flue gas reheaters (GGH) are often employed in desulfurization processes. Namely, the hot waste gas entering the desulfurizing tower and the purified gas exiting the desulfurizing tower carry out gas-gas heat exchange, the hot waste gas entering the desulfurizing tower is cooled by adopting a rotary heat accumulating type heat exchange mode, and the purified gas exiting the desulfurizing tower is heated and warmed. Through the technology, the temperature of gas entering the desulfurizing tower is reduced, the absorption efficiency is improved, the temperature of gas exiting the desulfurizing tower is increased, and liquid drops are eliminated, so that the corrosion to subsequent equipment is reduced. However, this technique causes blockage and operational problems because the solid dust carried in the hot flue gas is easily deposited in the heat accumulator; and the gas at the outlet of the desulfurizing tower is heated, so that the dew point of the gas can not be effectively reduced, on one hand, water vapor and a desulfurizing agent carried by the gas are still greatly lost, and cause pollution after being introduced into the atmosphere, and on the other hand, the gas has a high condensation probability in a low-temperature environment, and is easy to corrode and deposit to block pipelines and equipment.
Disclosure of Invention
The invention aims to solve the technical problem in the prior art and provides a system and a method for recovering a desulfurizing agent in gas after catalytic cracking regeneration waste gas desulfurization.
The technical scheme for solving the technical problems is as follows: the system for recovering the desulfurizer in the gas after the desulfurization of the catalytic cracking regenerated waste gas comprises a desulfurization tower, a condensation heat exchanger, a mechanical separation purifier, a heating heat exchanger and a filter, wherein a gas outlet of the desulfurization tower is communicated with a gas inlet of the mechanical separation purifier through a first pipeline, and the condensation heat exchanger is arranged in the first pipeline; the heating heat exchanger is arranged in an exhaust pipeline of the mechanical separation purifier; and the condensing heat exchanger and the mechanical separation purifier are respectively communicated with the filter through a second pipeline.
The invention has the beneficial effects that: by arranging the condensing heat exchanger, the invention can effectively reduce the dew point of the gas at the outlet of the desulfurizing tower, reduce the water vapor content in the gas at the outlet and the concentration of the carried desulfurizing agent and catalyst particles, recover most of the desulfurizing agent, reduce the emission loss of the desulfurizing agent, reduce the operation cost and reduce the environmental pollution; through setting up heating heat exchanger, can prevent that the exhaust gas from getting into the temperature and still can condense out the liquid drop at once less than gas temperature environment, avoid forming the white fog.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the condensing heat exchanger is a plate heat exchanger or a fin type heat exchanger or a tube type heat exchanger.
Furthermore, the material of the condensing heat exchanger is austenitic stainless steel or duplex stainless steel or molybdenum-containing high-silicon iron or Hastelloy or titanium alloy or titanium.
Furthermore, the windward side of the condensation heat exchanger is embedded or covered with an enamel piece or a ceramic piece.
The beneficial effect of adopting the further scheme is that: because the windward side of the front end of the condensing heat exchanger is contacted with the gas, because the condensed water is less, a water film is not formed yet, the erosion effect of catalyst particles in the gas on the surface of equipment is obvious, and the abrasion and the corrosion can be effectively reduced by embedding or covering an enamel piece or a ceramic piece on the windward side of the air inlet of the condensing heat exchanger.
Furthermore, the mechanical separation purifier is a sieve plate or a grid plate or a louver baffle.
The beneficial effect of adopting the further scheme is that: the sieve plate, the grid plate or the baffle plate are adopted, liquid and fixed particles carried in gas impact on a wire mesh, the grid plate or the baffle plate of the sieve plate, and after the liquid and the fixed particles are gathered into large particles or liquid drops, the large particles or the liquid drops flow and are collected in a container below the large particles or the liquid drops, and then the large particles or the liquid drops can be periodically discharged.
Furthermore, the material of mechanical separation clarifier is enamel or ceramic material.
