CN106975340A - Higher concentration COS low temperature removal methods in gas - Google Patents
Higher concentration COS low temperature removal methods in gas Download PDFInfo
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- CN106975340A CN106975340A CN201710318900.4A CN201710318900A CN106975340A CN 106975340 A CN106975340 A CN 106975340A CN 201710318900 A CN201710318900 A CN 201710318900A CN 106975340 A CN106975340 A CN 106975340A
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- 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
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/75—Multi-step processes
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Abstract
The present invention provides the low temperature removal methods of higher concentration COS in gas a kind of, mainly includes：Process gas maintains or is heated to 30 80 DEG C, water inlet solution desulfurizing tower processing；Loaded in mixture in hydrolysis desulfurizing tower or lamination filling COS hydrolytic reagents and H2S oxidation desulfurizing agents；The H2S oxidation desulfurizing agents can carry out blowing sulphur hot recycling under 200 300 DEG C of temperature conditionss, and COS hydrolytic reagents hydraulic performance decline after desulfurizing agent hot recycling process is less or does not reduce substantially；It is described hydrolysis desulfurizing tower set two or more, can connection in series-parallel use, hydrolysis desulfurizing tower have between vertical heating muff, sleeve pipe be hydrolytic reagent desulfurizing agent bed；Hydrolyze desulfurizing tower to blow out the elemental sulfur trapped fusing, gasification in 200 300 DEG C of hot recyclings, sulphur is collected as through regenerating condenser.The sweetening process of this method is simple and reliable, and COS removal efficiencies are easily maintained at more than more than 90%, or even 95%, it is easy to controlled, and processing capacity elasticity is big, to H2S, COS content height and fluctuation strong adaptability, safety and environmental protection, operating cost are low.
Description
Technical field
The present invention relates to process for desulfurizing gas, and in particular to higher concentration COS low temperature removal methods in a kind of gas.
Background technology
In chemical process, there are many gases to contain H2S, COS sulfides, are typically first used when sulfide quantity is larger
MDEA methods, low-temp methanol the method such as wash and separate most of sulfide, then by suitable recovery technology of sulfur at
Reason；But when tolerance is smaller, the technique of this first separation and concentration, again sulphur recovery, just because flow is complicated, investment is big, operation control
System is cumbersome and is difficult to apply.
When tolerance is not very big, H2It is general that COS is hydrolyzed to by H using low temperature tempreture organic sulphur hydrolysis agent when S, COS concentration are relatively low2S,
Elemental sulfur adsorbing and removing is converted into by oxidation desulfurizing agent again.The operating condition of COS low temperature hydrolysis agent is generally -80 DEG C of normal temperature,
The higher hydrolysing activity of typical temperature is higher, such as 50-70 DEG C, but sulfation can occur for more than 80 DEG C of temperature, cause water-disintegrable
It can decline and the lost of life.
H2S oxidation sweetening, using wide, advantage is that operation temperature is low, to H2S concentration levels and flowed fluctuation it is suitable
Ying Xingqiang, be usually and the SO contained by process gas2、O2Reaction is converted into elemental sulfur and adsorbs, is deposited on the endoporus or table of desulfurizing agent
Face, can be by H2S is handled to below 1ug/L, sulfur capacity general more than 20%, or even more than 30% or higher.
As COS or H2S concentration is higher, and such as COS concentration is higher than 500ug/L or H2When S concentration is higher than 1000ug/L, low temperature has
COS hydrolysis in machine sulphur hydrolytic reagent can be suppressed, and percent hydrolysis is difficult to be maintained at more than 90%, is less susceptible to be maintained at more than 95%.
The desulfurizing agent of inversion absorption type can also handle this gas in a short time, but Sulfur capacity is relatively low or time of break-through is shorter, and
Often reproducibility is bad.
Some process gas, the CO gas such as produced by coke, carbon dioxide and oxygen in Gas-making Furnace, coke is high with calcium oxide
Temperature prepares the calcium carbide furnace gas of calcium carbide, and yellow phosphorus electric furnace tail gas, CO contents are high, and most of sulphur exists in COS forms, and concentration is more
In more than 1000ug/L, or even more than 2000ug/L, the percent hydrolysis using COS during low temperature tempreture organic sulphur hydrolysis agent is not high enough, and COS takes off
Except rate is difficult to be maintained at more than 90%, it is less susceptible to be maintained at more than 95%, residual concentration is still higher；But according to middle temperature, high temperature
Hydrolytic reagent and condition, expense are again relatively higher；Because tolerance is smaller, sulfide quantity very little, the side of first separation and concentration sulphur recovery again
Method is not applied to yet.The initial pressure of this kind of gas is often normal pressure or low pressure, if not removing big portion first under normal pressure, lower pressure
Point sulfide, then sulfide leakage is more in follow-up pressurization and separation process, and environmental odors are larger, to equipment and compressor
Corrosion is also heavier, thus should remove COS as much as possible in normal pressure, periods of low pressure, by H2S tries one's best whole removings.
Thus, it is necessary to develop the low temperature removing gas that a kind of COS removal efficiencies are easily maintained at more than more than 90%, or even 95%
Middle higher concentration COS method.
