CN110446542A - The Wet-type desulfuration method of H 2 S-containing gas - Google Patents
The Wet-type desulfuration method of H 2 S-containing gas Download PDFInfo
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- CN110446542A CN110446542A CN201780088427.3A CN201780088427A CN110446542A CN 110446542 A CN110446542 A CN 110446542A CN 201780088427 A CN201780088427 A CN 201780088427A CN 110446542 A CN110446542 A CN 110446542A
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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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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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
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- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The Wet-type desulfuration method of the H 2 S-containing gas, it is by contacting H 2 S-containing gas with desulfurization catalyst agent solution made of the dissolution desulphurization catalyst in alkaline solution, the Wet-type desulfuration method for carrying out the desulfurization of the H 2 S-containing gas uses at least one of methylnaphthohydroquinone and toluiquinone as the desulphurization catalyst.
Description
Technical field
The present invention relates to a kind of Wet-type desulfuration methods of H 2 S-containing gas, are removed from H 2 S-containing gas using damp process
Devulcanization hydrogen, and so that the hydrogen sulfide removed is become sulphur or the salt of sulfur-bearing etc. using desulphurization catalyst and recycled.
Background technique
It is taken as the main method that damp process removes hydrogen sulfide from the H 2 S-containing gas based on coke-stove gas, is had
This method of Plutarch Haake and Fu Makesifa.Which kind of all it is often used in method comprising absorption tower 1 as shown in Figure 1 and regenerator 2
Equipment.Absorption tower 1 makes H 2 S-containing gas 3 and dissolves desulfurization catalyst agent solution 5 made of desulphurization catalyst in alkaline solution
Contact.Regenerator 2 contacts oxygen-containing gas 6 with the desulfurization catalyst agent solution 5.
In absorption tower 1, by contacting H 2 S-containing gas 3 with desulfurization catalyst agent solution 5, make in H 2 S-containing gas 3
Contained hydrogen sulfide dissolves in desulfurization catalyst agent solution 5.Hydrogen sulfide is removed from H 2 S-containing gas 3 as a result, and obtains purified gas
Body 4.The hydrogen sulfide for dissolving in desulfurization catalyst agent solution 5, and being reacted with the desulphurization catalyst for being dissolved in desulfurization catalyst agent solution 5 by
Oxidation, becomes the ion of the sulphur of solid-like or the salt of sulfur-bearing or sulfur-bearing.At this point, desulphurization catalyst itself is reduced, from oxysome
Variation is Reduction Body.
In addition, being contacted, being made with the desulfurization catalyst agent solution 5 for having hydrogen sulfide is dissolved in by making oxygen-containing gas 6 in regenerator 2
Oxygen contained in the oxygen-containing gas 6 of contact dissolves in desulfurization catalyst agent solution 5.The oxygen of desulfurization catalyst agent solution 5 is dissolved in as a result,
Gas reacts with the desulphurization catalyst of Reduction Body after reacting contained in desulfurization catalyst agent solution 5 with hydrogen sulfide.It is tied
Fruit, desulphurization catalyst revert to oxysome, and being regenerated as can be with the shape that is dissolved in the hydrogen sulfide of desulfurization catalyst agent solution 5 secondary response again
State.
Desulphurization catalyst by with the hydrogen sulfide or oxygen alternation response that are dissolved in desulfurization catalyst agent solution 5, Reduction Body with
It is round-trip between oxysome, it is utilized repeatedly.5 one side of desulfurization catalyst agent solution recycles between absorption tower 1 and regenerator 2, on one side
It is utilized repeatedly.The desulfurization catalyst agent solution 7 of the ion of salt or sulfur-bearing dissolved with sulphur generated or sulfur-bearing is to system outlet
Out.
In this method of Plutarch Haake described in Patent Document 1, mainly in tool, there are two the naphthalene of aromatic rings, tool, there are three aromatic rings
Anthracene or quinones, hydroquinones or their salt with luxuriant and rich with fragrance skeleton in, using showing standard oxidationreduction potential E0=0.45
The substance of~0.7V is as desulphurization catalyst.At this point, aromatic rings has two or more in the molecule, lead to the solubility for water
It reduces, therefore uses to improve by acidic-groups such as importing sulfonic acid, carboxylic acids and the deliquescent substance of water is urged as desulfurization
Agent.
In the past, in this method of Plutarch Haake, usually using 1,4-naphthoquinone -2- sulfonate or its Reduction Body as catalyst.Water
The quinonyl of catalyst compounds in solution is aoxidized and is restored repeatedly, by 1,4-naphthoquinone -2- sodium sulfonate and its Reduction Body it
Between it is round-trip, or between 1,4-naphthoquinone -2- ichthyodin and its Reduction Body it is round-trip, thus make to be dissolved in desulfurization catalyst agent solution
Hydrogen sulfide is as the sulphur of solid or the salt comprising sulphur or the aqueous solution comprising ion.
When the invention of patent document 1 is completed, purpose is mainly the recycling of solid sulfur, but the market value by solid sulfur
Fluctuation etc., generalized recently as the technology that the salt comprising sulphur or the aqueous solution comprising ion are recycled.Non- patent text
Offer in 1, develop the catalyst for being recovered more easily as aqueous solution, to only with aromatic rings 1,2,4-trihydroxybenzene,
4- methyl pyrocatechol is studied.1,2,4-trihydroxybenzene shows good desulphurizing activated, but valence in normal state
Lattice are expensive, and there are problems in practical use.On the other hand, 4- methyl pyrocatechol can also decompose in air in the past in addition to expensive,
Therefore it needs to save under inert gas atmosphere, cost when storing, conveying increases.