The beneficial effect of adopting the further scheme is that: the mechanical separation purifier made of enamel or ceramic materials can effectively avoid erosion and abrasion of catalyst particles carried in gas to the mechanical separation purifier.
A method for recovering desulfurizer in gas after catalytic cracking regeneration waste gas desulfurization by adopting the recovery system comprises the following steps:
s1, after the catalytic cracking regeneration waste gas enters the desulfurizing tower for desulfurization treatment, the generated desulfurization gas is discharged into the condensing heat exchanger;
s2, cooling the desulfurization gas in the condensation heat exchanger, and condensing to separate out a mixed liquid A containing water and a desulfurizer to obtain a cooled gas;
s3, discharging the temperature-reduced gas into the mechanical separation purifier, and separating a mixed liquid B in the temperature-reduced gas to obtain purified gas;
s4, discharging slurry obtained by mixing the mixed solution A and the mixed solution B into the filter, filtering to remove solid particles in the slurry, returning filtrate containing the desulfurizer to the desulfurizing tower, mixing the filtrate with a newly added desulfurizer, and recycling the mixture;
and S5, discharging the purified gas into the heating heat exchanger, heating and raising the temperature, and then discharging.
The invention has the beneficial effects that: the method for recovering the desulfurizer can cool the gas discharged from the desulfurizing tower, and the saturated vapor pressure of the cooled gas is reduced, so that on one hand, the saturated vapor is condensed, and the dew point of the gas is reduced; on the other hand, the condensed water forms a water film to adsorb desulfurizer and catalyst particles in the adhesion gas, and the useful desulfurizer can be recovered; the slurry is filtered by a filter to remove solid particles in the slurry, and the filtrate containing the desulfurizer is returned to the desulfurizing tower to be mixed with the newly added desulfurizer for reuse, so that the consumption of the desulfurizer can be effectively reduced, and the problem of environmental pollution caused by the emission of the desulfurizer is reduced.
Further, the temperature of the desulfurized gas is reduced by at least 3 ℃ after the desulfurized gas is cooled.
Further, the temperature of the purified gas is increased by at least 5 ℃ after being heated and increased.
Drawings
FIG. 1 is a schematic process flow diagram of the recovery system of the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. a desulfurizing tower; 11. a first pipeline; 2. a condensing heat exchanger; 3. a mechanical separation purifier; 31. an exhaust line; 4. heating a heat exchanger; 5. a filter; 51. a second pipeline.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, the system for recovering a desulfurizing agent from a gas after catalytic cracking regeneration waste gas desulfurization comprises a desulfurizing tower 1, a condensing heat exchanger 2, a mechanical separation purifier 3, a heating heat exchanger 4 and a filter 5, wherein a gas outlet of the desulfurizing tower 1 is communicated with a gas inlet of the mechanical separation purifier 3 through a first pipeline 11, and the condensing heat exchanger 2 is installed in the first pipeline 11; the heating heat exchanger 4 is arranged in an exhaust pipeline 31 of the mechanical separation purifier 3; the condensing heat exchanger 2 and the mechanical separation purifier 3 are respectively communicated with the filter 5 through a second pipeline 51.
The condensing heat exchanger 2 is a plate heat exchanger or a fin type heat exchanger or a shell and tube heat exchanger.
The material of the condensing heat exchanger 2 is austenitic stainless steel or duplex stainless steel or molybdenum-containing high-silicon iron or Hastelloy or titanium alloy or titanium.
The material of the mechanical separation purifier 3 is enamel or ceramic. The mechanical separation purifier made of enamel or ceramic materials can effectively avoid erosion and abrasion of catalyst particles carried in gas to the mechanical separation purifier.