The content of the invention
In order to solve the above technical problems, the present invention provides the low temperature removal methods of higher concentration COS in gas a kind of, COS
Removal efficiency is easily maintained at more than more than 90%, or even 95%, is mainly included：Process gas maintains or is heated to 30-80 DEG C, and water inlet is freed
The processing of sulphur tower；Loaded in mixture in desulfurizing tower or lamination filling COS hydrolytic reagents and H2S oxidation desulfurizing agents, the COS hydrolytic reagents are by COS bases
Originally it is hydrolyzed to H2S, the oxidation desulfurizing agent hydrolyzes COS the H of generation2H contained by S and process gas2S, with the SO contained by process gas2、
O2Reaction is converted into elemental sulfur absorption, is deposited in the endoporus of desulfurizing agent or surface；The H2S oxidation desulfurizing agents can be in 200-300
Carry out blowing sulphur hot recycling under DEG C temperature conditionss, by by the elemental sulfur for adsorbing, deposit fusing, gasification finish and recover substantially de-
Sulphur performance, COS hydrolytic reagents hydraulic performance decline after the desulfurizing agent hot recycling process of 200-300 DEG C of temperature conditionss is less or basic
Do not reduce；
Wherein, the hydrolysis desulfurizing tower sets two or more, can connection in series-parallel use, specially vertical pipes heat supply regeneration is de-
Sulphur tower, if between the vertical pipes of sufficient amount and heat exchange area, sleeve pipe being hydrolytic reagent-desulfurizing agent bed；COS percent hydrolysis drops to
Setting and/or sulfur content of working off one's feeling vent one's spleen, which are risen to after setting, to be cut out, and thermal source is passed through into sleeve pipe and improves hydrolytic reagent-desulfurizing agent bed
Layer temperature carries out hot recycling；The vertical pipes heat supply regenerative sulfur binding tower includes hydrolytic reagent-desulfurizing agent bed and process gas is passed in and out
Passage and interface, hydrolytic reagent-desulfurizing agent construct for handling, top has set distribution and upper and lower two of collection heating medium effect add
Thermal medium room；Vertical pipes are formed by inner and outer tubes nesting, and inner tube upper end open is in upper chamber bottom plate, and outer tube upper end open is under
Room bottom plate；Sleeve pipe extends down into hydrolytic reagent-desulfurizing agent bed, until under the bottom of hydrolytic reagent-desulfurizing agent bed, outer tube
End closure, inner tube lower end extends on the sealing end of outer tube and is open；Melted during hot recycling, gasify the elemental sulfur flowed out
Collected through regenerating condenser；Hydrolyze after the completion of desulfurizing tower hot recycling, change in natural cooling cooling or sleeve pipe after cooling medium cooling
Standby or incision comes into operation.
In gas of the present invention in higher concentration COS low temperature removal methods, the COS hydrolytic reagents can use common a variety of boards
Number commodity, macropore gama-alumina is typically carried on by alkali metal, the alkali of alkaline-earth metal or carbonate or activated carbon is made, lead to
Often through steam ageing and/or calcination process, but concrete operations condition need with reference to the performance of hydrolytic reagent and the specific of process gas into
Point as moisture situations such as determine, such as to consider because moisture in hydrolytic reagent endoporus excessive adsorption or condense caused by hydrolysis
Hydraulic performance decline, typically reduces this influence by properly increasing operation temperature.COS hydrolytic reagents primarily serve hydrolysis in the present invention
COS effect, generation is loaded in mixture with it or lamination filling oxidation desulfurizing agent can largely adsorb the H of conversion2S.The H2S oxidations are de-
Sulphur agent can use the commodity of common a variety of trades mark, generally by macropore activated carbon supported Fe, Mn, Cu, Zn, Co and/or alkali metal
The compositions such as oxide are modified and are made；It is that will hydrolyze the H generated that it, which is acted on,2H contained by S and process gas2S, with the SO contained by process gas2、
O2Reaction be converted into elemental sulfur absorption, be deposited in the endoporus of desulfurizing agent or surface and remove, typically can be by H21ug/L is arrived in S processing
Hereinafter, sulfur capacity general more than 20%, or even more than 30% or higher.Due to the COS hydrolytic reagents, H2S oxidation desulfurizing agents intolerant to
Acid, if containing HCl, HCN, NOx, SO in gas3Deng Acid constituents, should first it remove.
In gas of the present invention in higher concentration COS low temperature removal methods, the operating condition of hydrolysis desulfurizing tower mainly considers
The performance of hydrolytic reagent is played, because the difficulty of COS hydrolysis is higher than H2The difficulty of S oxidation generation elemental sulfurs；COS hydrolytic reagents, H2S oxygen
Change loading in mixture or lamination type of feed for desulfurizing agent, under the material condition of the higher COS concentration of the present invention, bed is reduced on the whole
Middle H2S concentration, especially in outlet section H2S concentration falls below extremely low level, so as to improve COS percent hydrolysis, and extends
Life-span of hydrolytic reagent；Wherein the effect of mixed packing is loaded better than lamination, and water can be improved by being mixed before being loaded to desulfurizing tower
The degree of mixedness in agent-desulfurizing agent bed is solved, it is better when shape and size are same or like.Hot recycling is to maintaining, extension
The performance of hydrolytic reagent and life-span, also play very crucial effect.The embodiment of the present invention is under the conditions of COS 0.16%, hydrolysis
Agent, desulphurizer mixing filling are easily guaranteed that more than 90% or even more than 95% COS percent hydrolysis, and the long period can be maintained by regeneration
Hydrolysis desulfurization operations；And percent hydrolysis when individually hydrolyzing is lower slightly, and hydrolysis ability decline is larger after the same operating time.