In addition, the Fu Makesifa of patent document 2 is using the more nitro compounds of aromatic series or aromatic series polyoxy compounds
The Wet-type desulfuration method of H 2 S-containing gas as shown in Figure 1 as catalyst, as its desulphurization catalyst, usually using bitter
It is sour.The recycling form of sulphur is not only the sulphur of solid, and also the salt frequently as sulfur-bearing or the aqueous solution dissolved with ion are recycled.
Citation
Patent document 1: Japanese Patent Publication 39-001015 bulletin
Patent document 2: Japanese Patent Publication 33-007084 bulletin
Patent document 3: Japanese Unexamined Patent Publication 8-059600 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2012-25900 bulletin
Non-patent literature 1: interior Tian Yang, Jin Liuyitong, river Tian Da are also, rugged too two youths in temple, island good fortune, pit shaft and a youth write
" using 2- nitroso-Neville acid Wet-type oxidation sweetening method " fuel association magazine, volume 60,1981, p.58-
64
Summary of the invention
Shape in Plutarch Haake this method, Fu Makesifa, when form when storing desulphurization catalyst, conveying desulphurization catalyst
State is all aqueous solution, therefore has the problem of cost cost etc in a large amount of storages, when conveying.Therefore, it is desired in storage,
The desulphurization catalyst for not becoming aqueous solution when conveying, becomes the desulphurization catalyst of solid-like.
But the picric acid of the desulphurization catalyst as Fu Makesifa has explosivity if drying if solidification,
Therefore it in storage, a large amount of picric situations of conveying, can only for security reasons be handled with aqueous solution state.
On the other hand, the desulphurization catalyst of this method of Plutarch Haake is as described in Patent Document 3, there are it is solidified can
Can property, but need once the product produced as aqueous solution to be made to saltout and crystallization, therefore make the desulfurization of this method of Plutarch Haake
The complex process of photocatalyst crystals and there is a problem of into it is of the invention, currently without for manufacturing, it is difficult to obtain solidification
Product.
Although price is high in addition, the 1,2,4-trihydroxybenzene studied in non-patent literature 1 is sold with solid-like, exist
Problem in practical use.4- methyl pyrocatechol price is also high, furthermore can decompose in air, it is therefore desirable in inert gas atmosphere
Lower preservation, cost when storing, conveying increase.
In view of the above subject, the object of the present invention is to provide a kind of uses to be handled with solid-like, there is no explosivities
Etc safety problem, be easy low cost obtain and with the desulfurization performance same with previous desulphurization catalyst desulfurization
The Wet-type desulfuration method of the H 2 S-containing gas of catalyst.
In view of the above subject, the present inventor to as it is explosive less and the catalyst of solid-like is conscientiously studied.Its
As a result, discovery uses one or both of methylnaphthohydroquinone and toluiquinone as desulfurization catalyst in Wet-type desulfuration method
Agent, desulphurizing ability are high.
The present inventor is from the viewpoint of storage, conveying cost, for chemical combination that can be few with solid-like processing, aromatic rings
Object is studied.In order to ensure water solubility in patent document 1, it is necessary to acidic-group is imported, but if being that intramolecular only has 1
The compound of aromatic rings, then do not need especially to import acidic-group be also able to carry out it is aqueous solubilized.In addition, in non-patent text
It offers and confirms that active 1,2,4-trihydroxybenzene due to valuableness, is difficult to functionization from the viewpoint of cost in 1.Therefore, right
In the position of with same substituent group and only functional group, different pyrogallols is studied, and could not be obtained adequately
Activity.So being not only the type of simple functional group, it is necessary to be studied in view of its positional relationship.
In hydroquinone or catechol by a methyl instead of compound, can in the same manner as 1,2,4-trihydroxybenzene
It is enough to be handled with solid-like, from the viewpoint of storage, conveying cost preferably.In non-patent literature 1, to 4- methyl pyrocatechol into
Research is gone, but 4- methyl pyrocatechol is unstable compound, can be decomposed in air, so needing in inert gas gas
It is saved under atmosphere, cost when storing, conveying increases.
Therefore, for as in other hydroquinones or catechol by a methyl instead of compound methyl hydrogen
Quinone is studied.As a result, recognizing that methylnaphthohydroquinone has adequately activity.Its reaction mechanism is as shown in Fig. 2, with previous
This catalyst of Plutarch Haake is same, occurs in the part of quinonyl by lysed hydrogen sulfide (H2S) reduction of 11 progress, Yi Jiyou
Oxygen (O2) 13 oxidations carried out, it changes between the toluiquinone 9 of oxysome and the methylnaphthohydroquinone 10 of Reduction Body.
Therefore, even if any one of toluiquinone, methylnaphthohydroquinone are used only in reaction system, the quinonyl of catalyst also can be anti-
Both it is oxidized and reduced again, it is round-trip between oxysome and Reduction Body, exist in reaction system, to carry out desulfurization.
In addition, methylnaphthohydroquinone is sold usually as solid powder, it is very easy to obtain.As previous purposes, there is polymerization
Raw material, polymerization inhibitor, polymerization inhibitor, stabilizer of object etc., therefore market value is protected, and can expect more stable confession
It gives.Also a large amount of manufactures are able to carry out, with 1/10th or less of the 1,2,4-trihydroxybenzene, a quarter of 4- methyl pyrocatechol
Left and right obtains cheaply.In addition, the toluiquinone of the oxysome as methylnaphthohydroquinone generally also can be in polymerization inhibitor, oxygen
It circulates in the purposes of agent, therefore can also be used as oxysome and obtain desulphurization catalyst, to more easily obtain desulfurization catalyst
Agent.
Like this, discovery is made in Wet-type desulfuration method by using one or both of methylnaphthohydroquinone and toluiquinone
For desulphurization catalyst, it is able to solve project of the invention, so as to complete the present invention.