The windward side of the condensation heat exchanger 2 is embedded or covered with an enamel sheet or a ceramic sheet, namely, the windward side of the air inlet of the condensation heat exchanger is provided with a layer of ceramic or enamel structure. For example, the enamel plates or ceramic plates are arranged into a complete structure and can be directly sleeved on the windward side of the condensation heat exchanger. Because the windward side of the front end of the condensing heat exchanger is contacted with the gas, because the condensed water is less, a water film is not formed yet, the erosion effect of catalyst particles in the gas on the surface of equipment is obvious, and the abrasion and the corrosion can be effectively reduced by embedding or covering an enamel piece or a ceramic piece on the windward side of the air inlet of the condensing heat exchanger.
The mechanical separation purifier 3 is a sieve plate, a grid plate or a louver baffle. The sieve plate, the grid plate or the baffle plate are adopted, liquid and fixed particles carried in gas impact on a wire mesh, the grid plate or the baffle plate of the sieve plate, and after the liquid and the fixed particles are gathered into large particles or liquid drops, the large particles or the liquid drops flow and are collected in a container below the large particles or the liquid drops, and then the large particles or the liquid drops can be periodically discharged.
The invention discloses a method for recovering a desulfurizer in gas after catalytic cracking regeneration waste gas desulfurization by adopting the recovery system, which comprises the following steps:
s1, after the catalytic cracking regeneration waste gas enters the desulfurizing tower for desulfurization treatment, the generated desulfurization gas is discharged into the condensing heat exchanger;
s2, cooling the desulfurization gas in the condensation heat exchanger, and condensing to separate out a mixed liquid A containing water and a desulfurizer to obtain a cooled gas; the temperature for cooling is 3-40 ℃;
s3, discharging the temperature-reduced gas into the mechanical separation purifier, and separating a mixed liquid B in the temperature-reduced gas to obtain purified gas;
s4, discharging slurry obtained by mixing the mixed solution A and the mixed solution B into the filter, filtering to remove solid particles in the slurry, returning filtrate containing the desulfurizer to the desulfurizing tower, mixing the filtrate with a newly added desulfurizer, and recycling the mixture;
s5, discharging the purified gas into the heating heat exchanger, heating and discharging after temperature rise; the temperature for heating is 5-50 ℃.
Because the catalytic cracking process is an important oil refining process, the catalytic cracking catalyst needs to be regenerated frequently, the regenerated waste gas contains carbon dioxide, sulfur dioxide, nitrogen oxide and catalyst particles, the waste gas can be discharged after denitration, desulfurization and purification processes, and the desulfurization adopts an alkali liquor neutralization process; the regenerated waste gas suitable for catalytic cracking is desulfurized by calcium hydroxide (calcium method), sodium hydroxide or sodium carbonate (sodium-alkali method) and ammonia water (ammonia method). The desulfurizing tower is generally a spray tower, the desulfurizing agent is sprayed from the top of the tower and then contacts with gas in a countercurrent manner, sulfur dioxide and the desulfurizing agent are subjected to neutralization reaction to generate sulfite, and the gas is discharged from the top after absorption treatment. The gas flow of large amount will carry alkali liquor, saturated vapor and residual catalyst particles, although treated by demister on the top of the desulfurizing tower, because the gas amount is large and the gas contains saturated vapor, the gas carries and discharges large amount of water and desulfurizing agent. When the desulfurizer adopts sodium hydroxide, unreacted desulfurizer can be recycled, and chlorine ions are accumulated due to the fact that the sodium hydroxide contains a small amount of chlorine ions, so that droplets containing the chlorine ions are carried in the exhaust gas at the top of the desulfurizing tower. When sodium hydroxide is used as a vulcanizing agent, a part of the condensing heat exchanger, which is in contact with gas, needs to be made of a material resistant to chloride ion corrosion, such as molybdenum-containing high silicon iron, duplex stainless steel, Hastelloy, titanium alloy, titanium and the like. Because the gas discharged after the catalytic cracking regeneration tail gas is desulfurized in the desulfurizing tower carries a large amount of water vapor and a desulfurizing agent, the desulfurizing agent loss and the environmental pollution are caused.
