CN104560223B - A kind of gas desulfurizer and method thereof - Google Patents
A kind of gas desulfurizer and method thereof Download PDFInfo
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- CN104560223B CN104560223B CN201410759406.8A CN201410759406A CN104560223B CN 104560223 B CN104560223 B CN 104560223B CN 201410759406 A CN201410759406 A CN 201410759406A CN 104560223 B CN104560223 B CN 104560223B
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- 239000003034 coal gas Substances 0.000 claims abstract description 64
- 230000003009 desulfurizing Effects 0.000 claims abstract description 62
- 230000008929 regeneration Effects 0.000 claims abstract description 61
- 238000011069 regeneration method Methods 0.000 claims abstract description 61
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 60
- 239000011593 sulfur Substances 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000003599 detergent Substances 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 229910017906 NH3H2O Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000006260 foam Substances 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 230000005484 gravity Effects 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 230000001172 regenerating Effects 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003197 catalytic Effects 0.000 abstract description 10
- 230000002378 acidificating Effects 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 49
- 239000000571 coke Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M Sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229940108066 Coal Tar Drugs 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N Diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 206010016256 Fatigue Diseases 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 206010033307 Overweight Diseases 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- -1 building block Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910000468 manganese oxide Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese(II,III) oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 235000020825 overweight Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000117 poly(dioxanone) Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/124—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing metal compounds other than alkali- or earth-alkali carbonates, hydroxides- or oxides- or salts of inorganic acids derived from sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The present invention provides a kind of gas desulfurizer and method thereof, utilizes three kinds of gaseous acidic, deliquescent difference, first uses Na2CO3Or the SO in the deliquescent alkaline detergent solution quick wash coal gas such as MgO2, then by having the hypergravity bed of selective absorbing washability, with Na2CO3Or NH3H2O etc. are alkali source, remove H with Wet Catalytic Oxidation Method washing2S, is finally reached the purpose of desulfurization.The dominant response equipment such as venturi tower, rotary packed bed, jet regeneration device of employing also uses the property of each equipment optionally to absorb H2S、SO2Gas, it is achieved that the sweetening process of coal gas.Reduce system alkaline consumption and energy consumption simultaneously.Desulfurized effect is good, and low cost, difficulty are little, can also reclaim finished product sulfur simultaneously, protects environment.If also needing to remove CO further2, available absorption analytic method is removed.
Description
Technical field
The present invention relates to a kind of containing H2S、SO2、CO2Deng the fuel such as the coal gas of impurity component, natural gas, shale gas or unstripped gas
Purification process technique and equipment, the purification process technique especially relating to a kind of semicoke coal gas and device.
Background technology
The raw materials such as coal gas natural gas, fuel gas have a wide range of applications mode, mainly have: produce other chemical industry as unstripped gas and produce
Product, produce special rolling-mill section, as fuel for the generating of coal gas steam turbine, magnesium metal gas making, coal tar processing, lime burning,
Machine brick, building block, solid caustic soda, gas turbines for power generation, internal combustion engine generating, methanol processed, city supply etc..Regardless of utilization
Mode, will carry out desulfurization, can be divided into front desulfurization and rear desulfurization according to the position of desulfurization.
Desulfurization after 1
Rear desulfurization mentioned here refers to again the waste gas produced, flue gas be carried out desulfurization after coal gas has utilized, as first used by coal gas
Generate electricity, then to the flue gas desulfurization produced after generating, at this moment because of H after burning2S is converted into SO2, after desulfurization process right
As if flue gas, main desulfurization is SO2.The method must be that coal gas is carried out as after fuel combustion, for coal gas as unstripped gas
The technique producing other chemical products is not suitable for.
Desulfurization before 2
Front desulfurization refers to that coal gas enters back into later use operation after first carrying out desulfurization, as coal gas first carries out desulfurization, then by after desulfurization
Coal gas generate electricity, magnesium metal processed or other utilizations etc..Front desulfurization process to as if coal gas, mainly slough is in coal gas
H2S and SO2。
3 front desulfurization and rear desulfurization are compared
First big 7～10 times of volume ratio burning after gas-fired, therefore, the required gas flow desulfurization earlier above processed of rear desulfurization is big, institute
Need equipment desulfurization the most earlier above big；Second, for coal gas need to be utilized as the technique of unstripped gas, it is impossible to desulfurization after employing；3rd,
Equipment, pipeline can be damaged by the sour gas contained in coal gas during rear desulfurization, and therefore, before using as far as possible, desulfurization processes coal
Desulfurization.