In gas of the present invention in higher concentration COS low temperature removal methods, hydrolysis desulfurizing tower most time carries out desulfurization fortune
Turn, hydrolytic reagent-desulfurizing agent bed uses 30-80 DEG C of relatively low operating temperature, and process gas flow can be edge to according to bed structure
The upper entering and lower leaving or bottom in and top out in casing axis direction, or the right side goes out, the right side is entered a left side and gone out to enter perpendicular to the left side in casing axis direction
Or from outer rim to center, from center to outer rim, it is vertical in desulfurization operation process usually along the upper entering and lower leaving in casing axis direction
Sleeve pipe does not play a part of to heat or cooled, and medium does not flow substantially in sleeve pipe.Desulfurizing tower cut out after penetrating carry out hot recycling when
Between it is shorter, the scattered sleeve pipes that flow into upper and lower two heating dielectric chamber of the heating medium through tower top simultaneously flow back to another room, by
Gradually bed is heated；Heated during hot recycling in vertical pipes in the flow direction of medium, its outer tube to be from top to bottom or on the contrary, interior
From bottom to top or on the contrary, typically using the flow direction in inner tube from top to bottom, in outer tube from bottom to top in pipe, make on the whole bed from
Lower and upper heating.Medium is heated used in the process of hot recycling can be hot blast, superheated steam, conduction oil, hot blast, superheated steam
Benefit is to be easier to change cold wind, cold water cooling into after the completion of regenerating.Steamed with the indifferent gas using same 200-300 DEG C of temperature, overheat
The method that vapour directly purges hydrolytic reagent-desulfurizing agent bed is compared, thermal regeneration method indirectly heat hydrolytic reagent-desulfurizing agent of the invention
Bed, the influence to hydrolytic reagent, desulfurizing agent performance is smaller；Compared with coil pipe mode of heating, vertical pipes heat supply regeneration of the present invention
Hydrolytic reagent that desulfurizing tower is loaded, desulfurizing agent are easier after hot recycling to draw off when scrapping.
In gas of the present invention in higher concentration COS low temperature removal methods, hydrolysis desulfurizing tower regenerative process in or wherein after
Phase, hydrolytic reagent-desulfurizing agent bed can introduce indifferent gas such as N2、CO2, CO make purge gass, to reduce in bed elemental sulfur and other
Material such as CS2, mercaptan, thioether, the partial pressure of the organic sulfur such as thiophene and heavy hydrocarbon such as tar, so as to reach higher blowing or desorption
Rate, more preferably recovers desulfurizing agent, the Sulfur capacity or hydrolysis property of hydrolytic reagent, or can suitably reduce hot regeneration temperature；It is preferred to use
Line operating hydrolysis desulfurizing tower work off one's feeling vent one's spleen or high temperature furnace reactor feed gas such as CO Gas-making Furnaces CO2Unstripped gas as hydrolytic reagent-
The hot recycling purge gass of desulfurizing agent bed, nothing after being to be easy to get and regenerate nearby in the advantage worked off one's feeling vent one's spleen of line operating hydrolysis desulfurizing tower
Need displacement, the CO of the reactor feed gas such as CO Gas-making Furnaces of high temperature furnace2The advantage of unstripped gas is that regeneration condenser tail gas can return gas making
Stove continues to serve as reactor feed gas.Sulphur hot recycling is blown by what is carried out under 200-300 DEG C of temperature conditionss, by H2S oxidation sweetenings
Elemental sulfur and a small amount of other materials such as CS that agent is adsorbed, deposited2, mercaptan, thioether, organic sulfur and the heavy hydrocarbon such as tar such as thiophene
Fusing, gasification finish, and recover it substantially and aoxidize H2S generates the performance of elemental sulfur；Also by hydrolytic reagent table during desulfurizing agent hot recycling
Generated in face or endoporus, absorption, deposition elemental sulfur and other materials such as CS2, mercaptan, thioether, the organic sulfur such as thiophene and again
Matter hydrocarbon such as tar is desorbed, blows down and recover its hydrolysis property.Regeneration condenser tail gas contains COS, CS of a small amount of thermal desorption2, sulphur
The heavy hydrocarbon such as the organic sulfurs such as alcohol, thioether, thiophene and tar, can go torch to burn up, or go the boiler with desulfurizer to burn.
