CN109336066A - A kind of viscose glue exhaust gas TRS Recovered sulphur combines the technique and system of relieving haperacidity with exhaust gas - Google Patents
A kind of viscose glue exhaust gas TRS Recovered sulphur combines the technique and system of relieving haperacidity with exhaust gas Download PDFInfo
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- CN109336066A CN109336066A CN201811433117.3A CN201811433117A CN109336066A CN 109336066 A CN109336066 A CN 109336066A CN 201811433117 A CN201811433117 A CN 201811433117A CN 109336066 A CN109336066 A CN 109336066A
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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
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/765—Multi-stage SO3-conversion
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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
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The technique that the present invention relates to a kind of viscose glue exhaust gas TRS Recovered sulphur to combine relieving haperacidity with exhaust gas, the present invention, which compensates for existing exhaust gas acid making system, influences system stable operation and the excessively high defect of cost because of the defect in raw material post, sulphur caused by viscose glue exhaust gas TRS recovery technology is efficiently used simultaneously, it solves the problems, such as not handled with routine techniques because TRS sulphur iron tramp containing complexing is more, realizes the development of company's circular economy technology.
Description
Technical field
The present invention relates to sulfuric acid manufacturing field, relates in particular to a kind of viscose glue exhaust gas TRS Recovered sulphur and combine with exhaust gas
The technique and system of relieving haperacidity.
Background technique
At this stage, the sulfuric acid production process of international community's mainstream has acid production with sulphur, exhaust gas (hydrogen sulfide) relieving haperacidity, troilite system
Acid produces sulfuric acid etc. with flue gas during smelting production sulfuric acid, with gypsum and ardealite.
My company is constructed and put into operation exhaust gas acid making system for 2014, belongs to environmental protection project, and current system is mainly useless using viscose glue
Gas (H2S it) carries out burning production sulfuric acid, system actual load only accounts for the 50% of Design cooling load.
Company in 2016, which carries out, recycles project in viscose glue exhaust gas TRS, using Complexing Iron auxiliary agent by viscose glue exhaust gas H2S carries out oxygen
Metaplasia is at elemental sulfur.TRS sulphur (elemental sulfur) is up to 40% because of Complexing Iron auxiliary agent content at this stage, is not available acid production with sulphur system
Burning of uniting is handled.The TRS sulphur sulfur melting groove that now can use brand-new design melts TRS sulphur, carries out after preliminary removal of impurities
It burns, the S0 of burning2Flue gas and H2Enter waste gas combustion furnace second-time burning after the mixing of S exhaust gas, adjusts SO2Concentration, then pass through purification
3 washings of system cooling, forms pure S02Flue gas absorbs finally by conversion and produces qualified sulfuric acid.
Chinese patent notification number: " CN104401947A " discloses a kind of method that sulphur combines relieving haperacidity with exhaust gas, comprising:
Sulfureted hydrogen burning, for the first time washing second are washed, are washed for the third time, going acid mist, drying, sulfur burning, conversion,
When mainly solving acid preparation method exclusive use in the prior art, the utilization rate of equipment is not high, and because of exhausted air quantity deficiency, leads to system
The problem of underload need to open electric furnace addition, and heat compensation leads to system operation fluctuation, and power consumption cost increases, by by two
The united mode of acid preparation method is covered, improves the utilization rate and working efficiency of two covering devices, while reducing production cost, raising is set
Standby service life, has advantage at low cost, high-efficient.
But the patent still has defect in actual use: (1) concentration of the sulphur used is up to 99%, still
The sulphur concentration of industrial waste gas production only has 79%, and impurity content is excessive, cannot directly melt filtering and come into operation；(2) industrial waste gas
The sulphur of production because impurity content is excessive, cannot use exhaust gas produce sulphur, can only outsourcing high-purity sulphur, produce structure list
One, cause production cost to increase；(3) exhaust gas acid making system is when cold conditions is driven, and because fire box temperature is too low, sulfureted hydrogen burning is generated
Water, SO2With a small amount of SO3Condensation acid can be generated, causes system equipment to corrode, reduces system equipment service life.Therefore it is opening
It needs to carry out baker to burner hearth using liquefied gas when vehicle that normal production can be put into 400 DEG C or more, is extending system and putting into just
The time often run.