The raising again and again of national environmental standard, it is desirable to coal gas, natural gas, coking industry need to optimize technique further, improves and purifies
Level, H2S concentration requirement is by original 200mg/m3Bring up to 20mg/m3.Future may require higher, less than 5mg/m3.Right
Semicoke coal gas in coking industry, owing to its gas composition is special, contains H simultaneously2S、SO2、CO2Deng sour gas, if
Use the treatment technology of high-temperature coking gas purification process, it is impossible to reach emission request.
1 semi-coke gas composition is analyzed
Semicoke is also referred to as semi-coke, and the principle of its producer is the highest with high-temperature coking, causes semi-coke coal because part coal gas melts down second-time burning
The coke-stove gas of gas ratio of components high-temperature retorting is complicated, and major impurity contains H2S、SO2、CO2、NxO etc..
The calorific value of gas that semi-coke coke oven produces is low, about 1609～2017kcal/Nm3, NH in coal gas3Content is relatively low, H2S and
SO2Content the lowest, but CO2Content is relatively big, and therefore, it is at high CO that this coal gas carries out desulfurization2De-H is carried out under concentration2S and
SO2Technique.
In above-mentioned three kinds of gases, SO2Acidity the strongest, because of H2S and CO2Being all weak diacid, their acidity is main with once
Ionization is main, H2The primary ionization constant of S is less than CO2Ionization constant once, i.e. H2The acidity of S compares CO2Weak, if so adopted
By traditional High-temperature carbonization coal QI prostration H2During the technique of S, due to CO2Existence can on desulfurized effect produce impact.Research finds,
H2The dissolubility of S compares CO2By force, the CO when response time is in 5s2Impact can ignore, but more than 5s after, CO2Impact
Can be super next superpower, consume alkali liquor amount and increase, cause desulfurized effect substantially to reduce.Therefore use traditional coal gas desulfurization technique to orchid
Charcoal coal gas carries out desulfurization and does not reaches preferable effect.
2 traditional coal desulfurization techniques are for the comparison of semi-coke desulfurization
2.1 catalytic wet oxidation techniques
Catalytic wet oxidation technique is the main coal gas desulfurization technique of current China coking industry, is under the effect of catalyst, profit
It is the H that alkali source absorbs in coal gas with the ammonia in coal gas or additional sodium carbonate2The technique of S.Absorb H2Doctor solution after S send regenerating section
Carry out oxidation regeneration, the H that will absorb2S separates out and forms sulfur simple substance, flows automatically the groove that defoams with the form of sulfur foam, then is centrifuged
Or melt process, generate raw sulfur or ripe sulfur.Generally catalytic wet oxidation technique has PDS, tannic extract, HPF, FRC etc.；Desulfurization sets
Standby form has high tower regeneration technology, regeneration tank regeneration technology, a tower desulfurization regeneration technique, a tower half formula desulfurization regeneration technique etc..
When using catalytic wet oxidation technique to be used for semi-coke coal gas desulfurization, doctor solution H in absorbing coal gas2Meeting and coal while S
SO in gas2Reaction, generates (NH3)2SO3Or Na2SO3, it cannot react de-with oxygen in regeneration tank or regenerator
Sulfur rich solution regeneration NH3·H2O or Na2CO3Solution, can generate (NH on the contrary3)2SO4Or Na2SO4Deng secondary salt, accordingly, because
SO2Existence, desulfurization regeneration effect is greatly reduced, and the consumption of doctor solution is greatly increased, and will keep identical assimilation effect,
More fresh desulfurization alkali liquor must be added continuously in system.
Further, since the packed tower tower speed that Wet Catalytic Oxidation Method desulfurization uses is usually 0.4～0.6m/s, absorber portion height is about
15m, the response time is much larger than 5s, CO2Impact very big, partial desulfurization alkali liquor can be consumed, make desulfurized effect reduce.
Therefore, the Wet Catalytic Oxidation Method of high temperature coke oven coal gas desulfurization is applied to semi-coke coal gas desulfurization is impracticable, need to be to it
It is adjusted, removes SO2And CO2Interference.