Using high temperature furnace unstripped gas as hydrolysis desulfurizing tower hydrolytic reagent-desulfurizing agent bed hot recycling purge gass when, can return high temperature furnace after
It is continuous to be used as reactor feed gas.If there is low-pressure steam supply, available for the heating at hot recycling initial stage, desulfurizing tower is included desulfurizing agent bed
Layer including be heated to 100 DEG C or so it is more convenient.Hydrolysis desulfurizing tower is down to regulation with multiple hot recycling performance by long-term use will
After asking, hot recycling can be carried out by cutting out before unloading agent, and elemental sulfur desulfurizing agent, hydrolytic reagent are adsorbed, deposited and other materials are such as
CS2, mercaptan, thioether, the organic sulfur such as thiophene and heavy hydrocarbon such as tar fusing, gasification, desorption, blow down, unload agent after cooling.Unload agent
Journey convenience, safety, health, free from extraneous odour, draw off useless agent without elemental sulfur, COS, CS2, mercaptan, thioether, the organic sulfur such as thiophene and again
Matter hydrocarbon, free from extraneous odour is safer, is also easily processed.
In gas of the present invention in higher concentration COS low temperature removal methods, the vertical pipes of hydrolysis desulfurizing tower are deeply hydrolyzed
The height 0.5-10m of agent desulfurizing agent bed, tube pitch 0.05-0.15m, heat exchange area 5-10m2/m3Hydrolytic reagent desulfurizing agent；Hydrolysis
The bottom of agent desulfurizing agent bed, can load inert ceramic balls and be supported, drawing off when being easy to the hydrolytic reagent desulfurizing agent to scrap；Under sleeve pipe
The end socket at end is spherical, spheroid shape or taper, it is to avoid its lower end pressure when being changed with temperature, the variation casing length of pressure
Broken hydrolytic reagent desulfurizing agent causes casing deformation to be damaged；Hydrolytic reagent desulfurizing agent filling pipe upper end, which is extended to, moves thermal medium distributing chamber
On bottom plate or on roof, or beds upper lateral part reactor outer wall.The position point of hydrolytic reagent desulfurizing agent filling pipe
Cloth, diameter dimension and it should be appropriately arranged with the relative position of vertical pipes, it is to avoid influence closes on the spacing of sleeve pipe, it is ensured that regeneration
When filling pipe below hydrolytic reagent desulfurizing agent bed temperature meet the requirements, filling pipe upper end may extend on the bottom plate of lower room or on
On ceiling wall, or bed upper lateral part reactor outer wall.
In gas of the present invention in higher concentration COS low temperature removal methods, hydrolysis desulfurizing tower enters the O in implication2Content, reaches
To by COS, H2S is completely converted into the reaction consumption needed for elemental sulfur, can be needed with slightly higher 0.01-0.10% (volume content)
It is controlled, including the amount of allocating of high temperature furnace oxygen or oxygen containing feed and specifically occurs for adjustment gas-generating apparatus such as These gases
The operating conditions such as supplying method.O2Content can reach desulphurization reaction requirement when not enough by filling into oxygen.O2Hydrolytic reagent when content is high
In easily generation elemental sulfur cause in activity decrease, desulfurizing agent elemental sulfur easily in surface or aperture deposition, block, cause Sulfur capacity
Decline, the sulfation of hydrolytic reagent and desulfurizer active component or carrier can also be accelerated, so as to shorten the regeneration period of desulfurizing tower
And service life.
In gas of the present invention in higher concentration COS low temperature removal methods, hydrolysis desulfurizing tower loads COS hydrolytic reagents, H2S
The ratio of oxidation desulfurizing agent, mainly according to the performance of hydrolytic reagent, desulfurizing agent, and H in process gas2S, COS content situation are true
It is fixed, obtain desulfurized effect, change the better balance of agent cycle, regeneration times and operating cost etc..
In gas of the present invention in higher concentration COS low temperature removal methods, remaining COS during hydrolysis desulfurizing tower is worked off one's feeling vent one's spleen
Further removing, the following process that can combine gas is carried out.If contained other compositions will pass through pressure swing adsorption method, solvent absorption
Method is separated, and should simultaneously consider largely to remove remaining COS, such as the follow-up CO of CO gas is produced in foregoing Gas-making Furnace2
In separation process, it is preferred to use molecular sieve vacuum pressure swing adsorption process and polyglycol dimethyl ether process, in separation CO2While also will
Most of COS of last hydrolysis oxidation is segregated into gained richness CO in process gas2In gas.
In gas of the present invention in higher concentration COS low temperature removal methods, CS in process gas2, mercaptan, thioether, thiophene etc.