(1) Wet-type desulfuration method for the H 2 S-containing gas that a technical solution of the invention is related to, is by making Containing Sulfur
Hydrogen with desulphurization catalyst is dissolved in alkaline solution and the desulfurization catalyst agent solution that is formed contacts and carries out the Containing Sulfur
The Wet-type desulfuration method of the desulfurization of hydrogen uses at least one of methylnaphthohydroquinone and toluiquinone as the desulfurization catalyst
Agent.
(2) in the Wet-type desulfuration method for the H 2 S-containing gas that above-mentioned (1) is recorded, it is molten as the alkalinity that ammonia can be used
The alkali source of liquid.
(3) in the Wet-type desulfuration method for the H 2 S-containing gas that above-mentioned (1) or (2) is recorded, the desulfurization catalyst agent solution
It can be and at least one of the methylnaphthohydroquinone and described toluiquinone are put into the alkaline solution in a solid state make it
Dissolution and manufacture.
It (4), can will be described in the Wet-type desulfuration method for the H 2 S-containing gas that any one of above-mentioned (1)~(3) is recorded
At least one of methylnaphthohydroquinone and the toluiquinone put into the desulfurization catalyst agent solution in a solid state, supplement described de-
Sulfur catalyst.
(5) it in the Wet-type desulfuration method for the H 2 S-containing gas that any one of above-mentioned (1)~(4) is recorded, can be set to: benefit
With absorption tower and regenerator. while recycling the desulfurization catalyst agent solution between the absorption tower and the regenerator
Carrying out desulfurization contacts the H 2 S-containing gas with the desulfurization catalyst agent solution in the absorption tower, thus makes described
Hydrogen sulfide in H 2 S-containing gas is dissolved in the desulfurization catalyst agent solution, from the H 2 S-containing gas described in removing
Hydrogen sulfide obtains purified gases, makes the desulfurization catalyst agent solution dissolved with the hydrogen sulfide from the absorption tower to described
Regenerator circulation, in the regenerator, contacts oxygen-containing gas with the desulfurization catalyst agent solution, generates the salt of sulphur, sulfur-bearing
Or the ion of sulfur-bearing, the ion of the sulphur, the salt of the sulfur-bearing or the sulfur-bearing is recycled, then makes the desulphurization catalyst molten
Liquid is recycled to the absorption tower.
It (6), can be for the regenerator, by institute in the Wet-type desulfuration method for the H 2 S-containing gas that above-mentioned (5) are recorded
It states at least one of methylnaphthohydroquinone and the toluiquinone and the desulfurization catalyst agent solution is put into solid-like, supplement the desulfurization
Catalyst.
Above-mentioned each technical solution according to the present invention is capable of providing a kind of Containing Sulfur hydrogen using following desulphurization catalysts
The Wet-type desulfuration method of body, the desulphurization catalyst are used as desulfurization by using one or both of methylnaphthohydroquinone and toluiquinone
Catalyst is obtained and is had so as to be handled with solid-like, there is no the safety problem of explosivity etc, easy low cost
The same desulfurization performance with previous desulphurization catalyst.
Detailed description of the invention
Fig. 1 is the general configuration figure using the Wet-type desulfuration method of the H 2 S-containing gas of general desulphurization catalyst.
Fig. 2 is methylnaphthohydroquinone and toluiquinone and hydrogen sulfide (H2) and oxygen (O S2) presumption reaction equation.
Fig. 3 is the schematic diagram of the desulphurization plant of the regenerator with the input port provided with solid-like desulphurization catalyst.
Fig. 4 is the schematic diagram for having both the desulphurization plant of function on absorption tower and regenerator.
Fig. 5 is the schematic diagram of HDS catalysts active evaluation experimental device used in embodiment 1,2 and comparative example 1~7.
Fig. 6 is the schematic diagram of desulfurization test device used in embodiment 3~5 and comparative example 8,9.
Specific embodiment
Hereinafter, being illustrated to one embodiment of the present invention.As shown in Figure 1, the Wet-type desulfuration method of present embodiment
It is same as previous Wet-type desulfuration method, it is made of absorption process and step for regeneration this two big process.
The absorption process of one is the desulfurization catalyst agent solution 5 for making hydrogen sulfide contained in H 2 S-containing gas 3 and alkalinity
Contact, makes hydrogen sulfide dissolve in the process of desulfurization catalyst agent solution 5, executes on absorption tower 1.
H 2 S-containing gas 3 is mainly the various exhaust gas from discharges such as gas retort, heating furnace, power plants, is containing 10ppm
The gas of the hydrogen sulfide of~10000ppm or so.In addition, about H 2 S-containing gas 3, from hydrogen sulfide to the dissolution of alkaline solution
The problem of balance, sets out, and the gas of the hydrogen sulfide containing high concentration can be realized high hydrogen sulfide removal rate to a certain extent, because
This is more preferably the gas containing 1000ppm or more and 10000ppm hydrogen sulfide below.In addition to vulcanization in H 2 S-containing gas 3
Other than hydrogen, hydrogen, methane, carbon monoxide, carbon dioxide, nitrogen, ammonia, hydrogen cyanide etc. can be contained.The coke being discharged from coke oven
Producer gas usually contains the hydrogen sulfide of above-mentioned degree, is the good example using the H 2 S-containing gas 3 of present embodiment.
By contacting H 2 S-containing gas 3 with desulfurization catalyst agent solution 5, make vulcanization contained in H 2 S-containing gas 3
Hydrogen to desulfurization catalyst agent solution 5 dissolve, even if at this point, other sour gas such as hydrogen cyanide contained in H 2 S-containing gas 3 to
The dissolution of desulfurization catalyst agent solution 5 is also not related, and especially removing hydrogen cyanide simultaneously, also there is no problem as a purpose.