Summary of the invention
It is an object of the invention to solve the above-mentioned problems in the prior art, a kind of viscose glue exhaust gas TRS recycling is provided
Sulphur combines the technique and system of relieving haperacidity with exhaust gas.It is unstable excessively high with cost that the present invention compensates for existing exhaust gas acid making system
Defect, while sulphur caused by viscose glue exhaust gas TRS recovery technology is efficiently used, is solved because TRS sulphur is containing network
The problem that conjunction iron tramp is more and routine techniques can not be used to handle, realizes the development of company's circular economy technology.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of technique that viscose glue exhaust gas TRS Recovered sulphur combines relieving haperacidity with exhaust gas, which comprises the steps of:
(1) in TRS reactor, the exhaust gas and complexing agent that generate in viscose glue production process are subjected to oxidation reaction, stood, separation
Supernatant, bottom precipitation enter first separation slot；
(2) it in first separation slot, stands, supernatant is sent to reactor, and bottom precipitation enters a centrifuge, is carried out primary
Dehydration separation；
(3) precipitating after primary dewatering separation enters once washing slot, and clear water is added, and once washing is completed in stirring；
(4) precipitating after once washing enters the second-order separation slot, stands, and supernatant is sent to level-one separating tank, and bottom precipitation enters
Secondary centrifuging machine carries out second dehydration separation；
(5) precipitating after second dehydration separation enters secondary washing slot, and clear water is added, and secondary washing is completed in stirring；
(6) precipitating after secondary washing enters three-level separating tank, stands, and supernatant is sent to the second-order separation slot, and bottom precipitation enters
Centrifuge three times carries out triple dewatering separation；
(7) precipitating after triple dewatering separation enters sink three times, and clear water, stirring is added, and completion is washed three times；
(8) precipitating after washing three times enters filter press, obtains TRS sulphur；
(9) TRS sulphur is passed through in sulfur melting groove, heating, stirring, fusing, Complexing Iron auxiliary agent are denaturalized, and rise to trivalent by divalent iron
Iron；
(10) Molten sulphur of sulfur melting groove lower layer is sent to sulfur furnace and is burned, obtain SO2Gas；
(11) by SO2Gas send to incinerator and burns, while being passed through exhaust gas to incinerator, the SO after exhaust gas and burning2Gas into
Row is sufficiently mixed, the SO after adjustment burning2The concentration of gas is 6%；
(12) by SO in step (11)2Gas carries out being cooled to 260 DEG C by waste heat boiler；
(13) by the SO in step (12)2Gas passes sequentially through washing tube spray washing, literary formula washing tube reducing temperature twice washing, fills out
Material tower cools down washing three times；
(14) finally pass through electrostatic precipitator acid-mist-removing, enter converter after drying tower is dry, produce pure S03；
(15) sulfuric acid is produced finally by absorption tower.
Further, in the step (9) heating temperature to 135-145 DEG C.
Further, density is less than Molten sulphur after the denaturation of Complexing Iron auxiliary agent in the step (9), and impurity floats on table
Face arranges one layer of stainless steel cloth to trap Complexing Iron auxiliary agent in sulfur melting groove upper horizontal.
Further, the SO after burned in the step (10)2The temperature of gas is 950 DEG C -1050 DEG C, SO2Gas
Concentration is 10%.
Further, the exhaust gas in the step (11) is H2S。
The system that a kind of viscose glue exhaust gas TRS Recovered sulphur combines relieving haperacidity with exhaust gas, it is characterised in that: including sequentially connected
Sulfur melting groove, sulfur furnace, boiler, spray equipment, washing tube, Wen's bucket, packed tower, electrostatic precipitator, drying tower, converter and absorption
Tower.
The sulfur melting groove upper horizontal arranges one layer of stainless steel cloth.
Using the present invention has the advantages that
One, the present invention compensates for the defect that existing exhaust gas acid making system is unstable and cost is excessively high, while to viscose glue exhaust gas TRS
Sulphur caused by recovery technology is efficiently used, and routine can not be used because TRS sulphur iron tramp containing complexing is more by solving
The problem of technical treatment realizes the development of company's circular economy technology.
Two, Complexing Iron auxiliary agent remaining in TRS sulphur in the present invention is purified by 3 washings, may be implemented continuous
Normal production.
Three, the present invention in sulfur melting groove upper horizontal arrange one layer of stainless steel cloth, TRS sulphur in fusion process, wherein
Complexing Iron is lower than Molten sulphur by being heated at high temperature and being formed ferrous contaminants, density, can form one layer on Molten sulphur upper layer
Impurity layer after ferrous contaminants are trapped by stainless steel cloth, due to still containing sulphur inside it, is formed solid after being pre-chilled in air
Body impurity can be gone out impurity by replacing silk screen.
