CN106881003A - A kind of Br in the separation and recovery flue gas of after-burning zone2Method - Google Patents
A kind of Br in the separation and recovery flue gas of after-burning zone2Method Download PDFInfo
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- CN106881003A CN106881003A CN201510944067.5A CN201510944067A CN106881003A CN 106881003 A CN106881003 A CN 106881003A CN 201510944067 A CN201510944067 A CN 201510944067A CN 106881003 A CN106881003 A CN 106881003A
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- flue gas
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- superfine fibre
- fibre fabric
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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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
Superfine Fibre Fabric Br in the separation and recovery flue gas of after-burning zone is utilized the invention discloses one kind2Method.The method includes Br in " absorption " separating flue2The adsorbed Br of-" desorption "2- steps such as " strippants " is separated, can finally obtain bromine.Superfine Fibre Fabric " absorption " Br2Principle it is different from conventional adsorbent, the Br of " absorption "2Weight can exceed well over the 30% of own wt." absorption " is carried out at low temperature, the Br in flue gas2It is more easy to separate out.Superfine Fibre Fabric material corrosion resistance is strong, thus long service life, the discarded object that is produced using process are little.Discarded Superfine Fibre Fabric can incineration disposal.Compared with traditional adsorbing separation recovery method, separation recovery efficiencies of the invention are high, operation operating cost is low and does not produce newborn discarded object substantially, realizes the unification of environmental benefit, economic benefit.
Description
Technical field
The invention belongs to the energy and environment-friendly engineering technical field, and in particular to bromo-containing substance high-temp combustion disposal system after-burning zone
The method of inorganic bromine in separation, recovered flue gas.
Background technology
Environmental pollution that electron wastes are brought, problem of resource waste have caused the extensive concern of government, scholar, the common people.
In the presently relevant research various disposal of abandoned printed circuit board, method of resource of interest, compared to other method, with
The fire metallurgy process that high-temp combustion is characterized has noble metal rate of recovery considerable advantage high, while metal can be reclaimed effectively
Copper, it is possible to achieve resource is farthest recycled.But, due to the use of organic bromine fire-retardant agent, discard print
When brush wiring board (usual Br contents are 3~8wt.%) high-temp combustion is disposed, the pollutant of generation removes receive much concern two
Dislike outside English class material, the also inorganic bromine (HBr+Br of flue gas middle and high concentration2), inorganic Br is at concentrations up to number in usual flue gas
Thousand mg/Nm3.Although part bromine fire-retardant agent product is disabled in many countries, various halogen-free flame retardants are constantly pushed away
Go out, but be constantly pushed out because cost performance is high, small bromine series new varieties are directly affected to environment, bromide fire retardant exists
It is still main fire retardant that printed substrate is used in longer period of time.
At present, for dioxin-like chemical, removed using optimization burning process, optimization after-burning zone operation operating mode and end
Technology can effectively control its emission level.Inorganic bromine in flue gas mainly exists in HBr forms in the case of a high temperature,
With flue-gas temperature reduction, HBr is gradually oxidized to Br in after-burning zone2.Generally, flue gas is less than in after-burning zone
200 DEG C of temperature range is stopped after 5min, and 90% HBr is converted into Br2, extend the residence time, HBr conversion ratios
Can also increase.Generally treatment flue gas when, using alkaline matter (such as sodium hydroxide solution, aqua calcis, ammonia
Water etc.) absorb flue gas in inorganic halogen, this will produce substantial amounts of waste liquid (or waste residue) to be difficult to dispose, while bromine resource
It is wasted.Patent 2013102517041 proposes the adsorbent used and can be recycled, molecular sieve, activated carbon etc., absorption
Br in flue gas after cooling2, then condense Br containing high concentration2Desorption gas to Br2Boiling temperature (about 59 DEG C) with
Under, thus in recovered flue gas most of inorganic bromine process route.If Br that is adsorbed, reclaiming2Contained Br is accounted for
More than the 90% of inorganic Br contents in flue gas, often processing 1 ton of abandoned printed circuit board can reclaim more than about 26 kilograms
Bromine, more than 500 yuan of direct yield, more than 270 yuan of profit, economic benefit is considerable.