2.2 absorption and desorption techniques
Conventional absorption and desorption method has hydramine method, vacuum carbonate method, AS method etc., is to utilize absorbing liquid and coal gas counter current contacting,
Absorb the H in coal gas2S, absorbs H2Sulfur removing pregnant solution after S send desorption and regeneration in generating apparatus again, and the lean solution of generation send desulfurizing tower to circulate
Absorb the H in coal gas2S, the sour gas of generation removes acid-producing apparatus, produces sulphuric acid.
Because semi-coke coal gas contains SO2、CO2And O2, substantial amounts of circulation desulfurization liquid can be consumed, and make the sulfurous acid thing of generation aoxidize
Becoming sulphuric acid thing, secondary salt growing amount strengthens；Substantial amounts of CO2Exist and make H in desorbing acid gas2The concentration of S reduces, and increases the cost of antacid
And difficulty, need to optionally absorb H2S, therefore, absorption and desorption technique is applied to semi-coke desulfurization and is also problematic in that.
2.3 dry desulfurization
Dry process is to utilize the hydrogen sulfide in solid absorbent removing coal gas and organic sulfur, and the degree of purification of desulfurization is higher, it is adaptable to
Lean sulphurous gas processes, and is used for fine de-sulfur, and operation is simple and reliable, and the most conventional desulfurizing agent is inexpensive ferrum oxide, and its
He such as desulfurizing agents such as activated carbon, molecular sieve, manganese oxide, zinc oxide the most costly, less use；For identical coal gas treating capacity,
The equipment of dry desulfurization is huge, and desulfurizing agent is changed frequently, and consumption is big, is difficult to regeneration, causes operating cost to increase, and work is strong
Degree is big, can not reclaim finished product sulfur, waste desulfurizing agent, waste gas, waste water serious environment pollution simultaneously, and therefore general tolerance is more than
20000Nm3The coal gas of/h does not consider dry desulfurizing process.
Summary of the invention
The problem existed for prior art, the present invention provides a kind of gas desulfurizer and method thereof, utilize three kinds of gaseous acidic,
Deliquescent difference, first uses Na2CO3Or the SO in the deliquescent alkaline detergent solution quick wash coal gas such as MgO2, then by having choosing
Selecting property absorbs the hypergravity bed of washability, with Na2CO3Or NH3H2O etc. are alkali source, remove H with Wet Catalytic Oxidation Method washing2S,
It is finally reached the purpose of desulfurization.Desulfurized effect is good, and low cost, difficulty are little, can also reclaim finished product sulfur simultaneously, protects environment.
The technical scheme is that a kind of gas desulfurizer, including venturi tower, circulation liquid pool, rotary packed bed, rich
Liquid bath, jet regeneration device, regeneration tank, lean solution and H2S sink；
Be provided with rough gas import bottom described venturi tower, middle part is venturi district, top is spraying layer；In described spraying layer
Portion is provided with the first alkaline detergent solution, and spraying layer sidewall opening connects cleaning mixture pipe gravity flow pipeline, and described cleaning mixture pipe gravity flow pipeline sets
It is equipped with SO2Cleaning circulation pump and waste liquid outlet and the other end are communicated to circulate liquid pool；
It is provided with the first alkali liquor feed tube on described circulation liquid pool, is internally provided with oxidation unit, oxidation unit is provided with oxidation
Air intake duct；
Gas outlet, described venturi tower top pipeline is connected to rotary packed bed air inlet, and rotary packed bed gas outlet pipeline is even
Being connected to external equipment, rotary packed bed rich solution outlet conduit is connected to rich solution groove；
The liquid outlet of described rich solution groove is connected to the inlet of jet regeneration device, described jet regeneration device by rich solution circulating pump pipeline
On be provided with air from suction inlet, the mixed liquor after rich solution and the air reaction of self-priming is delivered to regeneration through the liquid outlet of jet regeneration device
In groove；
Described regeneration tank top is provided with level regulator and sulfur foam outlet, and the liquid outlet pipeline of level regulator is connected to lean solution
And H2S sink, described lean solution and H2The liquid outlet of S sink passes through lean solution and H2S washing pump pipeline is connected to rotary packed bed
Inlet, and described lean solution and H2The second alkali liquor feed tube it is provided with on S sink；
Described sulfur foam outlet is connected to desulfuration foam processing system.
Further, described venturi district includes that the venturi type pipe in space is left in several centres side by side.
Further, described jet regeneration device is venturi playpipe.