Four, exhaust gas relieving haperacidity waste gas combustion furnace, using rich in H2S exhaust gas burns, in normal production technology, due to H2S
Burning can generate water, SO2With a small amount of SO3, when fire box temperature is lower, will form strong corrosive condensation acid, cause flue and boiler
Corrosion, influences service life.Therefore every subsystem drive when, need to heat burner hearth using liquefied gas, until 400 DEG C with
On can put into exhaust gas and produced.SO after burned2The temperature of gas is 950 DEG C -1050 DEG C, extends system and normally transports
The capable time.After the fusing of exhaust gas sulphur, impurity is trapped by stainless steel cloth, the temperature after sulfur furnace burns, after burning
Degree is that 950 DEG C of -1050 DEG C of flue gases are sent to exhaust gas relieving haperacidity waste gas combustion furnace, by flue gas continuous heating burner hearth, in H2S stops burning
Afterwards, it remains to continue to ensure that waste gas combustion furnace keeps normal process temperature, it is therefore prevented that condensation acid generates, while being next exhaust gas investment
Burning reduces furnace drying time, can faster put into normal production.
Five, by SO2Gas send to incinerator and burns, while being passed through exhaust gas to incinerator, the SO after exhaust gas and burning2Gas
It is sufficiently mixed, the SO after adjustment burning2The concentration of gas is 6%.Due to H2S then process be two-step reaction, oxygen not
In the case where foot, H2H is first produced after S burning2O and simple substance S is H in oxygen abundance2S burning production H2O and SO2.According to converter
Interior catalyst configuration, to ensure to react thermal balance in converter, to S02Concentration has related request.Gas is dense too low, will lead to conversion
It is hot insufficient, it can not achieve system heat balance, require supplementation with external heat source, will increase system cost.If desired SO is improved2The dense mistake of gas
Height then needs to reduce into stove air, can make H2S is unable to full combustion, produces sublimed sulfur, sublimed sulfur is in rear end purification and washing
Sulphur simple substance can be sublimated into because temperature drastically reduces, causes system jams.Therefore by S02Gas concentration is controlled 6%, it can be ensured that
While conversion system operates normally, H also can guarantee2S full combustion.
Six, H2S and S02Into after burned waste gas burning, control outlet total moisture content is 950 DEG C -1050 DEG C, passes through waste heat pot
Demineralized water exchanges heat in furnace and boiler tube, produces 3.6Mpa middle pressure steam, and middle pressure steam is finally produced into 0.5Mpa by depressurized system
Low-pressure saturated steam realizes heat recovery, brings benefits.And the flue-gas temperature after being cooled down by boiler is 260 DEG C, because
Purifying liquid medium in post is dilute sulfurous acid, metal material is corroded it is more serious, therefore purify all stationary equipments in post and
Pipeline is all made of glass reinforced plastic production, cannot bear excessive temperature.60 DEG C are cooled to by washing tube water spray, is sprayed using literary formula
Acid mist is removed by electrostatic precipitator after leaching and packed tower spray, into follow-up system for producing H2SO4.Control heat boiler outlet
S02260 DEG C of gas temperature, heat production steam can be effectively recycled, while can guarantee that purification post gas temperature will not be to setting
It is standby to damage.
Seven, the present invention not only reduces production cost, also by the acid production with sulphur of the exhaust gas production in viscose glue production process
Reduce the discharge of exhaust gas, science environmental protection.
Eight, the present invention has an advantage in that (1) prior art for the higher exhaust gas TRS sulphur of impurity content compared with the prior art
Sulphur is trapped by collecter ring on molten sulphur post, removes a large amount of impurity, reduce the production of ash content in exhaust gas acid making system
It is raw, more conducively produce；(2) original patent is only used for high-purity sulphur and combines relieving haperacidity with exhaust gas, and existing technique is suitable for giving up
Gas TRS sulphur and high-purity sulphur joint relieving haperacidity, with more comprehensive；(3) original patent access point, 360 DEG C of flue gases are direct
Access purification post, is cooled down by purification and washing, and the prior art, by 950 DEG C of -1050 DEG C of flue gases and H2Shape after S is mixed and burned
At flue gas then need to be cooled to 260 DEG C by waste heat boiler, 100 DEG C of flue gas heats can be recycled more, reduce purification post
Operating load simultaneously can more byproduct steams, bring benefits.
Detailed description of the invention
Fig. 1 is system diagram of the invention；
Figure label are as follows: 1, sulfur melting groove, 2, sulfur furnace, 3, incinerator, 4, boiler, 5, spray equipment, 6, washing tube, 7, Wen
Bucket, 8, packed tower, 9, electrostatic precipitator, 10, drying tower, 11, converter, 12, absorption tower, 13, stainless steel cloth.