The desulfurization catalyst agent solution 5 for dissolving in hydrogen sulfide by contacting H 2 S-containing gas 3, is by methylnaphthohydroquinone and first
One or both of benzoquinones is dissolved in alkaline solution as desulphurization catalyst and is formed.At this point, in order to obtain adequately
Activity, the concentration of desulphurization catalyst are preferably 0.01mmol/L or more.In addition, since solubility of the toluiquinone for water is little,
Therefore the upper limit is preferably 100mmol/L or less.
In addition, needing the pH value by desulfurization catalyst agent solution 5 to remain to absorb hydrogen sulfide from H 2 S-containing gas 3
Alkalinity, but if becoming excessively high alkalinity then will lead to the activity reduction of desulphurization catalyst.Therefore, desulfurization catalyst agent solution 5
PH value is preferably kept at 7.5~11.0 range.
By using one or both of methylnaphthohydroquinone and toluiquinone be used as desulphurization catalyst, such as with used as tower
The case where 1,4-naphthoquinone -2- sodium sulfonate of the desulphurization catalyst of this method of gram Haake, is compared, in the existing of 1,4-naphthoquinone -2- sodium sulfonate
Sale form (1mol/L sodium-salt aqueous solution) in, every 1kg include about 1mol 1,4-naphthoquinone -2- sodium sulfonate, in contrast,
Every 1kg includes the methylnaphthohydroquinone of 8mol in methylnaphthohydroquinone powder.In the molecule of any desulphurization catalyst, have relative to 1 molecule
There are 1 active site, therefore the active site about Unit Weight, methylnaphthohydroquinone powder is relative to the Isosorbide-5-Nitrae-that usually can be obtained
Naphthoquinones -2- sulfonic acid sodium water solution is 8 times, can reduce the expense of storage, transport.Consider from this viewpoint, preferably ring
The material that quantity is few, substituent group is few.One or both of methylnaphthohydroquinone and toluiquinone used in the present invention, the number of aromatic rings
Amount is 1, and substituent group also only one methyl can effectively reduce the expense of storage, transport.
As the alkali source for the alkaline solution for constituting desulfurization catalyst agent solution 5, using sodium hydroxide, sodium carbonate, ammonia etc..This
In embodiment, alkali metal can be contained as one or both of the methylnaphthohydroquinone of desulphurization catalyst and toluiquinone.Therefore,
Especially by alkali source is used ammonia as, the effect that desulfurization is carried out using the desulfurization catalyst agent solution of not alkali metal containing can be played
Fruit.This recycles sulfate ion or the process or desulphurization catalyst is molten of its salt after this process from desulfurization catalyst agent solution 5
In the process that liquid 5 is handled as waste liquid, the damage etc. that equipment is caused by alkali metal is needed not worry about.Be conducive to subtract as a result,
Light equipment, operational limitation, therefore it is preferable to use ammonia as alkali source.
As the contact method of desulfurization catalyst agent solution 5 and H 2 S-containing gas 3, the lower guide from absorption tower 1 can be
Enter H 2 S-containing gas 3, spreads desulfurization catalyst agent solution 5 from the top on absorption tower 1, desulfurization catalyst agent solution 5 is made to absorb vulcanization
The method of hydrogen.Alternatively, it is also possible to be to store desulfurization catalyst agent solution 5 in absorption tower 1, to the desulfurization catalyst agent solution 5 of storage
The method for being blown into H 2 S-containing gas 3.Alternatively, it is also possible to use other methods without contact.In the lower guide from absorption tower 1
Enter H 2 S-containing gas 3, in the case where spreading desulfurization catalyst agent solution 5 from the top on absorption tower 1, in order to further increase sulfur-bearing
Change the contact area between hydrogen 3 and desulfurization catalyst agent solution 5, can use filler etc..
Step for regeneration is illustrated referring especially to Fig. 3, for clear and Fig. 1 corresponding relationship, in the following description
Label in Fig. 1 is attached to bracket sometimes and indicates.Furthermore Fig. 3 is with the input port provided with solid-like desulphurization catalyst
The schematic diagram of the desulphurization plant of regenerator.
Step for regeneration is to be blown into oxygen-containing gas 20 (6) to the desulfurization catalyst agent solution 5 for absorbing hydrogen sulfide, makes desulfurization catalyst
Agent regeneration, and make the hydrogen sulfide being dissolved in desulfurization catalyst agent solution 5 as the process of sulphur or the ion of the salt or sulfur-bearing of sulfur-bearing.
Step for regeneration is implemented in regenerator 19 (2).Oxygen-containing gas 20 for making methylnaphthohydroquinone be oxidized to toluiquinone, can be used air,
Oxygen or oxygen enrichment air etc..
For in desulfurization catalyst agent solution 5 as the toluiquinone of the oxysome of desulphurization catalyst and as the methyl of Reduction Body
The function of quinhydrones is illustrated.In absorption tower 16 (1), if dissolved hydrogen sulfide in the alkaline solution comprising desulphurization catalyst,
Then the toluiquinone in desulfurization catalyst agent solution 5 reacts with hydrogen sulfide and becomes methylnaphthohydroquinone.Alkalinity is dissolved in absorption tower 16
The amount of the hydrogen sulfide of solution is higher than the concentration of desulphurization catalyst, therefore from the desulfurization catalyst agent solution 5 that absorption tower 16 is taken out
Desulphurization catalyst almost all becomes methylnaphthohydroquinone, in the state that the processing of the hydrogen sulfide of whole amount is not completed, Xiang Zaisheng
Tower 19 carries out liquor charging.In regenerator 19, as described above, by being blown into oxygen-containing gas 20, in methylnaphthohydroquinone and oxygen-containing gas
Oxygen reacts and becomes toluiquinone, therefore can react again with hydrogen sulfide.