The gas discharged from the desulfurizing tower is firstly cooled by a condensing heat exchanger arranged in a pipeline, and the condensing heat exchanger is a plate heat exchanger or a plate-fin heat exchanger or a tubular heat exchanger. The cooling medium is cooling water. The temperature of the desulphurised gas exiting the desulphurisation column is typically 50-80 ℃ and after cooling by the condensing heat exchanger, the temperature of the desulphurised gas is reduced by at least 3 ℃, preferably by more than 5 ℃. Because the desulfurization gas discharged from the desulfurization tower contains saturated vapor, the vapor is condensed after being cooled, and entrained desulfurizing agents such as sodium hydroxide and the like are settled and dissolved in the condensate. The droplets produced by condensation are small in size and, if not treated, are easily entrained by the gas and vented to the atmosphere. Therefore, after the condensation heat exchanger cools the gas, the gas needs to be treated by a mechanical separation purifier. The mechanical separation purifier is a gas-solid separator or a gas-liquid separator and is used for separating liquid and solid components in gas. The mechanical separation purifier is in the form of a sieve plate, a grid plate or a baffle plate. The liquid and solid particles impact on the wire mesh of the sieve plate, or the grid of the grid plate, or the baffle plate, are gathered into large particles or liquid drops, flow due to the liquid drops, are collected into a container below, and are periodically discharged. Because catalyst particles are carried in the gas, the hardness is high, and the abrasion is fast. The mechanical separation purifier is made of enamel or ceramic materials, and can reduce erosion and abrasion of catalyst particles.
Wherein, the arrangement of sieve, grid tray and louver baffle is respectively: the sieve plate is a porous plate, and the shape of the holes can be set to any shape according to requirements, such as long round holes, triangular holes, round holes, square holes and the like; the grid plate is a net structure formed by interweaving and fixedly connecting a plurality of grid plate strips; the louver type baffle comprises a fixing rod and a plurality of louvers which are arranged in parallel, the louvers are all vertically fixed on the fixing rod, the louvers are all obliquely arranged and are all parallel to each other, and when gas containing liquid drops and fixed particles impacts the louvers, the fixed particles and the liquid drops are intercepted by the louvers and converge into a filter along the louvers to be filtered.
Because the windward side of the front end of the condensing heat exchanger is contacted with the gas, because the condensed water is less, a water film is not formed yet, the erosion effect of catalyst particles in the gas on the surface of equipment is obvious, and the abrasion and the corrosion can be effectively reduced by embedding or covering an enamel piece or a ceramic piece on the windward side of the air inlet of the condensing heat exchanger. The catalytic cracking catalyst has very fine particles, the particle size is generally between 40 and 80 mu m, and the catalyst is very easy to be entrained by gas. The main components of the catalyst are alumina and silicate, the hardness is high, the abrasion and corrosion to equipment are large, the impact on the windward side of a heat exchange plate of the heat exchanger opposite to airflow is large, and the abrasion is maximum. Therefore, the ceramic or enamel shielding plate is embedded or covered on the windward side of the heat exchange plate, so that the abrasion of the part can be reduced, and the service life of the equipment is prolonged.
The purified gas is obtained after cooling by a condensing heat exchanger and purifying treatment by a mechanical separation purifier, the purified gas has reduced temperature and removed solid particles, but still contains saturated water vapor, and liquid drops can be immediately condensed out when entering an environment with the temperature lower than the gas temperature to form white mist. Therefore, the purified gas needs to be heated to become unsaturated water vapor-containing gas, the gas is contacted with a low-temperature environment, liquid drops are not condensed immediately, the gas is cooled to the dew point temperature after a period of temperature reduction, the dew point is reduced due to the diffusion effect after the water vapor content in the gas is reduced, the probability of forming white mist is greatly reduced, and the formed white mist is less. The more the temperature of the gas rises, the less the probability of white mist generation. However, the temperature rise consumes heat energy, and the operation cost is increased, so the temperature rise range is not suitable to be too large. The temperature rise is not less than 3 deg.C, preferably not less than 5 deg.C.
