CN103555375A - Coking gas secondary deep desulphurization device and coking gas secondary deep desulphurization method - Google Patents

Coking gas secondary deep desulphurization device and coking gas secondary deep desulphurization method Download PDF

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Publication number
CN103555375A
CN103555375A CN201310527686.5A CN201310527686A CN103555375A CN 103555375 A CN103555375 A CN 103555375A CN 201310527686 A CN201310527686 A CN 201310527686A CN 103555375 A CN103555375 A CN 103555375A
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China
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gas
ammonia
desulfurization
ammonia still
solution
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CN201310527686.5A
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Chinese (zh)
Inventor
袁磊
王为为
张超群
代恒超
赵兵
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袁磊
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Publication of CN103555375A publication Critical patent/CN103555375A/en

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Abstract

The invention discloses a coking gas secondary deep desulphurization device and a coking gas secondary deep desulphurization method, and belongs to the technical field of coke oven gas desulfurization and fixed ammonia decomposition. According to the invention, the desulfurization is carried out by adopting a mode that hydrogen sulfide is absorbed by a sodium hydroxide solution; an alkali liquor source is an alkali liquor tank positioned on an ammonia distillation workshop section; a desulfurizing solution which absorbs the hydrogen sulfide is partially returned to the ammonia distillation workshop section to be used as alkali liquor which decomposes fixed ammonia salt; a small amount of the hydrogen sulfide and ammonia which are separated out by evaporating alkali and fixed ammonia salt which are contained in a waste desulfurizing solution in an ammonia distillation tower enter the process of a desulfurization system or an ammonia absorption system together. The coking gas secondary deep desulphurization device disclosed by the invention adopts the high-gravity machine as a reaction device and has the characteristics of small occupied area, low investment and low operating cost. According to the coking gas secondary deep desulphurization method, any catalyst is unnecessary to add, the content of the hydrogen sulfide contained in gas can be directly reduced from 200-500 mg/m<3> to 20 mg/m<3> and even to 0, so that the effect without waste desulfurizing solution discharge is realized.

