CN110624399A - Catalytic membrane contactor and gas desulfurization and denitrification method - Google Patents
Catalytic membrane contactor and gas desulfurization and denitrification method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 108
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 18
- 230000023556 desulfurization Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 41
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 124
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 13
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
-
- 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
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen 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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
-
- 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
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
Abstract
The invention relates to a catalytic membrane contactor for desulfurization and denitrification of ship tail gas, and a process for simultaneously desulfurizing and denitrifying sulfur-containing and nitrate-containing tail gas by using the membrane contactor. The membrane contactor comprises a cylinder, a ceramic membrane tube and a catalyst plate. The upper end and the lower end of the cylinder body are respectively provided with a gas feed port and a gas discharge port, and a denitration catalyst is loaded on the catalyst plate. The desulfurization and denitrification coupling process adopts the membrane contactor, the absorbent is injected from the liquid inlet end socket, flows out from the liquid outlet end socket through the ceramic membrane pipe, then enters the absorbent cooler and circularly enters the catalytic membrane contactor. The tail gas enters the catalytic membrane contactor through the gas inlet, and is discharged from the gas outlet after reacting in the contactor. The absorbent is mainly used for desulfurization and solving the problem of ammonia escape in the process, and the supported catalyst is mainly used for catalytic denitration. The method couples the SCR technology with the membrane absorption technology, and has the advantages of high integration, strong controllability, high removal efficiency, compact structure, easy amplification and improvement of desulfurization and denitrification efficiency.
Description
Technical Field
The invention relates to a catalytic membrane contactor for desulfurization and denitrification of ship tail gas, in particular to a process for simultaneously desulfurizing and denitrifying sulfur-containing and nitrate-containing tail gas by using the catalytic membrane contactor.
Background
Nitrogen oxides (NO, NO)2、N2O, etc., abbreviated as NOx) Is one of the main atmospheric pollutants, and in recent years, the national issue of environmental pollution is more and more important, such as NO of a moving source such as a shipxEmission standards are also becoming more stringent. During operation of the diesel engine, NOxThe main reason for the generation is that nitrogen reacts with oxygen in the air at high temperature and high pressure to generate, so NO can not be eliminated from the sourcexAnd (4) generating. The tail gas must be denitrated, and the Selective Catalytic Reduction (SCR) is used for treating NOxAn effective method of (1).
According to the statistical data of the International Maritime Organization (IMO) in 2014, the annual SO emission of the ship tail gas is shownxAccounting for 13% of the total global emissions and 5% -10% of the total atmospheric pollution, even up to 30% -40% in some port cities with developed shipping industry. The atmospheric pollution of the ship reaches the stage which cannot be ignored, and the tail gas emission of the ship is controlled to be slow.
The treatment of ship tail gas by tail gas washing technology is an important means for controlling the SOx emission of ships. The amendment of MARPOL attached rule VI passed by IMO is as follows: since 2015, the SOx emission standard upper limit for Emission Control Area (ECA) vessels was reduced to 0.1%; in all European sea areas except ECA, the upper limit of the emission standard is reduced to 0.5 percent, and the emission standard is further reduced to 0.1 percent in 2020; by 2020 or 2025, 0.5% SOxThe new rule of the upper limit of the discharge willEffective on a global scale. The additional installation of the tail gas washing device has the characteristics of high feasibility, low cost, wide practicability and the like, and becomes the first choice for controlling the emission of oxysulfide.
The membrane contactor serving as novel gas-liquid absorption equipment has the advantages of large gas-liquid contact area, compact equipment, flexibility in operation, easiness in control and the like, and is suitable for treating ship tail gas. The traditional absorption method needs larger equipment volume, the direct contact of high-temperature tail gas and absorption liquid easily causes the gasification of the absorption liquid, and the uneven flow of the tail gas can cause the problems of flooding and the like. The membrane contactor avoids direct contact of gas and liquid, gas and liquid phases can be independently controlled, and waste heat can be recovered in the absorption process.