The gas after temperature reduction, separation and purification and temperature rise treatment can be discharged. The liquid condensed by the condensing purifier is filtered, the liquid contains soluble desulfurizer, and can be returned to the desulfurizing tower to be mixed with fresh desulfurizer for reuse, and the filter cake mainly contains water-insoluble catalyst particles and a small amount of crystallized desulfurizer, and can be returned to other processes for recovery treatment or used as solid waste treatment.
In a common flow of boiler treatment of catalytic cracking regeneration waste gas, the waste gas is cooled by a flue gas heat exchanger (GGH) before entering a desulfurizing tower, is dewatered by a demister after being desulfurized, is heated to 70-80 ℃ by the flue gas heat exchanger (GGH), and is discharged. Before discharging, because the temperature is not reduced, the actual water vapor content is not changed, the demister can only remove liquid droplets, namely liquid droplets carried by gas, saturated water vapor cannot be removed, and only a small amount of carried desulfurizing agent and catalyst particles in the form of tiny particles can be removed. The GGH technology adopted by the existing boiler waste gas desulfurization tower gas treatment has high operation cost and is easy to block, discharged gas still generates liquid drop condensation and white fog generated by a desulfurizer, and the discharged gas is easy to condense into liquid at a chimney and the like to cause equipment material corrosion. The process can only eliminate 'white fog' in the exhaust gas, but cannot recover the desulfurizer in the exhaust gas, and is easy to block and corrode. The technology adopted by the invention can recover the desulfurizer, reduce the emission pollution and reduce the operation cost; the recovered desulfurizer can be returned to the desulfurizing tower to be mixed with fresh desulfurizer for reuse, and the filter cake is mainly water-insoluble catalyst particles and a small amount of desulfurizer separated out by crystallization, and can be returned to other processes for recovery treatment or used as solid waste treatment.
The invention adopts the condensing heat exchanger to carry out cooling treatment on the desulfurization gas discharged from the desulfurization tower to obtain the cooling gas, the saturated vapor pressure of the cooling gas is reduced, on one hand, the saturated vapor is condensed to reduce the dew point of the gas, on the other hand, the condensed water forms a water film which can adsorb and absorb the desulfurizer and catalyst particles in the gas, and useful desulfurizer is recovered. Because the desulfurizing agent is a water-soluble alkaline substance, the catalyst particles are water-insoluble alumina, silicate and the like, the condensate mixed with the desulfurizing agent and the catalyst particles can remove the catalyst particles in the condensate by a filtering mode and the like, and the obtained filtrate is an aqueous solution containing the desulfurizing agent. The water solution can be returned to the desulfurizing tower for reuse, thereby reducing the consumption of the desulfurizing agent and also reducing the problem of environmental pollution caused by the discharge of the desulfurizing agent.
In addition, the desulfurization exhaust gas of the regeneration waste gas due to catalytic cracking is different from the exhaust gas generated by desulfurization of boiler flue gas. The desulfurization exhaust gas of the catalytic cracking regeneration exhaust gas contains catalyst particles, the main components of the catalyst particles are alumina and silicate, the hardness is high, and the effect of the catalyst particles on pipeline erosion is obvious. And the boiler flue gas contains fewer inorganic matter components with high hardness and has larger particles which are easy to remove in a wet desulphurization process, so that compared with other gas treatment processes after desulphurization, the gas after catalytic cracking regeneration tail gas desulphurization needs to adopt a technology for reducing or eliminating the erosion effect of the particles aiming at the catalyst particles. When the sodium-alkali method is adopted for desulfurization, the desulfurizer contains chlorine, the condensate contains chloride ions, the corrosivity is strong, and the requirement on the material of separation and purification equipment is high.