The desulphurization catalyst in the desulfurization catalyst agent solution 5 of regenerator 19 is imported from 16 liquor charging of absorption tower, as described above,
Almost all becomes methylnaphthohydroquinone, reacts and reacts with hydrogen sulfide with oxygen but if being repeated in regenerator 19, takes off
Vulcanization hydrogen amount in sulfur catalyst solution 5 gradually decreases, then toluiquinone can not be reacted with hydrogen sulfide.On the other hand, due at any time
Oxygen is supplied, only carrying out methylnaphthohydroquinone becomes the reaction of toluiquinone, therefore in the desulphurization catalyst in desulfurization catalyst agent solution 5
The ratio of toluiquinone is gradually increasing.The desulfurization catalyst agent solution 5 that the ratio of toluiquinone rises, from regenerator 19 to absorption tower 16
Liquor charging simultaneously recycles.Therefore, the hydrogen sulfide in desulfurization catalyst agent solution 5, part of it are oxidized in absorption tower 16, big half portion
Divide and be oxidized in regenerator 19, becomes the salt of sulphur or sulfur-bearing or the ion of sulfur-bearing.
In addition, due to being above-mentioned such mechanism, as the desulphurization catalyst for being dissolved in desulfurization catalyst agent solution 5,
Both either any one of methylnaphthohydroquinone and toluiquinone, be also possible to.This is because by reaction, absorption tower 16,
Among regenerator 19 is respective, can all it stablize as existing forms as described above.
The contact method of desulfurization catalyst agent solution 5 and oxygen-containing gas 20 can be and store desulfurization catalyst in regenerator 19
Agent solution 5, the method for being blown into oxygen-containing gas 20 to the desulfurization catalyst agent solution 5 of storage.Alternatively, it is also possible to being from regenerator 19
Oxygen-containing gas 20 is included in lower part, spreads desulfurization catalyst agent solution 5 from the top of regenerator 19, absorbs desulfurization catalyst agent solution 5
Furthermore the method for hydrogen sulfide is also possible to other methods.
Equipment as process and step for regeneration absorb, as set forth above, it is possible to by absorption tower 16 (1) and regenerator 19
(2) be formed as individual structure, as shown in figure 4, if it is considered that not making the H 2 S-containing gas 24 being blown into and oxygen-containing gas 30
Mixing then can also implement (referring for example to patent document 4 etc.) by an equipment for having both the function of regenerator and absorption tower.
In Fig. 4, the spaced walls 27 than being arranged in tower play a role by top as absorption tower, implement to absorb on the top
Process.In addition, playing a role by lower part as regenerator than spaced walls 27, implement step for regeneration.
Top is being leaned on than spaced walls 27, is being blown into H 2 S-containing gas 24 from the position close to spaced walls 27.By out of tower
Top the desulfurization catalyst agent solution 28,31 dissolved with desulphurization catalyst recycled is spread, make itself and Containing Sulfur
Hydrogen 24 contacts.As a result, the hydrogen sulfide in H 2 S-containing gas 24 is desulfurized the absorption of catalyst solution 28,31, eliminate
The H 2 S-containing gas 24 of hydrogen sulfide is recovered near tower top as purified gases 25.At this point, in order to increase Containing Sulfur hydrogen
Contact area between body 24 and desulfurization catalyst agent solution 28,31, can be in the introduction part of the H 2 S-containing gas 24 on tower top
The setting filling oxidant layer 26 between the leading-out portion of purified gases 25.The desulfurization catalyst agent solution 28,31 for absorbing hydrogen sulfide passes through
Spaced walls 27 are stored in tower lower part via hermetically sealed can 29.It is blown into the desulfurization catalyst agent solution 28 for being stored in tower lower part oxygen-containing
Gas 30 carries out the regeneration of desulphurization catalyst.Oxygen-containing gas 30 in desulfurization catalyst agent solution 28 after passing through, as exhaust gas 33
Discharge.It is stored in the desulfurization catalyst agent solution 28,31 of tower lower part, be discharged from tower lower part and passes through liquid-feeding pump 32 from tower upper guide
Enter, is thus recycled.By spaced walls 27 and hermetically sealed can 29, make the H 2 S-containing gas 24 being blown into and oxygen-containing gas 30
It does not mix.
Desulfurization catalyst agent solution 5 in the desulphurization catalyst used device by solid-like of the present embodiment, 28,
When 31, the desulphurization catalyst that can be made it dissolve in advance after becoming aqueous solution in water or alkaline solution again in used device is molten
Liquid 5,28,31.Alternatively, can also by the desulphurization catalyst of solid-like in the state used device desulfurization catalyst agent solution 5,
28,31.By the desulphurization catalyst of solid-like with desulfurization catalyst agent solution 5,28,31 in the state used device the case where
Under, it does not need to make the desulphurization catalyst of solid-like to become aqueous solution, avoids the complication of process, thus preferably.
Desulphurization catalyst can deteriorate or pass through desulfurization in the process of the ion recycling of sulfur-bearing after by the salt of sulphur or sulfur-bearing
A part of catalyst solution is discharged and fades away, therefore is preferably continuously or intermittently supplemented in equipment work.In
When supplement, it may be considered that the discharge rate of the desulfurization catalyst agent solution 5,28,31 of circulation, the ingredient of the solution of discharge, circulation it is de-
Additive amount and the timing of desulphurization catalyst is suitably determined in the oxidation-reduction potential etc. of sulfur catalyst solution 5,28,31.