Absorbing SO with alkaline absorption liquidxIs a common tail gas desulfurization method, and NO is absorbed by an absorption methodxThe efficiency of (2) is low, and the gas-phase oxidation-reduction reaction is needed, so that secondary pollution is easily caused.
A system for scrubbing marine engine exhaust gas using membrane technology has been proposed in chinese patent CN 101104130A. The technology in the patent is used for removing oxysulfide and particulate matters in ship exhaust gas, and carrying out real-time monitoring, acquisition and storage on the ship exhaust gas treatment effect, but the method cannot simultaneously and effectively remove nitric oxide in the exhaust gas.
China patent CN 106076072A has proposed a ceramic membrane gas purification device for ships and application thereof. The method of the patent mainly uses a sodium hydroxide solution as an absorbent to absorb the tail gas, but the method has the problems that the nitrogen oxides and the sulfur oxides need to be removed by a membrane absorption method at the same time, so that the absorption efficiency is low and the removal rate is not good.
Disclosure of Invention
The purpose of the invention is: the SCR technology is coupled to the membrane absorption process using a catalytic membrane contactor.
In a first aspect of the present invention, there is provided:
a catalytic membrane contactor, comprising:
the membrane contactor is internally provided with a tubular ceramic membrane;
and a catalyst plate is arranged outside the tubular ceramic membrane, and an SCR denitration catalyst layer is arranged on the catalyst plate.
In one embodiment, an ammonia-containing species addition component is further included for adding the ammonia-containing species to the gas fed to the membrane contactor.
In one embodiment, the ammonia-containing species is selected from ammonia or urea.
In one embodiment, a protective layer is further disposed outside the SCR denitration catalyst layer.
In one embodiment, the protective layer is a porous material.
In one embodiment, the protective layer is formed by laminating an outer quartz cotton layer and an inner quartz sand layer.
In one embodiment, the catalyst plates are provided with openings and the tubular ceramic membranes are sleeved in the openings.
In one embodiment, the exterior of the membrane contactor is a cylinder.
In one embodiment, an upper end enclosure and a lower end enclosure are respectively arranged at two ends of the cylinder body, and the internal channel of the tubular ceramic membrane is respectively communicated with the upper end enclosure and the lower end enclosure.
In one embodiment, the cylinder body and the upper end enclosure are fixedly connected through an upper sealing plate, and the cylinder body and the lower end enclosure are fixedly connected through a lower sealing plate; the upper and lower sealing plates separate the tubular ceramic membrane into a tube side and a shell side.
In one embodiment, a liquid inlet and a liquid outlet are provided on the upper head and the lower head, respectively.
In one embodiment, a gas inlet and a gas outlet are provided on the cylinder, respectively.
In one embodiment, the material of the SCR denitration catalyst layer is selected from one or a mixture of more of a molecular sieve type SCR catalyst, a manganese-based SCR catalyst, a copper-based SCR catalyst, and a vanadium tungsten titanium type catalyst.
In one embodiment, the tubular ceramic membrane is an asymmetric porous ceramic microfiltration membrane.
In one embodiment, the pore diameter of the tubular ceramic membrane is 0.05-3 μm.
In a second aspect of the present invention, there is provided:
a method for desulfurizing and denitrating gas containing sulfur oxide and nitrogen oxide comprises the following steps:
introducing sulfur oxide absorption liquid into a channel of a tubular ceramic membrane in the catalytic membrane contactor;
adding ammonia gas into the gas, and then sending the gas into a gas inlet of a catalytic membrane contactor to enable nitrogen oxides in the gas to react with the ammonia gas on an SCR denitration catalyst, and absorbing sulfur oxides in the gas by an absorption liquid;
the gas is discharged from the gas outlet.
In one embodiment, the temperature of the gas at the gas inlet is higher than the temperature at the gas outlet.
In one embodiment, the gas and the absorption liquid flow in a counter-current direction.