The heating heat exchanger has less corrosion due to no condensate, has relatively low requirement on the corrosion resistance of materials, and can adopt austenitic stainless steel or duplex stainless steel, or molybdenum-containing high-silicon iron, or hastelloy, or titanium alloy, or titanium. Because the latter two materials are high in price, the two materials are preferably not adopted, so that the investment is saved and the equipment cost is reduced. The heating heat exchanger can also be made of enamel. The heating heat exchanger can adopt steam and heat conduction oil as heating media, and can also be combined with a cooling heat exchanger at the inlet of the desulfurizing tower, the heating heat exchanger can be used for heating the heating heat exchanger by taking heat from the cooling heat exchanger, and water or other heat transfer media such as heat conduction oil, glycol and the like are used.
The cooling medium of the condensing heat exchanger can be circulating cooling water, chilled water or cold brine. The temperature of the cooling medium is preferably not higher than 40 deg.C, more preferably not higher than 30 deg.C.
By arranging the condensing heat exchanger, the invention can effectively reduce the dew point of the gas at the outlet of the desulfurizing tower, reduce the water vapor content in the gas at the outlet and the concentration of the carried desulfurizing agent and catalyst particles, recover most of the desulfurizing agent, reduce the emission loss of the desulfurizing agent, reduce the operation cost and reduce the environmental pollution; through setting up heating heat exchanger, can prevent that the exhaust gas from getting into the temperature and still can condense out the liquid drop at once less than gas temperature environment, avoid forming the white fog.
Example 1
30000m3And (2) carrying out treatment and desulfurization on the regenerated waste gas subjected to catalytic cracking in a desulfurizing tower by a sodium-alkali method to obtain a desulfurized gas with the temperature of 50-55 ℃, and cooling the desulfurized gas by a condensing heat exchanger for 3 ℃ to obtain a cooled gas with the temperature of 47-52 ℃. Enabling the cooling gas to pass through a screen type mechanical separation purifier, and separating liquid drops and solid particles in the cooling gas to obtain purified gas; the slurry separated from the temperature-reducing gas and the condensed water produced by the condensing heat exchanger form slurry together,and returning the filtered filtrate containing the desulfurizer to the desulfurizing tower for continuous use. And finally, the purified gas enters a heating heat exchanger for heating, and is discharged after the temperature is raised by 5 ℃. The condensing heat exchanger is a plate-fin heat exchanger made of titanium alloy materials, and the windward side of the plate-fin heat exchanger is provided with enamel plates. The screen type separator is made of enamel. The heating heat exchanger is made of austenitic stainless steel.
Example 2
50000m3And h, carrying out treatment and desulfurization on the regenerated waste gas through a desulfurization tower by adopting a calcium method to obtain a desulfurized gas with the temperature of 50-55 ℃, and cooling the desulfurized gas by a condensing heat exchanger for 20 ℃ to obtain a cooled gas with the temperature of 30-35 ℃. Enabling the cooling gas to pass through a screen type mechanical separation purifier, and separating liquid drops and solid particles in the cooling gas to obtain purified gas; and the slurry separated from the cooling gas and the condensed water generated by the condensing heat exchanger form slurry together, and the filtered filtrate containing the desulfurizer returns to the desulfurizing tower for continuous use. And finally, the purified gas enters a heating heat exchanger for heating, and is discharged after the temperature is raised to 40 ℃. The condensing heat exchanger is a plate-fin heat exchanger made of a duplex stainless steel material, and a ceramic plate is arranged on the windward side of the plate-fin heat exchanger. The screen type separator is made of enamel. The heating heat exchanger is made of austenitic stainless steel.