In addition, needing to be used for the investment of investment by the desulphurization catalyst of solid-like with state investment
Mouth setting is in a device.For example, regenerator 19 and absorption tower 16 make as specific installation, implement to store in regenerator 19 de-
In the case where sulfur catalyst solution 5 and the Fig. 3 for the method for being blown into oxygen-containing gas 20 to the desulfurization catalyst agent solution 5 of storage, preferably
On the top of regenerator 19, the input port 21 of the desulphurization catalyst of investment solid is directly set.The desulfurization stored in regenerator 19 is urged
Agent solution 5 is that the majority of the desulfurization catalyst agent solution 5 recycled in a device by being blown into oxygen-containing gas 20 becomes rush
Into the state of stirring, therefore it so that desulphurization catalyst is dissolved to desulfurization catalyst agent solution 5 and spread.
In addition, by the desulfurization catalyst agent solution 5 in the desulphurization catalyst used device of solid-like of the present embodiment
When, it may include other catalyst in desulfurization catalyst agent solution 5.For example, implementing this reality using existing wet desulfurizer
In the case where the method for applying mode, desulfurization catalyst agent solution 5 is included as used in previous this method of Plutarch Haake
1,4-naphthoquinone -2- the sulfonate and its Reduction Body of desulphurization catalyst, but can also be of the present embodiment to solution addition
The desulphurization catalyst of solid-like.
Embodiment
(comparative example 1)
As shown in figure 5, being put into the simulation reaction liquid 35 of 400mL into 500mL beaker 34, stirred using magnetic stirring apparatus 36
Simulation reaction liquid 35, and air is blown into 0.3L/min by cylinder gas injection tube 37, observe reaction.It is anti-about simulation
NaSH is set as the concentration of 10mmol/L by the composition for answering liquid 35, the replacement of the hydrogen sulfide as dissolution, will as Plutarch Haake this
1,4- naphthoquinones -2- the sodium sulfonate of the desulphurization catalyst of method is set as the concentration of 0.2mmol/L.Hydrogen sulfide is being dissolved in alkaline solution
In the case of can become hydrogen sulfite ion, therefore use ionized when aqueous solubilized NaSH for sodium ion and hydrogen sulfite ion as
The replacement of hydrogen sulfide.Due to the alkalinity of NaSH, pH value when simulation reaction liquid 35 adjusts is in the range of 7.5~11.0, therefore
PH value adjustment is not carried out using alkali source.In order to keep the activity rating of desulphurization catalyst constant, using hot bath 40 by reaction solution
Temperature is constant to remain 30 DEG C.Furthermore this test is bulge test, and the hydrogen sulfite ion concentration in simulation reaction liquid 35 continues
It is carried out under conditions of reduction.
During 30 minutes 1 hour reaction time, the sampling of multiple simulation reaction liquid 35 is carried out, Capillary Electrophoresis is utilized
Device measures hydrogen sulfite ion concentration.According to the ongoing change of hydrogen sulfite ion concentration, the slip of hydrogen sulfite ion is obtained
1.50mmol·L-1·hr-1.Furthermore by hydrogen sulfite ion concentration relative to the reaction time relationship by least square method into
Row straight line approximation finds out the size of negative slope, and the size of obtained slope is subtracted and is not put into catalyst and carries out same
The size of the slope obtained when experiment, the slip by obtained value as hydrogen sulfite ion.
(embodiment 1)
It is put into the methylnaphthohydroquinone of solid-like instead of 1,4-naphthoquinone -2- sodium sulfonate, makes it dissolve in simulation reaction liquid 35, it is real
Comparative example 1 is granted similarly to test.Concentration, alkali source, reaction temperature are all identical as comparative example 1.At this point, as hydrogen sulfite ion
Slip obtains 1.81mmolL-1·hr-1.This indicate methylnaphthohydroquinone can have with this catalyst 1 of previous Plutarch Haake,
The same above hydrogen sulfite ion processing capacity of 4- naphthoquinones -2- sodium sulfonate.
(embodiment 2)
It is put into toluiquinone instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.It is concentration, alkali source, anti-
Answer temperature all identical as comparative example 1.At this point, the slip as hydrogen sulfite ion obtains 1.63mmolL-1·hr-1.This table
The toluiquinone for being shown as the oxysome of methylnaphthohydroquinone can have and previous Plutarch Haake this catalyst 1,4- naphthoquinones -2- sulfonic acid
The same above hydrogen sulfite ion processing capacity of sodium, even if indicating using the methylnaphthohydroquinone as Reduction Body and the first as oxysome
Any form investment in benzoquinones can be utilized as desulphurization catalyst.
(comparative example 2)
It is put into hydroquinone instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.Concentration, alkali source,
Reaction temperature is all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 1.02mmolL-1·hr-1.This is indicated
As the hydroquinone of most one of simple compounds with roller base, it is unable to get and this catalyst Isosorbide-5-Nitrae-of previous Plutarch Haake
The same performance of naphthoquinones -2- sodium sulfonate.
(comparative example 3)
It is put into catechol instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.Concentration, alkali source,
Reaction temperature is all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 0.87mmolL-1·hr-1.This is indicated
Catechol as most one of simple compounds with quinonyl is unable to get and previous this catalyst of Plutarch Haake 1,4-
The same performance of naphthoquinones -2- sodium sulfonate.
(comparative example 4)
It is put into 1,2- naphthoquinones -4- sodium sulfonate instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.It is dense
Degree, alkali source, reaction temperature are all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 1.46mmolL-1·hr-1.It is same with previous Plutarch Haake this catalyst 1,4- naphthoquinones -2- sodium sulfonate that this indicates that 1,2- naphthoquinones -4- sodium sulfonate can have
Deng hydrogen sulfite ion processing capacity.But since the amount of the active site of Unit Weight is 0.477 times of methylnaphthohydroquinone, because
Methylnaphthohydroquinone used in this present invention can obtain activity same with more low weight.