In one embodiment, the gas comprises a composition consisting essentially of: SO (SO)xTotal content of 100-2000 ppm, NOxThe total content is 100-1000 ppm.
In one embodiment, the absorption liquid can be a sodium hydroxide solution or a calcium hydroxide solution, and the concentration is 0.1-5 mol/L.
In one embodiment, the gas is subjected to a pre-dedusting treatment prior to entering the catalytic membrane contactor.
In a third aspect of the present invention, there is provided:
the catalytic membrane contactor is used for gas desulfurization and denitrification.
Advantageous effects
Compared with the prior art, the project has the following advantages: the SCR process is coupled with the membrane absorption process, so that the integration degree is high; the ship tail gas purification degree is high, and 99.9 percent of SO can be removedxAnd 98% NOxAnd no secondary pollution is generated; the device is modularized and can be matched with various ship exhaust emission systems; easy conditions, catalytic conditions and absorption conditions can be controlled independentlyThe application range is wider; the turbulence degree of the gas in the membrane contactor is increased by adding the catalyst and the fixed plate, the mass transfer efficiency and SO are improved2The removal rate of (2); the method of membrane absorption can absorb the redundant heat in the waste gas, thus achieving the purpose of recovering the waste heat; the method of catalytic absorption coupling can solve the common ammonia slip problem in the SCR process.
Drawings
FIG. 1 shows a schematic diagram of a catalytic membrane contactor device.
Fig. 2 shows a sectional structure view of the catalyst plate.
Fig. 3 shows a plan view of the catalyst plate.
Figure 4 shows a process flow diagram for a catalytic membrane contactor unit.
Wherein, 1, an upper end enclosure; 2. an upper sealing plate; 3. a tubular ceramic membrane; 4. a catalyst plate; 5. a barrel; 6. a lower sealing plate; 7. a lower end enclosure; 8. a gas inlet; 9. a gas outlet; 10. an SCR denitration catalyst layer; 11. a porous protective layer; 111. a quartz cotton layer 112 and a quartz sand layer; 12. and (6) opening holes.
Detailed Description
As shown in fig. 1 to 3, the catalytic membrane contactor provided by the present invention has the following structure:
an upper end enclosure 1 and a lower end enclosure 7 are respectively arranged at two ends of a cylinder body 5, a tubular ceramic membrane 3 is arranged inside the cylinder body 5, an internal channel of the tubular ceramic membrane 3 is respectively communicated with the upper end enclosure 1 and the lower end enclosure 7, the cylinder body 5 and the upper end enclosure 1 are fixedly connected through an upper sealing plate 2, and the cylinder body 5 and the lower end enclosure 7 are fixedly connected through a lower sealing plate 6; the upper sealing plate 2 and the lower sealing plate 6 divide the tubular ceramic membrane 3 into a tube pass and a shell pass;
the upper seal head 1 and the lower seal head 7 are respectively provided with a liquid inlet and a liquid outlet;
the cylinder body 5 is respectively provided with a gas inlet 8 and a gas outlet 9;
a catalyst plate 4 is also arranged in the cylinder body 5, an opening 12 is arranged on the catalyst plate 4, and the tubular ceramic membrane 3 is sleeved in the opening 12; the catalyst plate 4 is formed by laminating an SCR denitration catalyst layer 10 and porous protection layers 11 on both sides. The porous protective layer 11 serves to prevent the catalyst from being attached by impurities such as dust and to prevent the catalyst from being deactivated.
In one embodiment, the porous protection layer 11 is formed by laminating an outer quartz cotton layer 111 and an inner quartz sand layer 112.
In one embodiment, the material of the SCR denitration catalyst layer 10 is selected from one or a mixture of more of a molecular sieve type SCR catalyst, a manganese-based SCR catalyst, a copper-based SCR catalyst, and a vanadium tungsten titanium type catalyst.
In one embodiment, the tubular ceramic membrane 3 is an asymmetric porous ceramic microfiltration membrane.
In one embodiment, the pore diameter of the tubular ceramic membrane 3 is 0.05 to 3 μm.