Example 3
50000m3And h, carrying out desulfurization treatment on the regenerated waste gas subjected to catalytic cracking by an ammonia method through a desulfurization tower to obtain a desulfurized gas with the temperature of 70-80 ℃, and cooling the desulfurized gas by a condensing heat exchanger to 40 ℃ to obtain a cooled gas with the temperature of 30-40 ℃. Separating liquid drops and solid particles in the cooling gas by passing the cooling gas through a grid type mechanical separation purifier to obtain purified gas; and the slurry separated from the cooling gas and the condensed water generated by the condensing heat exchanger form slurry together, and the filtered filtrate containing the desulfurizer returns to the desulfurizing tower for continuous use. And finally, the purified gas enters a heating heat exchanger for heating, and is discharged after the temperature is raised to 45 ℃. The condensing heat exchanger is a plate heat exchanger made of austenitic stainless steel, and the windward side of the plate heat exchanger is provided with a ceramic lining. The grid type separator is made of enamel. The heating heat exchanger is made of austenitic stainless steel.
Example 4
100000m3And (2) carrying out treatment and desulfurization on the regenerated waste gas subjected to catalytic cracking in a desulfurizing tower by a sodium-alkali method to obtain a cooling gas at the temperature of 55-65 ℃, and cooling the cooling gas by a condensing heat exchanger for 15 ℃ to obtain the cooling gas at the temperature of 40-50 ℃. Separating liquid drops and solid particles in the cooling gas by passing the cooling gas through a baffle type mechanical separation purifier to obtain purified gas; and the slurry separated from the cooling gas and the condensed water generated by the condensing heat exchanger form slurry together, and the filtered filtrate containing the desulfurizer returns to the desulfurizing tower for continuous use. And finally, the purified gas enters a heating heat exchanger for heating, and is discharged after the temperature is raised by 20 ℃. The condensing heat exchanger is a tubular heat exchanger made of Hastelloy materials, and a ceramic plate is arranged on the windward side of the tubular heat exchanger. The baffle type separator is made of ceramic. The heating heat exchanger is made of duplex stainless steel.
Example 5
100000m3And (2) carrying out desulfurization treatment on the regenerated catalytic cracking waste gas by a desulfurizing tower by a sodium-alkali method to obtain a desulfurized gas with the temperature of 50-55 ℃, and cooling the desulfurized gas by a condensing heat exchanger for 4 ℃ to obtain a cooled gas with the temperature of 46-51 ℃. Separating liquid drops and solid particles in the cooling gas by passing the cooling gas through a baffle type mechanical separation purifier to obtain purified gas; and the slurry separated from the cooling gas and the condensed water generated by the condensing heat exchanger form slurry together, and the filtered filtrate containing the desulfurizer returns to the desulfurizing tower for continuous use. And finally, feeding the purified gas into a heating heat exchanger for heating, and discharging after the temperature is raised to 50 ℃. The condensing heat exchanger is a tubular heat exchanger made of a molybdenum-containing high-silicon iron material, and the windward side of the tubular heat exchanger is provided with a porcelain lining sheet. The baffle type separator is made of ceramic. The heating heat exchanger is made of duplex stainless steel.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (2)
1. The system for recovering the desulfurizer in the gas after the desulfurization of the catalytic cracking regenerated waste gas is characterized by comprising a desulfurization tower, a condensation heat exchanger, a mechanical separation purifier, a heating heat exchanger and a filter, wherein a gas outlet of the desulfurization tower is communicated with a gas inlet of the mechanical separation purifier through a first pipeline, and the condensation heat exchanger is arranged in the first pipeline; the heating heat exchanger is arranged in an exhaust pipeline of the mechanical separation purifier; the condensing heat exchanger and the mechanical separation purifier are respectively communicated with the filter through a second pipeline; the windward side of the condensation heat exchanger is embedded or covered with an enamel piece or a ceramic piece; the mechanical separation purifier is made of enamel or ceramic; the condensing heat exchanger is a plate heat exchanger or a fin type heat exchanger or a shell and tube heat exchanger; the material of the condensing heat exchanger is austenitic stainless steel or duplex stainless steel or molybdenum-containing high-silicon iron or Hash type alloy or titanium; the mechanical separation purifier is a sieve plate or a grid plate or a shutter baffle.