Description

The dark desulfurizer of a kind of coke gas secondary and method
Technical field
The present invention relates to the dark desulfurizer of a kind of coke gas secondary and method, be specifically related to a kind of absorption that circulates, alkali lye zero and consume the method for sulfide hydrogen amount, belong to coke oven gas desulfurization, fixing ammonium decomposition technique field.
Background technology
Current Environmental Protection in China index coke-oven plant chimney SO 2quantity discharged is less than 400mg/m3, and this just means that the coal gas sulfide hydrogen amount after thionizer will be below 200mg/m3; In addition, coke-oven gas is as the metallurgical thermal source of ironmaking, the domestic general requirement of coal gas sulfide hydrogen amount also below 200mg/m3, this just determine Liao Yijiaonai institute be representational thionizer when design, the sulfide hydrogen amount after coal gas desulfurization of often take is less than 200mg/m3 as standard.But along with running down of environment, emission request has improved in part environmental administration, some requires coal gas sulfide hydrogen amount to be less than 50mg/m3, even below 20mg/m3, improving emission standard has been trend of the times, and after thionizer, coal gas sulfide hydrogen amount can not meet the demands below 200mg/m3.Existing a lot of thionizer is because of long-time running, and sweetening effectiveness declines, and some has not reached intrinsic sweetening effectiveness far away, and therefore the coke-oven plant of the domestic overwhelming majority is all faced with the problem of gas secondary desulfuration.
Domestic existing wet catalyzed oxidation desulfuration technique, as secondary desulfuration technique, can produce following problem: 1, due to H 2s concentration is low, and absorption driving force is very little, absorbs usefulness low; 2, add and additionally enter new alkali, broken the original soda balance of system; 3, produce desulfurization waste liquor, increased the weight of biochemical system burden, increased quantity of wastewater effluent; 4, nervous on-the-spot place is difficult to hold complete the second cover desulphurization system; 5, investment cost is high.Therefore, traditional sulfur removal technology has not too been suitable as the selection of gas secondary desulfuration, and especially to coal gas, after once desulfurization, sulfide hydrogen amount is below 500mg/m3, and desulphurization cost is too high.
The invention provides thus a kind of do not break original soda balance, not spent catalyst, without discharging of waste liquid, floor space little be more suitable for the secondary deep sulfur method that old factory sulfur removal technology is transformed at present.
Summary of the invention
The problem existing for above-mentioned desulfurizer, the present invention be take existing coke-oven gas desulfurizer as basis, provides a kind of coke gas secondary dark desulfurizer.
The dark desulfurizer of a kind of coke gas secondary of the present invention, comprise gas-liquid separation groove, liquid seal trough, circulation liquid bath, recycle pump, salkali waste groove, salkali waste pump, new alkali groove, new alkali pump, ammonia still process lye vat, ammonia still, thionizer, described device also comprises sweetener.
Described sweetener is high gravity desulfurization machine, bubbling style tower, empty spray tower or packing tower.
Described high gravity desulfurization machine is to adopt the mode of filler rotation to make the rapid atomization of doctor solution, thereby reach gas-to-liquid contact area, becomes large, and mass transfer coefficient uprises, thereby desulfuration efficiency and speed of reaction are improved greatly.
The present invention also provides a kind of coke gas secondary deep desulfuration method, comprises the following steps:
The new alkali pump side line on the existing new alkali groove of A ,Cong ammonia still process workshop section side extracts the new alkali lye of a part and sends circulation liquid bath to;
After B, alkali lye are sent circulation liquid bath to, be delivered into sweetener through recycle pump, enter with coal gas stream or adverse current, absorption reaction moment completes; Gas and liquid enter gas-liquid separation groove in the lump, and gas is discharged from the top of gas-liquid separation groove, and liquid enters circulation liquid bath, again passes through recycle pump circulation absorbing hydrogen sulphide; Owing to containing a certain amount of water in the later coal gas of desulfurization, after coal gas enters main pipeline, liquid seal trough is set and collects the partial condensation water in coal gas;
C, reaction 6-16h, after the time, draw a part of sulfur removing pregnant solution to enter the storage of salkali waste groove from recycle pump side lines, and the new alkali lye that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 2-10m3, with salkali waste, is pumped into the decomposition that ammonia still process lye vat participates in solid ammonium-salt;
In D, ammonia still process lye vat, reacted rich solution enters and in ammonia still, participates in ammonia still process, the ammonia steaming from ammonia still carry out cooling after and hydrogen sulfide together enter again thionizer and carry out desulfurization, thereby complete desulfurization.