The present invention also provides for a kind of coal gas desulfurization method, specifically comprises the following steps that
(1) rough gas is entered bottom venturi tower by rough gas import, passes upward through and sprays with spraying layer after venturi district accelerates
The the first alkaline detergent solution reaction got off, removes the SO in gas after reaction2, generate sulphite, with the washing of sulphite
Liquid flows automatically to circulate liquid pool by cleaning mixture pipe gravity flow pipeline, then by SO2Cleaning circulation pump pressurization is sent to venturi tower circulated sprinkling；
(2) arranging oxidation unit in circulation liquid pool, oxidation air enters oxidation unit by oxidation air air inlet pipe, by sulfurous acid
Salt is oxidized to sulfate, when the sulfate concentration circulated in liquid pool reaches setting value, is discharged by waste liquid outlet, passes through simultaneously
First alkali liquor feed tube adds the first alkaline detergent solution in circulation liquid pool；
(3) SO is removed through venturi tower washing2Coal gas by gas outlet, top be delivered to rotary packed bed in, through rotation
Packed bed rotates the hypergravity reaction zone and lean solution and H produced2The second alkaline detergent solution reaction that S washing pump is delivered to, washing absorption
H in coal gas2S, the coal gas after purification is delivered to external equipment by rotary packed bed gas outlet；
(4) by rotary packed bed absorption H2Rich solution after S flows automatically to rich solution groove, then is sent into jet regeneration device by rich solution circulating pump,
H2S reaction rich solution is through the jet regeneration device reacted rich solution of mixing air self-suction further reaction regeneration in regeneration tank, after regeneration
Lean solution flows automatically to lean solution and H through regeneration tank top level regulator2S sink, by lean solution and H2S washing pump sends into rotary packed bed following
Washing-round is washed；
(5) the sulfur foam that sulfur removing pregnant solution regenerative response produces is delivered to sulfur foam processing system by the sulfur foam outlet at regeneration tank top,
Produce raw sulfur or sulfur；
(6) along with the carrying out of reaction, the alkali concn in system constantly reduces, by the second alkali liquor feed tube to lean solution and H2S washes
Wash and groove adds the second alkaline detergent solution.
Further, the coal gas after purifying in step (3) is delivered to external equipment, if need to remove the coal gas after purifying further
CO2, the method that absorption can be used to resolve is removed.
Further, described first alkaline detergent solution is Na2CO3、MgO、Ca(OH)2、CaCO3Or NH3H2O。
Further, described second alkaline detergent solution is Na2CO3Or NH3H2O。
The invention has the beneficial effects as follows: a kind of gas desulfurizer and method thereof are provided, utilize three kinds of gaseous acidic, deliquescent
Difference, first uses Na2CO3Or the SO in the deliquescent alkaline detergent solution quick wash coal gas such as MgO2, then by having selective absorbing
The hypergravity bed of washability, with Na2CO3Or NH3H2O etc. are alkali source, remove H with Wet Catalytic Oxidation Method washing2S, finally reaches
Purpose to desulfurization.The dominant response equipment such as venturi tower, rotary packed bed, jet regeneration device of employing also uses the spy of each equipment
The absorption H of different performance selectability2S、SO2Gas, it is achieved that the sweetening process of coal gas.Reduce system alkaline consumption and energy consumption simultaneously.
Desulfurized effect is good, and low cost, difficulty are little, can also reclaim finished product sulfur simultaneously, protects environment.If also needing to remove CO further2, can
Remove with absorption analytic method.
Accompanying drawing explanation
Fig. 1 is the system diagram of apparatus of the present invention.
Detailed description of the invention
The present invention is described further below in conjunction with the accompanying drawings.
The present invention utilizes three kinds of gaseous acidic, deliquescent difference, first uses Na2CO3Or the deliquescent alkaline detergent solution such as MgO is fast
SO in speed washing coal gas2, then by having the hypergravity bed of selective absorbing washability, with Na2CO3Or NH3H2O etc. are alkali source,
H is removed with Wet Catalytic Oxidation Method washing2S, is finally reached the purpose of desulfurization.Desulfurized effect is good, and low cost, difficulty are little, simultaneously
Finished product sulfur can also be reclaimed, protect environment.If also needing to remove CO further2, available absorption analytic method is removed.