2. A method for recovering a desulfurizing agent from a gas after catalytic cracking regeneration of flue gas desulfurization by using the recovery system of claim 1, characterized by comprising the steps of:
s1, after the catalytic cracking regeneration waste gas enters the desulfurizing tower for desulfurization treatment, the generated desulfurization gas is discharged into the condensing heat exchanger;
s2, cooling the desulfurization gas in the condensation heat exchanger, and condensing to separate out a mixed liquid A containing water and a desulfurizer to obtain a cooled gas;
s3, discharging the temperature-reduced gas into the mechanical separation purifier, and separating a mixed liquid B in the temperature-reduced gas to obtain purified gas;
s4, discharging slurry obtained by mixing the mixed solution A and the mixed solution B into the filter, filtering to remove solid particles in the slurry, returning filtrate containing the desulfurizer to the desulfurizing tower, mixing the filtrate with a newly added desulfurizer, and recycling the mixture;
s5, discharging the purified gas into the heating heat exchanger, heating and discharging after temperature rise;
in the step S2, after the temperature of the desulfurization gas is reduced, the temperature of the desulfurization gas is reduced by at least 3 ℃;
the temperature of the purified gas is increased by at least 5 ℃ after being heated and increased.
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| JPH10273681A (en) * | 1997-03-31 | 1998-10-13 | Toshiba Corp | Dry desulfurization system |
| FR2941630B1 (en) * | 2009-02-02 | 2012-06-01 | Inst Francais Du Petrole | METHOD AND DEVICE FOR DEULFURIZING GAS, COMPRISING A SULFUR REMOVAL STEP BY COOLING A GAS FLOW |
| CN101829494B (en) * | 2009-03-11 | 2012-10-31 | 上海立谊环保工程技术有限公司 | Dry ash wetting and recycling technology for desulfurizing sintered fume by rotary spraying and drying method |
| CN102151470B (en) * | 2011-01-28 | 2013-11-06 | 山东华鲁恒升集团德化设计研究有限公司 | Flue gas desulfurization method and device |
| CN102327726B (en) * | 2011-07-15 | 2013-06-12 | 攀钢集团有限公司 | Method for dewatering desorption gas for flue gas desulfurization and recycling condensate |
| KR101394113B1 (en) * | 2012-03-21 | 2014-05-15 | 한국전력공사 | Operation Apparatus and Method for Oxy-PC Combustion System |
| JP2014058426A (en) * | 2012-09-19 | 2014-04-03 | Panasonic Corp | Hydrogen generator and fuel cell system |
| CN203043815U (en) * | 2013-01-08 | 2013-07-10 | 洛阳瑞昌石油化工设备有限公司 | Device for condensing and desulfurizing smoke gas regenerated by catalytic cracking |
| CN104857820A (en) * | 2015-05-14 | 2015-08-26 | 广东华信达节能环保有限公司 | Method for eliminating white smoke of condensed flue gas and condenser for same |
| CN105056718B (en) * | 2015-07-27 | 2017-08-18 | 航天环境工程有限公司 | A kind of high-efficiency water-saving wet desulphurization absorption tower and application |
| CN106474860A (en) * | 2015-08-25 | 2017-03-08 | 贺方昀 | Wet desulfurization flue gas processing system and processing method |
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| CN205965468U (en) * | 2016-08-29 | 2017-02-22 | 西安热工研究院有限公司 | System for phase transition of wet flue gas desulfurization device is reunited in coordination with desorption fine particles |
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Effective date of registration: 20231013 Address after: Building 6, No. 64 and Bianmen, Chaoshou Hutong, Xicheng District, Beijing, 100032 Patentee after: Beijing Zhengxin Xingye Energy Technology Co.,Ltd. Address before: 100031 bungalow, building 27, 64 chaoshou Hutong, Xicheng District, Beijing Patentee before: BEIJING CREDITCONGRUITY ENERGY TECHNOLOGY CO.,LTD. |