Specific embodiment
Viscose glue exhaust gas is passed through TRS reactor and generates the slurry rich in complexing agent and sulphur, is entered by lower section discharge gate
Level-one separating tank, realizes slurry and supernatant separation by way of settle and separate.Bottom sauce is by slurry pumping to primary
Centrifuge carries out dehydration separation, and clear liquid is recycled to TRS reactor by pump above level-one separating tank.
TRS sulphur enters once washing slot after centrifuge dehydration, and clear water is added, real under the collective effect of stirring
Existing once washing.Mixed slurry enters the second-order separation slot, and slurry and supernatant separation are realized by way of settle and separate.Bottom
Sauce is pumped to secondary centrifuging machine by sauce and carries out dehydration separation.Clear liquid is recycled to a fraction by pump above the second-order separation slot
From slot.
TRS sulphur enters secondary washing slot after the dehydration of secondary centrifuging machine, and clear water is added, real under the collective effect of stirring
Existing secondary washing.Mixed slurry enters three-level separating tank, and slurry and supernatant separation are realized by way of settle and separate.Bottom
Sauce is pumped to centrifuge three times by sauce and carries out dehydration separation.Clear liquid is recycled to two fractions by pump above three-level separating tank
From slot.
TRS sulphur is passed through in sulfur melting groove 1, is melted under steam and the collective effect of stirring, technological temperature is controlled
At 135-145 DEG C, Complexing Iron auxiliary agent contained therein is denaturalized under the action of high temperature, rises to trivalent iron by divalent iron.
Because density is less than Molten sulphur after the denaturation of Complexing Iron auxiliary agent, impurity floats on surface, above novel sulfur melting groove 1
Horizontally disposed one layer of stainless steel cloth 13 is to trap Complexing Iron auxiliary agent.
The clean Molten sulphur of lower layer is sent to sulfur furnace 2 by pump and is burned, about 950 DEG C of hot fume-is crossed after burning
1050 DEG C, SO2Concentration is 10%, is sent to exhaust gas relieving haperacidity waste gas combustion furnace 3, while being sufficiently mixed into waste gas combustion furnace 3,
SO after adjustment burning2Gas concentration is 6%, mixed SO2Gas carries out being cooled to 260 DEG C by waste heat boiler 4, waste heat boiler 4
Byproduct steam.
The SO for being 260 DEG C by the cooling of waste heat boiler 42Gas passes through 6 spray washing of washing tube, literary formula washing tube 6 two again
Washing that secondary cooling is washed, packed tower 8 cools down three times enters conversion after drying tower 10 is dry using 9 acid-mist-removing of electrostatic precipitator,
Produce pure S03, sulfuric acid is produced finally by absorption tower 12.And Complexing Iron auxiliary agent remaining in TRS sulphur passes through 3 washings
It is purified, continuous normal production may be implemented.
Claims (7)
1. a kind of technique that viscose glue exhaust gas TRS Recovered sulphur combines relieving haperacidity with exhaust gas, which comprises the steps of:
(1) in reactor, the exhaust gas and complexing agent that generate in viscose glue production process are subjected to oxidation reaction, stood, in separation
Clear liquid, bottom precipitation enter first separation slot；
(2) it in first separation slot, stands, supernatant is sent to reactor, and bottom precipitation enters a centrifuge, is carried out primary
Dehydration separation；
(3) precipitating after primary dewatering separation enters once washing slot, and clear water is added, and once washing is completed in stirring；
(4) precipitating after once washing enters the second-order separation slot, stands, and supernatant is sent to level-one separating tank, and bottom precipitation enters
Secondary centrifuging machine carries out second dehydration separation；
(5) precipitating after second dehydration separation enters secondary washing slot, and clear water is added, and secondary washing is completed in stirring；
(6) precipitating after secondary washing enters three-level separating tank, stands, and supernatant is sent to the second-order separation slot, and bottom precipitation enters
Centrifuge three times carries out triple dewatering separation；
(7) precipitating after triple dewatering separation enters sink three times, and clear water, stirring is added, and completion is washed three times；
(8) precipitating after washing three times enters filter press, obtains TRS sulphur；
(9) TRS sulphur is passed through in sulfur melting groove (1), heating, stirring, fusing, Complexing Iron auxiliary agent are denaturalized, are risen to by divalent iron
Trivalent iron；
(10) Molten sulphur of sulfur melting groove (1) lower layer is sent to sulfur furnace (2) and is burned, obtain SO2 gas；
(11) SO2 gas is sent to incinerator (3) and is burned, while being passed through exhaust gas to incinerator (3), the SO2 after exhaust gas and burning
Gas is sufficiently mixed, and the concentration of the SO2 gas after adjustment burning is 6%；
(12) SO2 gas in step (11) is carried out being cooled to 260 DEG C by waste heat boiler (4)；
(13) the SO2 gas in step (12) is passed sequentially through into washing tube (6) spray washing, literary formula washing tube (6) reducing temperature twice
Washing, packed tower (8) cool down washing three times；
(14) finally pass through electrostatic precipitator (9) acid-mist-removing, enter converter (11) after drying tower (10) is dry, produce pure
S03；
(15) sulfuric acid is produced finally by absorption tower (12).