The content of organic sulfur and its processing are also a major issue, the filling low temperature COS hydrolytic reagents hydrolysis and H2S oxidation desulfurizing agents
Desulfurizing tower it is generally not ideal enough to the processing of this kind of organic sulfur or not economical enough, should try one's best by adjusting gas-generating apparatus
As These gases occur high temperature furnace operating condition suitably reduce the content of this kind of organic sulfur in process gas, should also subsequently through
This kind of organic sulfur is isolated simultaneously as far as possible during pressure swing adsorption method, the contained other main components of solvent absorption separation
Go, the CO of CO gas techniques is such as produced in the Gas-making Furnace2Suitable adsorbent, absorbing liquid and operating condition are used in separation process
Most this kind of organic sulfurs are removed simultaneously.It is available for CO2Separate the different kinds of molecules sieve adsorbant selected, NHD
Base absorbing liquid also has compared with high score from CS2And the ability of the other polarity organic sulfurs in part, this is techniques known.Rich CO2
Gas returns contained COS, CS when Gas-making Furnace is recycled2Isopolarity organic sulfur is also circulated, and this part organic sulfur and coke are former
The sulfide that material strip enters, except ashes are partly into, remaining keeps or formd the H in raw gas2S、COS、CS2、SO2Composition,
Wherein overwhelming majority COS in hydrolysis desulfurizing tower generation elemental sulfur and is recovered as sulphur in hot recycling.Hydrolysis desulfurizing tower was operated
To the CS that works off one's feeling vent one's spleen in journey2Content can be controlled not.
In gas of the present invention in higher concentration COS low temperature removal methods, hydrolysis desulfurizing tower after by pressure swing adsorption method,
The outlet process gas of the contained other main component processes of solvent absorption separation, carries out fine de-sulfur processing, makes the gas after fine de-sulfur
Body total sulfur (in terms of S)≤0.1ug/L, or even≤0.05 ug/L.
Higher concentration COS low temperature removal methods in gas of the present invention, preferably solve desulfurization side where prior art
Contained H in the problem of face is present, gas2The substantially all reaction of S, COS is converted into elemental sulfur removing, while consuming process gas
In O2, sweetening process is simple and reliable, it is easy to control, and processing capacity elasticity is big, to H2S, COS content height and fluctuation strong adaptability,
Safety and environmental protection, operating cost is low, it is adaptable to the processing of low discharge gas, including advantages below：
(1) in hydrolysis desulfurizing tower, COS hydrolytic reagents, H2S oxidation desulfurizing agents mixed packing or lamination filling are used in combination, and pass through
Oxidation desulfurizing agent is H2S concentration control in relatively low level, make COS percent hydrolysis be maintained at for a long time more than 90% or even 95% with
On；Hydrolytic reagent maintains higher COS hydrolysis properties also by hot recycling；
(2) regenerated during more than 90% or even more than 95% total sulfur is converted into elemental sulfur, hot recycling by hydrolysis desulfurizing tower
Condenser trapping is sulphur；
(3) hydrolysis desulfurizing tower filling hydrolytic reagent, desulfurizing agent especially using big mesoporous activated carbon as the desulfurizing agent of carrier, additionally it is possible to inhale
Attached CS2, mercaptan, thioether, organic sulfur and the heavy hydrocarbon such as tar such as thiophene, and blown down during hot recycling or part is blown down, only
Process gas is changed；
(4) first normal pressure, the most of sulfide of low pressure removing, sulfide leakage is few during process gas pressurization and following process,
Environmental odors are smaller, and the corrosion to compressor is lighter；
(5) remaining a small amount of COS, CS2Largely removed in subsequent separation process Deng organic sulfur, it is more reasonable that technique is set
(6) sulfide content of gas obtained by later separation is easily reached such as the reduced levels within 30ppm or even 10ppm, is entered
The processing of row fine de-sulfur is more convenient, and whole cost is relatively low.
Brief description of the drawings
A kind of structure of hydrolysis desulfurizing tower used in the low temperature removal methods that Fig. 1 is higher concentration COS in gas of the present invention.
Fig. 1 hydrolyzes the legend of desulfurizing tower：1 hydrolysis desulfurization tower shell, 2 hydrolytic reagent reactive desulfurizing agent beds, 3 hydrolytic reagent desulfurization
Agent filling pipe, 4 heating medium upper chambers, 5 vertical pipes inner tubes, 6 vertical pipes outer tubes, 7 heating medium upper chambers, lower room bottom plate, 10
Vertical pipes, 11 support porcelain balls, 12 Crude product inputs, 13 heating medium inlets, 14 hydrolytic reagent desulfurizing agents unload agent mouthful, and 15 contain
COS process gas is imported and exported, room under 21 heating media.
Embodiment
Tested below with the removing of COS in raw gas, technical scheme is illustrated.
Embodiment
Raw gas is derived from gas making workshop, is produced by coke, carbon dioxide and oxygen in Gas-making Furnace, gasifier control system point
1100~1200 DEG C of temperature, the raw gas that 600~700 DEG C of furnace roof cools through the useless pot of high temperature, the useless pot byproduct steam of low temperature, then through following
Ring water- to-water heat exchanger is further cooled to 30-40 DEG C, and tar removing, dust impurities, tolerance 5000-6000Nm are removed through electro detarrer3/
H, gauge pressure 10-15kPa；Raw gas is constituted substantially（Volume content）For CO 68%, CO229%th, O2 0.20%、H21.2%th,
H2S0.07%, COS0.16%, CS20.003%th, H2O 0.8%, and micro HCl, HCN, NOx, SO3And AsH3、PH3。
Sideline test device, the 50L protective agents tank, heater, 100L for mainly including being sequentially connected along airflow direction is hydrolyzed
Desulfurizing tower, 50L regeneration condensers（Water cooling, coil area 3m2）, wherein protective agent it is canned fill out XDL-3 calcium based dechlorinating agent and
RAs988 copper systems Hydrodearsenic Catalyst (sulphided state) each 20L, hydrolysis desulfurizing tower uniformly loads in mixture A911G tempreture organic sulphur hydrolysis agent 50L and Z801 work
Property charcoal desulfurizing agent 50L, wherein hydrolytic reagent, desulfurizing agent is all Φ 3x (3-6) mm bar shaped, hydrolysis agent carrier be macropore gamma oxidation
Aluminium, main active is K2CO3, its hydrolyze COS ability it is stronger, desulfurizing agent is H2S oxidation desulfurizing agents, can be by H2S and technique
SO contained by gas2、O2Reaction is converted into elemental sulfur absorption, is deposited in the endoporus of desulfurizing agent or surface.