The catalytic membrane contactor is mainly applied to gas desulfurization and denitrification, such as ship exhaust.
In one embodiment, the composition of the gas comprises essentially of: SO (SO)xTotal content of 100-2000 ppm, NOxThe total content is 100-1000 ppm. The gas flow is 50-300 m3/h。
When the desulfurization and denitrification operations are carried out, firstly, tail gas is supplied from a gas inlet 8 on a cylinder 5, the tail gas passes through the shell pass of the tubular ceramic membrane 3, absorption liquid is supplied into a tube (tube pass) of the tubular ceramic membrane 3, and sulfur oxides in the tail gas can be subjected to mass transfer and absorption with the absorption liquid at a membrane hole and are absorbed by the absorption liquid through the membrane hole; meanwhile, tail gas is also subjected to SCS denitration reaction in the shell side; after desulfurization and denitrification treatment, the tail gas is discharged from the gas outlet 9 on the cylinder 5. Since the method of the present invention employs a coupled desulfurization and denitrification treatment method, when the gas enters, a reducing substance is added to the gas to perform the SCR reaction (for example, ammonia gas is used, and the amount of the ammonia gas to be fed can be calculated and adjusted according to the amount of the tail gas, the source composition, and the outlet temperature).
In the above device, the desulfurization absorption liquid passes through the tube pass, and the absorption liquid is sent into the channel of the tubular ceramic membrane 3, and sulfur dioxide, sulfur trioxide and the like in the gas can be absorbed in the absorption processEntering the absorption liquid through the reaction and absorption processes with the absorption liquid; the absorption liquid can be sodium hydroxide solution or calcium hydroxide solution, and the concentration is 0.1-5 mol/L. The flow rate of the liquid is 100-300 m3/h。
In the treatment process, the gas temperature at the gas inlet can be 150-; the catalyst plate has the effects of enabling gas to generate turbulence in the flowing process and improving the mass transfer effect on one hand, and on the other hand, the catalyst plate also plays a role of supporting the catalyst so that nitrogen oxides in the gas can react with the SCR catalyst; for the SCR reaction, the raw material ammonia gas added is excessive under normal conditions, so that after the catalytic reaction of nitrogen oxides is completed, the excessive ammonia is generally not removed by a method and still remains in the gas to cause exogenous pollution, but the problem can be better solved by the technology in the invention, because the temperature of the flue gas at the gas inlet is higher (for example, the gas temperature can be 150-; the gas continuously moves forward and exchanges heat with the absorption liquid, when reaching the gas outlet, the temperature is obviously reduced (for example, the gas temperature can be 100-. It can be seen that the technical concept of such a coupled process of the present invention also takes into account the temperature difference between the gas inlet and outlet ends of the membrane absorber; the difference between the reaction speed and the absorption speed caused by the temperature difference is cooperated with the SCR reaction process and the ammonia absorption process, so that the integral denitration process is more in line with the actual requirement.
In addition, for the SCR reaction, the catalyst is easily affected by sulfur to cause catalyst poisoning.
In conclusion, in the technical scheme of the invention, the SCR catalytic reaction denitration and the membrane absorption desulfurization are coupled through the designed catalytic membrane contactor, and the nitrogen oxide is removed in the process of absorbing the sulfur oxide by the hydrophilic membrane, so that the influence of sulfur on the SCR catalyst is reduced; meanwhile, the SCR reaction is carried out by utilizing the characteristics that the temperature of the flue gas inlet is higher and ammonia gas is not easily dissolved in water, and when the reaction is finished and the temperature of the gas is reduced after heat transfer is carried out at the outlet, the gas is more easily dissolved in water at the outlet, so that the problem of ammonia escape is avoided; the technical characteristics form a synergistic relationship with each other.