With Na2CO3As a example by absorbing detergent, its technological principle is:
SO2Absorption reaction principle:
SO2+Na2CO3+H2O→2NaHSO3
SO2+Na2CO3→Na2SO3+CO2
2NaHSO3+Na2CO3→2Na2SO3+CO2+H2O
2Na2SO3+O2→2Na2SO4
H2S absorber portion reaction principle:
H2S+Na2CO3→NaHS+NaHCO3
Na2CO3+H2S→Na2S+H2O+CO2
Na2CO3+CO2+H2O→2NaHCO3
H2The fundamental reaction occurred in S regeneration tank is as follows:
NaHS+1/2O2→NaOH+S↓
Na2S+1/2O2+H2O→2NaOH+S↓
Na2SX+1/2O2+H2O→2NaOH+SX
Outside divided by upper reaction, also carry out following side reaction:
2NaHS+2O2→Na2S2O3+H2O
2Na2S2O3+O2→2Na2SO4+2S↓
As it is shown in figure 1, the system construction drawing of the present invention, a kind of gas desulfurizer, including venturi tower 2, circulation liquid pool 9,
Rotary packed bed 5, rich solution groove 10, jet regeneration device 12, regeneration tank 13, lean solution and H2S sink 14；Described venturi tower
Be provided with rough gas import 1 bottom 2, middle part is venturi district 3, top is spraying layer 4；Described spraying layer 4 is internally provided with
First alkaline detergent solution 7, spraying layer sidewall opening connects cleaning mixture pipe gravity flow pipeline 7, described cleaning mixture pipe gravity flow pipeline 7 is provided with
SO2Cleaning circulation pump 8 and waste liquid outlet 19 and the other end are communicated to circulate liquid pool 9；It is provided with first on described circulation liquid pool 9
Alkali liquor feed tube 20, is internally provided with oxidation unit, and oxidation unit is provided with oxidation air air inlet pipe 17；Described venturi tower
2 gas outlet, top pipelines are connected to the air inlet of rotary packed bed 5, and the gas outlet pipeline of rotary packed bed 5 is externally connected to be set
Standby, the rich solution outlet conduit of rotary packed bed 5 is connected to rich solution groove 10；The liquid outlet of described rich solution groove 10 is circulated by rich solution
Pump 11 pipeline is connected to the inlet of jet regeneration device 12, described jet regeneration device 12 is provided with air from suction inlet 18, richness
Mixed liquor after the air reaction of liquid and self-priming is delivered in regeneration tank 13 through the liquid outlet of jet regeneration device 12；Described regeneration tank
13 tops are provided with level regulator and sulfur foam outlet 16, and the liquid outlet pipeline of level regulator is connected to lean solution and H2S washs
Groove 14, described lean solution and H2The liquid outlet of S sink 14 passes through lean solution and H2S washing pump 15 pipeline is connected to rotary packed bed 5
Inlet, and described lean solution and H2The second alkali liquor feed tube 21 it is provided with on S sink 14；Described sulfur foam outlet 16 is even
It is connected to desulfuration foam processing system.
Wherein: the venturi tower of this device is different from a conventional venturi tower, its reactivity venturi district is by a series of
Between leave the pipe arranged in parallel in space and combine, define upper and lower space relatively big, middle narrower venturi phenomenon, thus
Produce Venturi effect.Upper strata is sprayed by nozzle simultaneously, forms range of atomization, improves reaction effect further.In this equipment,
At strong acidic environment SO2Under atmosphere, CO2And H2S gas is not involved in reaction substantially, it is achieved that selective acceptance condition.
The powerful centrifugal force (or hypergravity) that the rotary packed bed packed bed utilizing high speed rotating produces makes flow velocity and the filler of gas-liquid
Effective ratio area be greatly improved, liquid in the case of high dispersive, high mixing, strong turbulence and interface update rapidly with gas
Body contacts in curved channel with great relative velocity, greatly strengthening transfer process, is embodied in:
Gas tangentially enters rotor exocoel through gas feed, is entered filler by rotor periphery under the effect of gas pressure.Liquid
Rotor internal cavity is introduced, through shower nozzle sprinkle on rotor inner edge by liquid inlet tube.The liquid entering rotor is filled out by rotor
The effect of material, circumferential speed increases, and produced centrifugal force pushes it against rotor periphery.In the process, filled point of liquid
Dissipate, crushing-type becomes greatly, the surface area of continuous renewal, and tortuous runner exacerbates the renewal of liquid surface.Liquid is at high score
Dissipate, high turbulence, strong mixing and interface update rapidly in the case of with gas with great relative velocity in bending duct reverse
Contact, greatly enhances mass transport process.So, defining fabulous mass transfer and reaction condition at internal rotor, liquid is turned
Son is thrown and is left overweight machine through liquid outlet tube after shell collects.Gas leaves rotor from rotor center, gas outlet tube draw,
Complete mass transfer and course of reaction.