Hydrolyze desulfurizing tower structure as shown in Figure 1, including hydrolytic reagent desulfurizing agent bed, vertical pipes and top rise distribution
With the upper and lower two heating dielectric chamber for collecting heating medium effect, and process gas access way and interface, hydrolytic reagent desulfurizing agent
Construct for handling；Vertical pipes are formed by inner and outer tubes nesting, and inner tube upper end open is in upper chamber bottom plate, and outer tube upper end open is under
Room bottom plate；Sleeve pipe extends down into hydrolytic reagent-desulfurizing agent bed, until under the bottom of hydrolytic reagent-desulfurizing agent bed, outer tube
End closure, inner tube lower end extends on the sealing end of outer tube and is open；Hydrolytic reagent desulfurizing agent bed external diameter 400m, height
900m；Vertical pipes spacing 30mm, sleeve pipe inner tube Φ 6x1mm, outer tube Φ 12x1.5mm, sleeve pipe radical 75, heat exchange area 2.8
m3, it is highly all 100mm to move room and upper chamber under thermal medium；It is hydrolytic reagent desulphurizer mixing bed, the filling of bed bottom between sleeve pipe
Φ 6mm inert ceramic balls 20L is supported, and bottom of towe unloads agent mouthful 200mm lower than its lower end plane suitable for reading.Separately match somebody with somebody air blower and electrical heating
Hot-blast stove.Process gas flow is in being upper entering and lower leaving along casing axis direction, desulfurization operation process in hydrolytic reagent-desulfurizing agent bed
Vertical pipes do not play a part of to heat or cooled.
The main operating process conditions of sideline test device are：Raw gas tolerance 25Nm3/h（Tempreture organic sulphur hydrolysis agent, activity
The gas space velocity of charcoal desulfurizing agent is all 500h-1）, protective agent normal-temperature operation, 60 DEG C of hydrolysis desulfurizing tower inlet temperature.Hydrolyze desulfurizing tower
First make heating media with 80 DEG C of hot blasts before coming into operation for the first time and bed is preheated to 60 DEG C or so through cannula system.In process of the test, slightly
Coal gas and hydrolysis desulfurizing tower enter implication, composition of working off one's feeling vent one's spleen, and per 5h, detection once, determines CO, CO2、O2、H2、H2S、COS、CS2、SO2、
Other sulfide（The organic sulfurs such as mercaptan, thioether, thiophene）、H2O content situation；The HCl of gas before and after protective agent tank, HCN, NOx,
SO3And AsH3、PH3Content situation, contrast in every 5 days is once.Operating to COS percent hydrolysis is less than 95% or H2S+SO2Reach 1.0ug/L
When, stop the supple of gas or steam and cut out hydrolysis desulfurizing tower progress hot recycling, switchback, which is supplied gas, after hot recycling terminates and cooled remains in operation, and hydrolyzes desulfurizing tower
Successively operated and regenerated each 10 times altogether, the wherein duration of runs amounts to 950h, and the recovery time amounts to 180h.
The hot recycling of hydrolytic reagent desulfurizing agent bed in desulfurizing tower is hydrolyzed, heating medium, air quantity 25- are made with 300 DEG C of hot blasts
30Nm3/ h, in vertical pipes the flow direction of heating medium be in inner tube from top to bottom, in outer tube from bottom to top or；Bed is warming up to
After 120 DEG C 3-5 m are incorporated through process gas entrance3/ h CO2Gas is purged, and continues to regenerate after 250 DEG C of reactivation outlet temperature degree
5h, drops 60 DEG C of progress bed coolings of hot blast temperature, regenerates completion to regenerating implication and being down to after 80 DEG C, switchback experimental rig afterwards
Proceed technique gas disposal.
Experiment is found, during continuously running, hydrolysis desulfurizing tower gateway CO, CO2、H2Content has essentially no difference, H2S、
COS decrement and O2Decrement it is substantially suitable, COS percent hydrolysis >=95%, H2S≤1.0ug/L, SO2≤ 0.2ug/L, is calculated
Simple substance Recovery ratio >=96.5%, activated carbon desulphurization agent Sulfur capacity 23-25%.The hydrolysis desulfurizing tower one way duration of runs depends primarily on technique
Gas COS+H2Can be substantially extensive after the decline but regeneration of visible COS percent hydrolysis in the height fluctuation situation of S contents, one way operation process
It is multiple.The 45-50h of each operation process carries out low-speed experiment, drop raw gas tolerance 10Nm3/h（Tempreture organic sulphur hydrolysis agent, work
The gas space velocity of property charcoal desulfurizing agent is all 200h-1）, as a result all it is COS percent hydrolysis >=97%.From COS percent hydrolysis during each operating
Situation sees that the COS hydrolysing activities of tempreture organic sulphur hydrolysis agent decline unobvious after 10 operatings and 9 regeneration.