(comparative example 5)
It is put into 1,2,4-trihydroxybenzene instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.Concentration,
Alkali source, reaction temperature are all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 1.53mmolL-1·hr-1.This
Indicate that 1,2,4- trihydroxy benzene there can be the hydrogen sulfide same with previous Plutarch Haake catalyst 1,4- naphthoquinones -2- sodium sulfonate
Ion processing ability.But due to more expensive than methylnaphthohydroquinone, methylnaphthohydroquinone used in the present invention can be cheaper to obtain
Activity same.
(comparative example 6)
It is put into 4- methyl pyrocatechol instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.Concentration,
Alkali source, reaction temperature are all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 1.72mmolL-1·hr-1.This
Indicate that 4- methyl pyrocatechol there can be the hydrogen sulfide same with previous Plutarch Haake catalyst 1,4- naphthoquinones -2- sodium sulfonate
Ion processing ability.But due to more expensive than methylnaphthohydroquinone, methylnaphthohydroquinone used in the present invention can be cheaper to obtain
Activity same.In addition, the problem of 4- methyl pyrocatechol is due to stability, needs to protect under inert gas atmosphere
It deposits, will lead to storage cost and increase.
(comparative example 7)
It is put into pyrogallol instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 1.Concentration, alkali source,
Reaction temperature is all identical as comparative example 1.At this point, the slip of hydrogen sulfite ion becomes 0.03mmolL-1·hr-1.This is indicated
Pyrogallol does not have hydrogen sulfite ion processing capacity, compared with the result of 1,2,4-trihydroxybenzene, even if indicating to have same
Functional group, according to its position difference, hydrogen sulfite ion processing capacity can also be had differences.
(comparative example 8)
Experimental provision is shown in Fig. 6.Absorption tower 42, which becomes to the glass system tower of tower diameter 60mm, height 900mm, inserts 10mm
Packed column of the Raschig ring of φ until the height of 750mm.Regenerator 48 is set as the glass system bubble of tower diameter 80mm, height 1300mm
Tower uses cylinder gas injection tube as gas mouth blown, effective a height of 1000mm of liquid.In addition, use the vial of 10L as
The circulation liquid bath 45 of experiment.
About the composition of simulation gas 41, prepare the nitrogen comprising 10000ppm ammonia, 5000ppm hydrogen sulfide, from above-mentioned suction
The lower part of tower 42 is received with 0.8Nm3/ hr is blown into.In addition, the flow for the air 49 being blown into from the lower part of regenerator 48 is 50NL/hr.
Simulation reaction liquid 46 is recycled in system with the flow of 45L/hr by liquid-feeding pump 47.About simulation reaction liquid 46, tower will be used as
1,4-naphthoquinone -2- sulfonic acid the na concn of the desulphurization catalyst of this method of gram Haake is set as 2mmol/L, uses ammonium hydroxide will be first as alkali source
The pH value of phase is adjusted to 9.0.Alkali source after on-test is only to simulate ammonia contained in gas 41, is not implemented in addition to this
The adjustment of pH value.
Using the gas chromatograph 44 of subsidiary flame photometric detector, the top from absorption tower 42 is measured at regular intervals
The concentration of hydrogen sulfide of discharge treated purified gases 43, finds out the concentration of hydrogen sulfide being removed among the hydrogen sulfide of importing
Ratio, that is, hydrogen sulfide removal rate.As a result, be 100.0% in 5 hours on-tests after cure hydrogen removal rate, the sulphur after 15 hours
Changing hydrogen removal rate is 99.2%.
(embodiment 3)
It is put into methylnaphthohydroquinone instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 8.It is experimental facilities, dense
Degree, alkali source, reaction temperature are all identical as comparative example 8.At this point, after 5 hours on-tests and respectively obtaining vulcanization after 15 hours
Hydrogen removal rate is 99.8% and 99.4%.This indicates that methylnaphthohydroquinone has and previous Plutarch Haake this catalyst 1,4- naphthoquinones-
The same hydrogen sulfite ion processing capacity of 2- sodium sulfonate.
(comparative example 9)
It is put into hydroquinone instead of 1,4-naphthoquinone -2- sodium sulfonate, implements similarly to test with comparative example 8.It is experimental facilities, dense
Degree, alkali source, reaction temperature are all identical as comparative example 8.At this point, after 5 hours on-tests and respectively obtaining vulcanization after 15 hours
Hydrogen removal rate is 87.3% and 62.8%.This indicates that hydroquinone is unable to get and previous Plutarch Haake this catalyst 1,4- naphthalene
The same performance of quinone -2- sodium sulfonate.This is because the hydrogen sulfide dissolved in alkaline solution as simulation reaction liquid is not urged
Agent is sufficiently handled, and is caused to accumulate in alkaline solution, as a result could not be fully absorbed hydrogen sulfide.
(embodiment 4)
In experiment similarly to Example 3, the composition for simulating gas is set as comprising 12000ppm ammonia, 4000ppm sulphur
In the case where the nitrogen for changing hydrogen, 1000ppm hydrogen cyanide, 25000ppm carbon dioxide, 3000ppm methane, the hydrogen sulfide after 5 hours
Removal rate is 99.2%.This indicates hydrogen cyanide, carbon dioxide or the conduct as other sour gas contained by coke-stove gas etc.
The methane of hydrocarbon gas contained by coke-stove gas etc. does not affect desulfurization performance.