Described alkali lye is NaOH solution or KOH solution.
Described alkali lye adopts NaOH solution, and for ammonia desulfurizing process, the ammonia still process gas of desulfurization waste liquor returns to desulphurization system.
Described alkali lye adopts NaOH solution, and for sodium method sulfur removal technology, the ammonia still process gas of desulfurization waste liquor enters ammonia absorption system.
Described alkali lye adopts NaOH solution, and for AS sulfur removal technology, desulfurization waste liquor enters the ammonia sulphur system of AS system, decomposes solid ammonium-salt.
Described alkali lye adopts KOH solution, and for vacuum potassium carbonate sulfur removal technology, desulfurization waste liquor enters its desulphurization system.
The related principles of chemistry of coke gas secondary deep desulfuration method of the present invention represent as follows:
Desulfurization absorption reaction:
NaOH?+?H 2S?==NaHS?+?H 2O
Solid ammonium-salt chemical decomposition mechanism:
react with NaOH: 2NaOH+(NH 4) 2sO 4==Na 2sO 4+ 2NH 3 + 2H 2o
react with NaHS: 2NaHS+(NH 4) 2sO 4==Na 2sO 4+ 2NH 3 + 2H 2s
The inventive method adopts sodium hydroxide solution as absorption agent absorbing hydrogen sulphide, owing to participating in the NaOH of reaction in absorption process, can all change into NaHS, and NaHS and NaOH have the ability of decomposing solid ammonium-salt equally, therefore realized zero consumption of alkali lye and do not broken original soda balance.
In method reaction process of the present invention, can produce a small amount of water, together enter ammonia still, participate in forming evaporated waste ammonia liquid, because the hydrogen sulfide absorbing is less, the water yield of generation on waste liquid amount without impact, negligible; The coal gas that every processing is 10,000 cubes, approximately has more the water of 2kg ~ 5kg.
The ammonia steaming in described ammonia still and hydrogen sulfide together enter before thionizer, the extra H increasing 2s amount has increased by approximately 2% system desulfurization load, can not have a negative impact to desulfurization.
Method of the present invention is applicable to gas and adopts the situation that desulfurization does not reach effect or need to transform after Wet Catalytic Oxidation Method sulfur removal technology process, is equally also applicable to the transformation of AS coal gas desulfurization technique and vacuum potassium carbonate technique.
Beneficial effect of the present invention:
(1) the present invention adopts hypergravity machine as reaction unit, has to take up an area to economize, invest the feature low, running cost is low, special in very strong adaptability and the selectivity of modernizing and expanding the existing factory;
(2) adopt secondary deep desulfuration method of the present invention, in coal gas, from 200-500mg/m3, can be directly down to 20mg/m3 be even 0 to hydrogen sulfide content;
(3) secondary deep desulfuration method of the present invention has overcome the drawback that traditional ammonia process and the desulfurization of sodium method bring, adopt the special conversion units such as high gravity desulfurization machine, tower, assimilated efficiency is high, process cost low (energy of processing a cube of gas consumption is about 9KJ, and the about 40.5KJ of energy of a cube of gas consumption is processed in the tower desulfurization of traditional wet);
(4) NaOH that secondary deep desulfuration method of the present invention adopts is highly basic, does not need to add any catalyzer, has therefore realized the not effect of spent catalyst; Absorb later sulfur removing pregnant solution the amount of same volume return to ammonia steaming system, therefore realized the effect without the discharge of desulfurization waste liquor.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
In figure: 1-absorption equipment, 2-gas-liquid separation groove, 3-liquid seal trough, 4-circulation liquid bath, 5-recycle pump, 6-salkali waste groove, 7-salkali waste pump, the new alkali groove of 8-, the new alkali pump of 9-, 10-ammonia still process lye vat, 11-ammonia still, 12-thionizer.
Embodiment
embodiment 1
A secondary deep desulfuration method, comprises the following steps:
New alkali pump 9 side lines on the existing new alkali groove of A ,Cong ammonia still process workshop section 8 sides extract the new NaOH solution of a part and send circulation liquid bath 4 to;
After B, NaOH solution are sent circulation liquid bath 4 to, be delivered into sweetener 1 through recycle pump 5, with coal gas and flow to into, absorption reaction moment completes; Gas and liquid enter gas-liquid separation groove 2 in the lump, and gas is discharged from the top of gas-liquid separation groove 2, and liquid enters circulation liquid bath 4, again passes through recycle pump 5 circulation absorbing hydrogen sulphides; Owing to containing a certain amount of water in the later coal gas of desulfurization, after coal gas enters main pipeline, the partial condensation water that liquid seal trough 3 is collected in coal gas is set;
C, reaction 6h, after the time, draw a part of sulfur removing pregnant solution to enter 6 storages of salkali waste groove from recycle pump 5 side lines, and the new NaOH solution that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 3m3, with salkali waste pump 7, sends into the decomposition that ammonia still process lye vat 10 participates in solid ammonium-salt;