The rotary packed bed response time is extremely short, just can react, therefore to CO in less than the time of 1s2And H2The mixing of S
Gas, can preferably selective absorbing H2S, is just suitable for semicoke etc. and contains CO simultaneously2And H2The special gas of S.
Jet regeneration device is a venturi playpipe, and sulfur removing pregnant solution produces negative pressure by being pumped into after jet regeneration device after its trunnion,
Air self-suction, with the air of self-priming in trunnion portion, expansion pipe portion strong hybrid reaction, a series of jet regeneration device collectively constitutes
The regenerative system of sulfur removing pregnant solution, it is achieved that the oxidation regeneration of sulfur removing pregnant solution.
Technological process: a kind of coal gas desulfurization method, specifically comprises the following steps that
(1) rough gas is entered bottom venturi tower by rough gas import, passes upward through under spraying with spraying layer after venturi district accelerates
The the first alkaline detergent solution reaction come, removes the SO in gas after reaction2, generate sulphite, with the cleaning mixture of sulphite
Flow automatically to circulate liquid pool by cleaning mixture pipe gravity flow pipeline, then by SO2Cleaning circulation pump pressurization is sent to venturi tower circulated sprinkling；
(2) arranging oxidation unit in circulation liquid pool, oxidation air enters oxidation unit by oxidation air air inlet pipe, by sulfurous acid
Salt is oxidized to sulfate, when the sulfate concentration circulated in liquid pool reaches setting value, is discharged by waste liquid outlet, passes through simultaneously
First alkali liquor feed tube adds the first alkaline detergent solution in circulation liquid pool；
(3) SO is removed through venturi tower washing2Coal gas by gas outlet, top be delivered to rotary packed bed in, through rotation
Packed bed rotates the hypergravity reaction zone and lean solution and H produced2The second alkaline detergent solution reaction that S washing pump is delivered to, washing absorption
H in coal gas2S, the coal gas after purification is delivered to external equipment by rotary packed bed gas outlet；
(4) by rotary packed bed absorption H2Rich solution after S flows automatically to rich solution groove, then is sent into jet regeneration device by rich solution circulating pump,
H2S reaction rich solution is through the jet regeneration device reacted rich solution of mixing air self-suction further reaction regeneration in regeneration tank, after regeneration
Lean solution flows automatically to lean solution and H through regeneration tank top level regulator2S sink, by lean solution and H2S washing pump sends into rotary packed bed following
Washing-round is washed；
(5) the sulfur foam that sulfur removing pregnant solution regenerative response produces is delivered to sulfur foam processing system by the sulfur foam outlet at regeneration tank top,
Produce raw sulfur or sulfur；
(6) along with the carrying out of reaction, the alkali concn in system constantly reduces, by the second alkali liquor feed tube to lean solution and H2S washes
Wash and groove adds the second alkaline detergent solution.
Wherein: the coal gas after purifying in step (3) is delivered to external equipment, if the coal gas after purifying need to be removed CO further2,
The method that absorption can be used to resolve is removed.Described first alkaline detergent solution is Na2CO3、MgO、Ca(OH)2、CaCO3Or NH3H2O。
Described second alkaline detergent solution is Na2CO3Or NH3H2O。
It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, also may be used
To make some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.In the present embodiment the clearest and the most definite
Each ingredient all can use prior art to be realized.