2. a kind of viscose glue exhaust gas TRS Recovered sulphur as described in claim 1 combines the technique of relieving haperacidity with exhaust gas, feature exists
In: heating temperature is to 135-145 DEG C in the step (1).
3. a kind of viscose glue exhaust gas TRS Recovered sulphur as described in claim 1 combines the technique of relieving haperacidity with exhaust gas, feature exists
In: density is less than Molten sulphur after the denaturation of Complexing Iron auxiliary agent in the step (1), and impurity floats on surface, in sulfur melting groove (1)
Upper horizontal arranges one layer of stainless steel cloth (13) to trap Complexing Iron auxiliary agent.
4. a kind of viscose glue exhaust gas TRS Recovered sulphur as described in claim 1 combines the technique of relieving haperacidity with exhaust gas, feature exists
In: in the step (2) it is burned after the temperature of SO2 gas be 950 DEG C -1050 DEG C, the concentration of SO2 gas is 10%.
5. a kind of viscose glue exhaust gas TRS Recovered sulphur as described in claim 1 combines the technique of relieving haperacidity with exhaust gas, feature exists
In: the exhaust gas in the step (3) is H2S.
6. the system that a kind of viscose glue exhaust gas TRS Recovered sulphur combines relieving haperacidity with exhaust gas, it is characterised in that: including sequentially connected molten
Sulphur slot (1), sulfur furnace (2), boiler (4), spray equipment (5), washing tube (6), Wen's bucket (7), packed tower (8), electrostatic precipitator
(9), drying tower (10), converter (11) and absorption tower (12).
7. the system that a kind of viscose glue exhaust gas TRS Recovered sulphur as claimed in claim 6 combines relieving haperacidity with exhaust gas, feature exist
In: sulfur melting groove (1) upper horizontal arranges one layer of stainless steel cloth (13).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811433117.3A CN109336066B (en) | 2018-11-28 | 2018-11-28 | Process and system for jointly preparing acid by recycling sulfur and waste gas from viscose waste gas TRS |
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| CN201811433117.3A CN109336066B (en) | 2018-11-28 | 2018-11-28 | Process and system for jointly preparing acid by recycling sulfur and waste gas from viscose waste gas TRS |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110844887A (en) * | 2019-11-25 | 2020-02-28 | 宜宾海翔化工有限责任公司 | Method and device for treating hydrogen sulfide |
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| EP0002737A1 (en) * | 1977-12-16 | 1979-07-11 | E.I. Du Pont De Nemours And Company | A process for making sulfuric acid anhydride and, if desired, sulfuric acid and/or oleum |
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| CN103030115A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | United acid manufacturing method by utilizing sulfuretted hydrogen and sulphur |
| CN104401947A (en) * | 2014-11-17 | 2015-03-11 | 宜宾海翔化工有限责任公司 | Method combining sulfur and exhaust gas to produce acid |
| CN106395756A (en) * | 2016-08-31 | 2017-02-15 | 华陆工程科技有限责任公司 | Novel method for processing ammonia, carbonyl sulfide and hydrogen sulfide-containing acid gases, and recycling sulfur |
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|---|---|---|---|---|
| EP0002737A1 (en) * | 1977-12-16 | 1979-07-11 | E.I. Du Pont De Nemours And Company | A process for making sulfuric acid anhydride and, if desired, sulfuric acid and/or oleum |
| CN1636866A (en) * | 2004-12-03 | 2005-07-13 | 湖南百利工程科技有限公司 | Combined dry and wet process of preparing high concentration sulfuric acid with hydrogen sulfide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110844887A (en) * | 2019-11-25 | 2020-02-28 | 宜宾海翔化工有限责任公司 | Method and device for treating hydrogen sulfide |
| CN110844887B (en) * | 2019-11-25 | 2023-03-21 | 宜宾海翔化工有限责任公司 | Method and device for treating hydrogen sulfide |
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| CN109336066B (en) | 2022-05-31 |
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