In D, ammonia still process lye vat 10, reacted rich solution enters in ammonia still 11 and participates in ammonia still process, the ammonia steaming from ammonia still 11 carry out cooling after and hydrogen sulfide together enter again thionizer 12 and carry out desulfurization, thereby complete desulfurization.
embodiment 2
It is all identical with embodiment 1 steps A, B, D, and difference is step C:
C, reaction 9h, after the time, draw a part of sulfur removing pregnant solution to enter 6 storages of salkali waste groove from recycle pump 5 side lines, and the new alkali that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 5m3, with salkali waste pump 7, sends into the decomposition that ammonia still process lye vat 10 participates in solid ammonium-salt.
embodiment 3
It is all identical with embodiment 1 steps A, B, D, and difference is step C:
C, reaction 13h, after the time, draw a part of sulfur removing pregnant solution to enter 6 storages of salkali waste groove from recycle pump 5 side lines, and the new alkali that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 8m3, with salkali waste pump 7, sends into the decomposition that ammonia still process lye vat 10 participates in solid ammonium-salt.
embodiment 4
It is all identical with embodiment 1 steps A, B, D, and difference is step C:
C, reaction 16h, after the time, draw a part of sulfur removing pregnant solution to enter 6 storages of salkali waste groove from recycle pump 5 side lines, and the new alkali that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 10m3, with salkali waste pump 7, sends into the decomposition that ammonia still process lye vat 10 participates in solid ammonium-salt.
embodiment 5
It is all identical with embodiment 1 steps A, B, D, and difference is step C:
C, reaction 11h, after the time, draw a part of sulfur removing pregnant solution to enter 6 storages of salkali waste groove from recycle pump 5 side lines, and the new alkali that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 7m3, with salkali waste pump 7, sends into the decomposition that ammonia still process lye vat 10 participates in solid ammonium-salt.
embodiment 6
A secondary deep desulfuration method, comprises the following steps:
New alkali pump 9 side lines on new alkali groove 8 sides of A ,Cong desulfurization workshop section extract the new KOH solution of a part and send circulation liquid bath 4 to;
After B, KOH solution are sent circulation liquid bath 4 to, be delivered into sweetener 1 through recycle pump 5, enter with coal gas stream or adverse current, absorption reaction moment completes; Gas and liquid enter gas-liquid separation groove 2 in the lump, and gas is discharged from the top of gas-liquid separation groove 2, and liquid enters circulation liquid bath 4, again passes through recycle pump 5 circulation absorbing hydrogen sulphides; Owing to containing a certain amount of water and mist in the later coal gas of desulfurization, after coal gas enters main pipeline, partial condensation water and mist sedimentation liquid that liquid seal trough 3 is collected in coal gas are set;
C, reaction 3h, after the time, draw a part of sulfur removing pregnant solution 5 to enter 6 storages of salkali waste groove from recycle pump side lines, and the new KOH solution that simultaneously supplements equal volume amount enters system; Waste liquid amount reaches after 3m3, with salkali waste pump 7, waste liquid is directly squeezed into sulfur removing pregnant solution groove;
The desulfurization waste liquor of the sulfur removing pregnant solution of D, thionizer 12 and step C, after sulfur removing pregnant solution groove mixes, together enters regenerator column and resolves regeneration, participates in forming high density H 2s, enters the processing workshop section of subsequent disposal high density acid gas, thereby completes desulfurization.
embodiment 7
It is all identical with embodiment 6 steps A, B, D, and difference is step C:
C, reaction 6h, after the time, draw a part of sulfur removing pregnant solution 5 to enter 6 storages of salkali waste groove from recycle pump side lines, and the new KOH solution that simultaneously supplements equal volume amount enters system; Waste liquid amount reaches after 3m3, with salkali waste pump 7, waste liquid is directly squeezed into sulfur removing pregnant solution groove.
embodiment 8
It is all identical with embodiment 6 steps A, B, D, and difference is step C:
C, reaction 10h, after the time, draw a part of sulfur removing pregnant solution 5 to enter 6 storages of salkali waste groove from recycle pump side lines, and the new KOH solution that simultaneously supplements equal volume amount enters system; Waste liquid amount reaches after 6m3, with salkali waste pump 7, waste liquid is directly squeezed into sulfur removing pregnant solution groove.
embodiment 9
It is all identical with embodiment 6 steps A, B, D, and difference is step C:
C, reaction 16h, after the time, draw a part of sulfur removing pregnant solution 5 to enter 6 storages of salkali waste groove from recycle pump side lines, and the new KOH solution that simultaneously supplements equal volume amount enters system; Waste liquid amount reaches after 10m3, with salkali waste pump 7, waste liquid is directly squeezed into sulfur removing pregnant solution groove.