Example 1
The catalytic membrane contactor is arranged at the tail gas outlet of the ship and behind the particle catcher. The absorbent is injected into the liquid inlet area from the liquid inlet end socket, flows out from the liquid outlet end socket through the ceramic membrane pipe, then enters the absorbent cooler and circularly enters the catalytic membrane contactor. After 500ppm of ammonia gas is added into tail gas, the tail gas enters a gas phase area of a catalytic membrane contactor through a gas inlet (the gas temperature is about 200 ℃ and the liquid temperature is about 95 ℃), and the tail gas is discharged from a gas outlet (the gas temperature is about 120 ℃ and the liquid temperature is about 60 ℃) after reaction through a catalyst. NaOH solution with concentration of 0.1mol/L is used as absorption liquid, and the flow rate is 100m3H is used as the reference value. The flow rate of the tail gas is 50m3H, in which SO2The concentration is 100ppm and the NO concentration is 100 ppm. The volume of the catalytic membrane contactor equipment is 4.5m3The aperture of the membrane tube is 0.1 mu m, the denitration catalyst is vanadium-tungsten-titanium SCR catalyst, the NO removal rate is 100 percent, and SO is removed after the denitration catalyst is treated by a catalytic membrane contactor2The removal rate is 100 percent, and the escape rate of ammonia is 0 percent.
Example 2
The catalytic membrane contactor is arranged at the tail gas outlet of the ship and behind the particle catcher. The absorbent is injected into the liquid inlet area from the liquid inlet end socket, flows out from the liquid outlet end socket through the ceramic membrane pipe, then enters the absorbent cooler and circularly enters the catalytic membrane contactor. After 800ppm of ammonia gas is added into tail gas, the tail gas enters a gas phase area of a catalytic membrane contactor through a gas inlet (the gas temperature is about 150 ℃ and the liquid temperature is about 90 ℃), and the tail gas is discharged from a gas outlet (the gas temperature is about 100 ℃ and the liquid temperature is about 50 ℃) after reaction through a catalyst. NaOH solution with concentration of 1mol/L is used as absorption liquid, and the flow rate is 300m3H is used as the reference value. The flow rate of the tail gas is 300m3H, in which SO2The concentration was 1000ppm and the NO concentration was 1000 ppm. The volume of the catalytic membrane contactor device is 78.6m3The aperture of the membrane tube is 0.05 mu m, and the denitration catalyst is a molecular sieve type SCR catalyst. After being treated by a catalytic membrane contactor, the NO removal rate is 98 percent, and the SO removal rate is 98 percent2The removal rate is 99.9 percent, and the escape rate of ammonia is 0 percent.
Example 3
The catalytic membrane contactor is arranged at the tail gas outlet of the ship and behind the particle catcher. The absorbent is injected into the liquid inlet area from the liquid inlet end socket, flows out from the liquid outlet end socket through the ceramic membrane pipe, then enters the absorbent cooler and circularly enters the catalytic membrane contactor. After 800ppm of ammonia gas is added into tail gas, the tail gas enters a gas phase area of a catalytic membrane contactor through a gas inlet (the gas temperature is about 180 ℃ and the liquid temperature is about 90 ℃), and the tail gas is discharged from a gas outlet (the gas temperature is about 120 ℃ and the liquid temperature is about 70 ℃) after reaction through a catalyst. Ca (OH) at a concentration of 0.5mol/L2The solution is used as absorption liquid with a flow rate of 100m3H is used as the reference value. The flow rate of the tail gas is 200m3H, in which SO2The concentration is 100ppm and the NO concentration is 100 ppm. The volume of the catalytic membrane contactor equipment is 35.7m3The aperture of the membrane tube is 3 mu m, and the denitration catalyst is a copper-based manganese-based mixed SCR catalyst. After being treated by a catalytic membrane contactor, the NO removal rate is 99 percent, and the SO removal rate is2The removal rate is 99.9 percent, and the escape rate of ammonia is 0 percent.
Compared with the ship tail gas purification system based on the membrane technology, the ship tail gas purification system based on the membrane technology has the advantages that the SCR technology is coupled with the membrane absorption technology, the integration is high, the controllability is strong, the removal efficiency is high, the structure is compact, the amplification is easy, and the desulfurization and denitrification efficiency is improved.