In process of the test, HCl, HCN, NOx, SO in gas after protective agent tank3All it is less than 0.1ug/L, AsH3、PH3All it is less than
0.02ug/L.Desulfurizing tower is hydrolyzed to CS2, mercaptan, thioether, the organic sulfur such as thiophene removal effect it is more general, with the duration of runs
Extension be gradually reduced, but hot recycling can also recover the removing ability to these organic sulfurs substantially.
After the 10th hot recycling for hydrolyzing desulfurizing tower is completed and cooled, open bottom of towe and unload agent sealing, hydrolytic reagent and take off
Sulphur agent can easily be drawn off, and unload agent process safety health, substantially without peculiar smell, and dust and murder by poisoning are lighter.
Comparative example
The hydrolytic reagent desulfurizing agent that the hydrolysis desulfurizing tower after agent changes the outfit new, upper strata dress hydrolytic reagent will be unloaded in embodiment sideline test device
Each 50L of lower floor's desulfurizing agent, puts into operation by the flow and temperature conditionss in embodiment（Raw gas tolerance 25Nm3/ h, tempreture organic sulphur hydrolysis
Agent, the gas space velocity of activated carbon desulphurization agent are all 500h-1, 60 DEG C of hydrolysis desulfurizing tower inlet temperature）, COS percent hydrolysis 90% is found,
COS percent hydrolysis is down to 85-86% after operating 40h, carries out hot recycling by the method in embodiment, COS percent hydrolysis is low after coming into operation again
In 90%；It is carried out continuously 40h operatings and each 6 times of hot recycling, COS percent hydrolysis 87% after coming into operation for the 7th time, hydrolytic reagent activity decrease is bright
It is aobvious.The 18-20h of each operation process carries out low-speed experiment, drop raw gas tolerance 10Nm3/h（Tempreture organic sulphur hydrolysis agent, work
The gas space velocity of property charcoal desulfurizing agent is all 200h-1）, as a result all it is COS percent hydrolysis less than 91% and increases with operating and regeneration times
And be substantially declined slightly.
Tempreture organic sulphur hydrolysis agent in hydrolysis desulfurizing tower is can be seen that from embodiment, the raw gas sideline test result of comparative example
And H2The mixed packing mode of S oxidation desulfurizing agents, hence it is evident that improve COS percent hydrolysis, hydrolytic reagent activity decrease is also slower.It is limited to side
Thread test condition, does not carry out CO2Separation test simultaneously investigates CS2, remnants COS and some other polarity organic sulfur be in CO2Separated
Removing situation in journey, but think preferably realize by combining the method using prior art, to obtain required composition
With the CO gas of purity；Think that hydrolysis desulfurizing tower is worked off one's feeling vent one's spleen contained CS2, remnants COS and some other polarity organic sulfur, can be in CO2
Largely enter richness CO in separation process2Gas, with rich CO2Gas returns Gas-making Furnace, and final basic generation sulphur is reclaimed；And think
Separate CO2The sulfide content of gained CO gas is easily reached such as the reduced levels within 30ppm or even 10ppm afterwards, carries out essence de-
Sulphuring treatment is more convenient, whole cost reduction.
Claims (10)
1. higher concentration COS low temperature removal methods, mainly include in a kind of gas：Process gas maintains or is heated to 30-80 DEG C,
Water inlet solution desulfurizing tower processing；Loaded in mixture in desulfurizing tower or lamination filling COS hydrolytic reagents and H2S oxidation desulfurizing agents, the COS hydrolytic reagents
COS is hydrolyzed to H substantially2S, the oxidation desulfurizing agent hydrolyzes COS the H of generation2H contained by S and process gas2S, with process gas institute
The SO contained2、O2Reaction is converted into elemental sulfur absorption, is deposited in the endoporus of desulfurizing agent or surface；The H2S oxidation desulfurizing agents can
Carry out blowing sulphur hot recycling under 200-300 DEG C of temperature conditionss, by the fusing of the elemental sulfur that will adsorb, deposit, gasification finish
It is basic to recover desulfurization performance, COS hydrolytic reagents hydraulic performance decline after the desulfurizing agent hot recycling process of 200-300 DEG C of temperature conditionss
It is less or do not reduce substantially；
Wherein, the hydrolysis desulfurizing tower sets two or more, can connection in series-parallel use, specially vertical pipes heat supply regeneration is de-
Sulphur tower, if between the vertical pipes of sufficient amount and heat exchange area, sleeve pipe being hydrolytic reagent-desulfurizing agent bed；COS percent hydrolysis drops to
Setting and/or sulfur content of working off one's feeling vent one's spleen, which are risen to after setting, to be cut out, and thermal source is passed through into sleeve pipe and improves hydrolytic reagent-desulfurizing agent bed
Layer temperature carries out hot recycling；The vertical pipes heat supply regenerative sulfur binding tower includes hydrolytic reagent-desulfurizing agent bed and process gas is passed in and out
Passage and interface, hydrolytic reagent-desulfurizing agent construct for handling, top has set distribution and upper and lower two of collection heating medium effect add
Thermal medium room；Vertical pipes are formed by inner and outer tubes nesting, and inner tube upper end open is in upper chamber bottom plate, and outer tube upper end open is under
Room bottom plate；Sleeve pipe extends down into hydrolytic reagent-desulfurizing agent bed, until under the bottom of hydrolytic reagent-desulfurizing agent bed, outer tube
End closure, inner tube lower end extends on the sealing end of outer tube and is open；Melted during hot recycling, gasify the elemental sulfur flowed out
Collected through regenerating condenser；Hydrolyze after the completion of desulfurizing tower hot recycling, change in natural cooling cooling or sleeve pipe after cooling medium cooling
Standby or incision comes into operation.
2. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that the organic sulfur water
Solution agent is carried on macropore gama-alumina by alkali metal, the alkali of alkaline-earth metal or carbonate or activated carbon is made.
3. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that the H2S oxidations are de-
Sulphur agent is made up of macropore activated carbon supported Fe, Mn, Cu, Zn, Co and/or alkali metal oxide modifying.
4. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that hydrolysis desulfurizing tower enters
O in implication2Volume content, than by COS, H2S is completely converted into the slightly higher 0.01-0.10% of reaction consumption needed for elemental sulfur.
5. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that in hydrolysis desulfurizing tower
Process gas flow is to for along the upper entering and lower leaving in casing axis direction.
6. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that hydrolysis desulfurizing tower is worn
When progress hot recycling is cut out after thoroughly, heating medium used is hot blast, superheated steam, conduction oil in sleeve pipe.
7. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that hydrolysis desulfurizing tower is again
During life or its middle and later periods, hydrolytic reagent-desulfurizing agent bed introduces indifferent gas and makees purge gass.
8. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that hydrolysis desulfurizing tower
Vertical pipes go deep into the height 0.5-10m of hydrolytic reagent-desulfurizing agent bed, tube pitch 0.05-0.15m, heat exchange area 5-10m2/m3
Hydrolytic reagent desulfurizing agent；And/or the bottom of hydrolytic reagent-desulfurizing agent bed, load inert ceramic balls and be supported；And/or its lower end
End socket be spherical, spheroid shape or taper；And/or hydrolytic reagent desulfurizing agent filling pipe upper end extends to the bottom for moving thermal medium distributing chamber
On plate or on roof, or beds upper lateral part reactor outer wall.
9. higher concentration COS low temperature removal methods in gas as claimed in claim 1, it is characterised in that hydrolysis desulfurizing tower goes out
Implication, during contained other main components are separated subsequently through pressure swing adsorption method, solvent absorption, by remaining COS,
CS2, mercaptan, thioether, the major part in the organic sulfur such as thiophene separate simultaneously.
10. higher concentration COS low temperature removal methods in gas as claimed in claim 9, it is characterised in that hydrolysis desulfurizing tower it
The outlet process gas of contained other main component processes is separated by pressure swing adsorption method, solvent absorption afterwards, is carried out at fine de-sulfur
Reason.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381513A (en) * | 2017-09-14 | 2017-11-24 | 长沙有色冶金设计研究院有限公司 | A kind of high concentration SO2Flue gas temperature control converter and its technique for applying |
| CN113493710A (en) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | Fine desulfurization device and method |
| CN115340887A (en) * | 2022-10-18 | 2022-11-15 | 山东鹏达生态科技股份有限公司 | Blast furnace gas fine desulfurization and sulfur recycling process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723365A (en) * | 2008-10-27 | 2010-06-09 | 上海寰球石油化学工程有限公司 | Energy-saving and emission-reduction refining process for high-purity CO |
| CN106582272A (en) * | 2016-12-14 | 2017-04-26 | 山东迅达化工集团有限公司 | Desulfuration purification process for acidic waste water steam stripping ammonia gas |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723365A (en) * | 2008-10-27 | 2010-06-09 | 上海寰球石油化学工程有限公司 | Energy-saving and emission-reduction refining process for high-purity CO |
| CN106582272A (en) * | 2016-12-14 | 2017-04-26 | 山东迅达化工集团有限公司 | Desulfuration purification process for acidic waste water steam stripping ammonia gas |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381513A (en) * | 2017-09-14 | 2017-11-24 | 长沙有色冶金设计研究院有限公司 | A kind of high concentration SO2Flue gas temperature control converter and its technique for applying |
| CN113493710A (en) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | Fine desulfurization device and method |
| CN113493710B (en) * | 2020-04-08 | 2022-10-04 | 中国石油天然气股份有限公司 | Fine desulfurization device and method |
| CN115340887A (en) * | 2022-10-18 | 2022-11-15 | 山东鹏达生态科技股份有限公司 | Blast furnace gas fine desulfurization and sulfur recycling process |
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