Claims (8)

1. the dark desulfurizer of coke gas secondary, comprise gas-liquid separation groove (2), liquid seal trough (3), circulation liquid bath (4), recycle pump (5), salkali waste groove (6), salkali waste pump (7), new alkali groove (8), new alkali pump (9), ammonia still process lye vat (10), ammonia still (11), thionizer (12), it is characterized in that, described device also comprises sweetener (1).
2. the dark desulfurizer of coke gas secondary according to claim 1, is characterized in that, described sweetener (1) is high gravity desulfurization machine, bubbling style tower, empty spray tower or packing tower.
3. a coke gas secondary deep desulfuration method according to claim 1, is characterized in that, said method comprising the steps of:
New alkali pump (9) side line on the existing new alkali groove of A ,Cong ammonia still process workshop section (8) side extracts the new alkali lye of a part and sends circulation liquid bath (4) to;
After B, alkali lye are sent circulation liquid bath (4) to, through recycle pump (5), be delivered into sweetener (1), enter with coal gas stream or adverse current, absorption reaction moment completes; Gas and liquid enter gas-liquid separation groove (2) in the lump, and gas is discharged from the top of gas-liquid separation groove (2), and liquid enters circulation liquid bath (4), again passes through recycle pump (5) circulation absorbing hydrogen sulphide; Owing to containing a certain amount of water in the later coal gas of desulfurization, after coal gas enters main pipeline, liquid seal trough (3) is set and collects the partial condensation water in coal gas;
C, reaction 6-16h, after the time, draw a part of sulfur removing pregnant solution to enter salkali waste groove (6) storage from recycle pump (5) side lines, and the new alkali that simultaneously supplements equal volume amount enters system; Rich solution amount reaches after 2-10m3, with salkali waste pump (7), sends into the decomposition that ammonia still process lye vat (10) participates in solid ammonium-salt;
In D, ammonia still process lye vat (10), reacted rich solution enters and participates in ammonia still process in ammonia still (11), the ammonia steaming from ammonia still (11) carry out cooling after and hydrogen sulfide together enter again thionizer (12) and carry out desulfurization, thereby complete desulfurization.
4. coke gas secondary deep desulfuration method according to claim 3, is characterized in that, described alkali lye is NaOH solution or KOH solution.
5. coke gas secondary deep desulfuration method according to claim 4, is characterized in that, for ammonia desulfurizing process, described alkali lye adopts NaOH solution, and the ammonia still process gas of desulfurization waste liquor returns to desulphurization system.
6. coke gas secondary deep desulfuration method according to claim 4, is characterized in that, for sodium method sulfur removal technology, described alkali lye adopts NaOH solution, and the ammonia still process gas of desulfurization waste liquor enters ammonia absorption system.
7. coke gas secondary deep desulfuration method according to claim 4, is characterized in that, for AS sulfur removal technology, described alkali lye adopts NaOH solution, and desulfurization waste liquor enters the ammonia sulphur system of AS system, decomposes solid ammonium-salt.
8. coke gas secondary deep desulfuration method according to claim 4, is characterized in that, for vacuum potassium carbonate sulfur removal technology, described alkali lye adopts KOH solution, and desulfurization waste liquor enters its desulphurization system.
CN201310527686.5A 2013-10-31 2013-10-31 Coking gas secondary deep desulphurization device and coking gas secondary deep desulphurization method CN103555375A (en)

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Application publication date: 20140205