Claims (4)
1. a coal gas desulfurization method, it is characterised in that: based on gas desulfurizer, described gas desulfurizer, including literary composition mound
In tower (2), circulation liquid pool (9), rotary packed bed (5), rich solution groove (10), jet regeneration device (12), regeneration tank (13),
Lean solution and H2S sink (14)；
Described venturi tower (2) bottom is provided with rough gas import (1), middle part is venturi district (3), top is spraying layer (4)；
Described spraying layer (4) is internally provided with the first alkaline detergent solution (7), and spraying layer sidewall opening connects cleaning mixture pipe gravity flow pipeline (7),
It is provided with SO on described cleaning mixture pipe gravity flow pipeline (7)2Cleaning circulation pump (8) and waste liquid outlet (19) and the other end are communicated to
Circulation liquid pool (9)；
It is provided with the first alkali liquor feed tube (20) on described circulation liquid pool (9), is internally provided with oxidation unit, on oxidation unit
It is provided with oxidation air air inlet pipe (17)；
Described venturi tower (2) gas outlet, top pipeline is connected to the air inlet of rotary packed bed (5), rotary packed bed (5)
The externally connected equipment of gas outlet pipeline, the rich solution outlet conduit of rotary packed bed (5) is connected to rich solution groove (10)；
The liquid outlet of described rich solution groove (10) is connected to the feed liquor of jet regeneration device (12) by rich solution circulating pump (11) pipeline
Mouthful, described jet regeneration device (12) is provided with air mixed liquor warp after the air reaction of suction inlet (18), rich solution and self-priming
The liquid outlet of jet regeneration device (12) is delivered in regeneration tank (13)；
Described regeneration tank (13) top is provided with level regulator and sulfur foam outlet (16), the liquid outlet pipeline of level regulator
It is connected to lean solution and H2S sink (14), described lean solution and H2The liquid outlet of S sink (14) passes through lean solution and H2S washs
Pump (15) pipeline is connected to the inlet of rotary packed bed (5), and described lean solution and H2It is provided with on S sink (14)
Two alkali liquor feed tubes (21)；
Described sulfur foam outlet (16) is connected to desulfuration foam processing system；
Described coal gas desulfurization method, specifically comprises the following steps that
(1) rough gas is entered bottom venturi tower by rough gas import, passes upward through and sprays with spraying layer after venturi district accelerates
The the first alkaline detergent solution reaction got off, removes the SO in gas after reaction2, generate sulphite, with the washing of sulphite
Liquid flows automatically to circulate liquid pool by cleaning mixture pipe gravity flow pipeline, then by SO2Cleaning circulation pump pressurization is sent to venturi tower circulated sprinkling；
(2) arranging oxidation unit in circulation liquid pool, oxidation air enters oxidation unit by oxidation air air inlet pipe, by sulfurous acid
Salt is oxidized to sulfate, when the sulfate concentration circulated in liquid pool reaches setting value, is discharged by waste liquid outlet, passes through simultaneously
First alkali liquor feed tube adds the first alkaline detergent solution in circulation liquid pool；
(3) SO is removed through venturi tower washing2Coal gas by gas outlet, top be delivered to rotary packed bed in, through rotation
Packed bed rotates the hypergravity reaction zone and lean solution and H produced2The second alkaline detergent solution reaction that S washing pump is delivered to, washing absorption
H in coal gas2S, the coal gas after purification is delivered to external equipment by rotary packed bed gas outlet；
(4) by rotary packed bed absorption H2Rich solution after S flows automatically to rich solution groove, then is sent into jet regeneration device by rich solution circulating pump,
H2S reaction rich solution is through the jet regeneration device reacted rich solution of mixing air self-suction further reaction regeneration in regeneration tank, after regeneration
Lean solution flows automatically to lean solution and H through regeneration tank top level regulator2S sink, by lean solution and H2S washing pump sends into rotary packed bed following
Washing-round is washed；
(5) the sulfur foam that sulfur removing pregnant solution regenerative response produces is delivered to sulfur foam processing system by the sulfur foam outlet at regeneration tank top,
Produce raw sulfur or sulfur；
(6) along with the carrying out of reaction, the alkali concn in system constantly reduces, by the second alkali liquor feed tube to lean solution and H2S washes
Wash and groove adds the second alkaline detergent solution.
A kind of coal gas desulfurization method the most according to claim 1, it is characterised in that: the coal gas after purifying in step (3)
It is delivered to external equipment, if the coal gas after purifying need to be removed CO further2, the method that absorption can be used to resolve is removed.
A kind of coal gas desulfurization method the most according to claim 1, it is characterised in that: described first alkaline detergent solution is Na2CO3、
MgO、Ca(OH)2、CaCO3Or NH3H2O。
A kind of coal gas desulfurization method the most according to claim 1, it is characterised in that: described second alkaline detergent solution is Na2CO3
Or NH3H2O。
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| CN109289462B (en) * | 2018-11-05 | 2021-06-08 | 北京化工大学 | Supergravity desulfurization system for multi-working-condition sulfur-containing gas emission |
| CN114515500B (en) * | 2022-03-15 | 2022-12-20 | 北京北科环境工程有限公司 | Device and method for removing blast furnace gas hydrogen sulfide |
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