(embodiment 5)
In experiment similarly to Example 3, circulation and the liquid of simulation gas were temporarily ceased after 5 hours on-tests
Circulation, air be blown into, take out 2L simulation reaction liquid from circulation liquid bath, investment 2L is diluted to the ammonium hydroxide of pH value 9.0.In addition,
From the solid-like desulphurization catalyst input port 50 on regenerator top, 497mg methylnaphthohydroquinone is put into the state of solid powdery
The solution being stored in regenerator.Then, the circulation and the circulation of liquid, air for starting again at simulation gas are blown into, then open 2
Hour after cure hydrogen removal rate becomes 99.5%.This is indicated will not be to desulfurization performance being put into the state of solid powdery
It affects.
Industry utilizability
It can be with solid-like is handled, there is no the safety of explosivity etc in accordance with the invention it is possible to provide a kind of used
Problem is easy low cost acquisition and has containing for the desulphurization catalyst of the desulfurization performance same with previous desulphurization catalyst
The Wet-type desulfuration method of hydrogen sulfide gas.
Description of symbols
1,16,42: absorption tower
2,19,48: regenerator
3,15,24: H 2 S-containing gas
4,17,25,43: purified gases
5,28,31: desulfurization catalyst agent solution
6,20,30: oxygen-containing gas
7,23: the desulfurization catalyst agent solution of the ion of salt or sulfur-bearing dissolved with sulphur or sulfur-bearing
8,22,33,51: exhaust gas
9: toluiquinone (oxysome)
10: methylnaphthohydroquinone (Reduction Body)
11: hydrogen sulfide
12: sulphur
13: oxygen
14: water
18,32,47: liquid-feeding pump
21,50: the input port of solid-like desulphurization catalyst
26: filler
27: spaced walls
29: hermetically sealed can
34:500mL beaker
35,46: simulation reaction liquid
36: magnetic stirring apparatus
37: cylinder gas injection tube
38:pH/ORP meter
39: dissolved oxygen meter
40: hot bath
41: H 2 S-containing gas (simulation gas)
44: the gas chromatograph with flame photometric detector
45: circulation liquid bath
49: air
Claims (6)
1. a kind of Wet-type desulfuration method of H 2 S-containing gas is taken off by making H 2 S-containing gas and dissolving in alkaline solution
Sulfur catalyst and the desulfurization catalyst agent solution contact that is formed and carry out the Wet-type desulfuration method of the desulfurization of the H 2 S-containing gas,
It is characterized in that,
Use at least one of methylnaphthohydroquinone and toluiquinone as the desulphurization catalyst.
2. the Wet-type desulfuration method of H 2 S-containing gas according to claim 1, which is characterized in that
Use ammonia as the alkali source of the alkaline solution.
3. the Wet-type desulfuration method of H 2 S-containing gas according to claim 1 or 2, which is characterized in that
The desulfurization catalyst agent solution is to throw at least one of the methylnaphthohydroquinone and described toluiquinone in a solid state
Enter the alkaline solution to make it dissolve and manufacture.
4. the Wet-type desulfuration method of described in any item H 2 S-containing gas according to claim 1~3, which is characterized in that
At least one of the methylnaphthohydroquinone and described toluiquinone are put into the desulfurization catalyst agent solution in a solid state,
Supplement the desulphurization catalyst.
5. a kind of Wet-type desulfuration method of H 2 S-containing gas is to make the desulfurization catalyst on one side using absorption tower and regenerator
Agent solution is recycled between the absorption tower and the regenerator described in any one for the Claims 1 to 4 for carrying out desulfurization on one side
H 2 S-containing gas Wet-type desulfuration method,
The Wet-type desulfuration method of the H 2 S-containing gas is characterized in that,
In the absorption tower, contacts the H 2 S-containing gas with the desulfurization catalyst agent solution, thus make the sulfur-bearing
The hydrogen sulfide changed in hydrogen is dissolved in the desulfurization catalyst agent solution, and the vulcanization is removed from the H 2 S-containing gas
Hydrogen obtains purified gases,
Recycle the desulfurization catalyst agent solution dissolved with the hydrogen sulfide from the absorption tower to the regenerator, described
It in regenerator, contacts oxygen-containing gas with the desulfurization catalyst agent solution, sulphur, the salt of sulfur-bearing or the ion of sulfur-bearing is generated, by institute
The ion recycling for stating sulphur, the salt of the sulfur-bearing or the sulfur-bearing, follows the desulfurization catalyst agent solution to the absorption tower
Ring.
6. the Wet-type desulfuration method of H 2 S-containing gas according to claim 5, which is characterized in that
For the regenerator, at least one of the methylnaphthohydroquinone and the toluiquinone are put into the desulfurization with solid-like
Catalyst solution supplements the desulphurization catalyst.
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|---|---|---|---|
| PCT/JP2017/011444 WO2018173150A1 (en) | 2017-03-22 | 2017-03-22 | Method for wet desulfurization from hydrogen sulfide-containing gas |
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| CN114672020A (en) * | 2022-03-10 | 2022-06-28 | 天津科技大学 | Preparation method of benzoxazine-based conjugated trapezoidal polymer and application of benzoxazine-based conjugated trapezoidal polymer in hydrogen sulfide detection |
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| CN110559815A (en) * | 2019-09-17 | 2019-12-13 | 深圳市水务规划设计院股份有限公司 | Method for removing hydrogen sulfide and mercaptan in gas |
| EP3903934A4 (en) | 2019-09-30 | 2022-05-11 | LG Chem, Ltd. | Catalyst for hydrogenation reaction and method for producing same |
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| CN101829604A (en) * | 2010-03-25 | 2010-09-15 | 广西大学 | Oxidation desulphurization catalyst for reducing sulphur content of diesel fraction and preparation method thereof |
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| WO2018173150A1 (en) | 2018-09-27 |
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