Claims (10)
1. A catalytic membrane contactor, comprising:
the membrane contactor is internally provided with a tubular ceramic membrane (3);
the catalyst plate (4) is arranged outside the tubular ceramic membrane (3), and the SCR denitration catalyst layer (10) is arranged on the catalyst plate (4).
2. The catalytic membrane contactor as claimed in claim 1, further comprising an ammonia-containing substance adding means for adding an ammonia-containing substance to the gas fed into the membrane contactor in one embodiment.
3. The catalytic membrane contactor as claimed in claim 1, wherein in one embodiment, the ammonia-containing species is selected from ammonia gas or urea.
4. A catalytic membrane contactor according to claim 1, wherein in one embodiment, the outside of the SCR denitration catalyst layer (10) is further provided with a protective layer (11); the protective layer (11) is made of porous material; the protective layer (11) is formed by laminating an outer quartz cotton layer (111) and an inner quartz sand layer (112).
5. A catalytic membrane contactor according to claim 1, wherein in one embodiment the catalyst plates (4) are provided with openings (12) and the tubular ceramic membranes (3) are sleeved in the openings (12).
6. A catalytic membrane contactor according to claim 1, wherein in one embodiment the outer part of the membrane contactor is a cylinder (4); an upper end enclosure (1) and a lower end enclosure (7) are respectively arranged at two ends of the cylinder body (5), and an internal channel of the tubular ceramic membrane (3) is respectively communicated with the upper end enclosure (1) and the lower end enclosure (7); the cylinder body (5) and the upper end enclosure (1) are fixedly connected through the upper sealing plate (2), and the cylinder body (5) and the lower end enclosure (7) are fixedly connected through the lower sealing plate (6); the upper sealing plate (2) and the lower sealing plate (6) separate the tubular ceramic membrane (3) into a tube side and a shell side.
7. A catalytic membrane contactor according to claim 1, wherein in one embodiment, a liquid inlet and a liquid outlet are provided on the upper head (1) and the lower head (7), respectively; a gas inlet (8) and a gas outlet (9) are respectively arranged on the cylinder body (5); the material of the SCR denitration catalyst layer (10) is selected from one or a mixture of a plurality of molecular sieve type SCR catalysts, manganese-based SCR catalysts, copper-based SCR catalysts and vanadium-tungsten-titanium type catalysts; the tubular ceramic membrane (3) is an asymmetric porous ceramic microfiltration membrane; the aperture of the tubular ceramic membrane (3) is 0.05-3 mu m.
8. A method for desulfurizing and denitrating gas is characterized in that the gas contains sulfur oxides and nitrogen oxides, and comprises the following steps:
feeding a sulfur oxide absorbent into the channels of the tubular ceramic membrane (3) in the catalytic membrane contactor according to claim 1;
adding ammonia gas into the gas, and then sending the gas into a gas inlet (8) of the catalytic membrane contactor to enable nitrogen oxides in the gas to react with the ammonia gas on the SCR denitration catalyst, and enabling sulfur oxides in the gas to be absorbed by the absorption liquid;
the gas is discharged from the gas outlet (9).
9. The method for desulfurization and denitrification of gases according to claim 9, wherein in one embodiment, the temperature of the gases at the gas inlet (8) is higher than the temperature at the gas outlet (9); in one embodiment, the gas and the absorption liquid flow in a counter-current direction; the gas mainly comprises the following components: SO (SO)xTotal content of 100-2000 ppm, NOxThe total content is 100-1000 ppm; the absorption liquid may be sodium hydroxideThe concentration of the solution or the calcium hydroxide solution is 0.1-5 mol/L; the gas is subjected to a pre-dedusting treatment before entering the catalytic membrane contactor.
10. Use of the catalytic membrane contactor of claim 1 for desulfurization and denitrification of gases.
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