But, there are many shortcomings in the adsorption separating method used in above-mentioned technique：The separating flues such as activated carbon, molecular sieve
In polluter mechanism, it is generally recognized that its micro channel inner surface by Van der Waals force etc. to flue gas in part gas
State molecule selective absorption.Because its huge specific surface area can separate some more gas components from flue gas.No
Same activated carbon, molecular sieve are different to various compositional selectings in flue gas.Molecular sieve is removed to entering in its internal channel by contrast
Molecule have outside Selective adsorption, can also be acted on by " interception " of micropore size, it is outer by flue gas in internal channel
Certain or certain several component (molecular dynamics is relatively large in diameter) separate with other components.Tested in conventional ADSORPTION IN A FIXED BED
In device, the Br of the only about adsorbable own wt 10~30% or so of molecular sieve, activated carbon2.Meanwhile, above-mentioned two class
Adsorbent is applied to lower temperature range (preferably lower than 30 DEG C), and the lower adsorption effect of temperature is better.Due to Br2's
Boiling point is relatively low (about 59 DEG C), when temperature is relatively low, a small amount of Br in flue gas2Easy condensation and block the micro- of adsorbent
Hole path, reduces adsorption area, reduces adsorption efficiency.Additionally, molecular sieve, activated carbon etc. are expensive (generally thousands of
Yuan/ton to up to ten thousand yuan/ton)；Weight is big, transport, operation inconvenience；Activated carbon, regenerating molecular sieve trouble, it is relatively costly；
Hydrobromic acid that molecular sieve is easily likely to form by micro HBr, HCl and flue gas cooling procedure of remaining in flue gas, hypobromous acid,
The corrosion such as acid that oxysulfide is formed, thus there are some to be lost when actually used.Discarded molecular sieve is not easily recycled utilization,
It is difficult disposal.Pertinent literature (and patent) simultaneously has not seen Br in other separation and recovery flue gases2Report.
The content of the invention
The present invention is for inorganic bromine resource demand in the above-mentioned problems in the prior art, and flue gas, there is provided a kind of
Using new material after-burning zone separation and recovery flue gas in Br2Method.The method separates Br2Efficiency high, Br2The rate of recovery is high,
Operating cost is low and easy to operate, and spillage of material used at the same time is small and micro discarded object is easy to disposal.
The technical scheme is that：
A kind of Br in the separation and recovery flue gas of after-burning zone2Method, comprise the following steps：
(1) after 1000~1400 DEG C of high-temperature flue gas from combustion chamber or/and dual firing chamber out first pass through preliminary cooling, purification
Into the flue gas depth cooling device of indirect heat exchange, it is gradually cooled as it passes through the cooler to less than 59 DEG C, and flue gas is put down in cooling device
The equal residence time was more than 5 minutes；
Less than (2) 59 DEG C flue gases enter Superfine Fibre Fabric Br2Separator, the Br in flue gas2It is ultra-fine in by device
Fabric " absorption ", separates from flue gas, then, fume emission or enters device for deep cleaning；
(3) after Superfine Fibre Fabric " absorption " saturation, desorbed with " strippant ", the Superfine Fibre Fabric circulation after desorption
Utilize.
Further, the preliminary cooling described in step (1), the device for being used is two sections of cooling devices, cooling medium
It is any one in running water, deionized water, industrial circulating water.
Further, the flue gas depth cooling device described in step (1) is the conventional indirect water-cooling formula of general industry production
Heat exchanger, the cooling medium for being used is any one in running water, deionized water, industrial circulating water, cooling medium
Can recycle；Or be the conventional indirect air cooling formula heat exchanger of general industry production, the cooling medium for being used is for empty
Gas；Or be the conventional indirect refrigeration formula heat exchanger of general industry production, first pass through indirect heat exchange mode and depth is cooled down into dress
Required cooling water temperature is put, depth cooling is then carried out to flue gas by indirect heat exchange mode with the cooling water after cooling, it is cold
But the used cooling medium of water cooling is any one in liquefied ammonia, lithium bromide refrigerating agent, cooling water and cooling water temperature
The cooling medium for being used can be recycled.
Further, the Superfine Fibre Fabric Br described in step (2)2Separator, is that common chemical industry non-pressure holds
Device storage tank equipment, device inside filling Superfine Fibre Fabric.In order to improve adsorption efficiency, Superfine Fibre Fabric layering filling
In a device, and between every layer it is provided with insulating frame, it is to avoid inside filling excessively consolidation, increases flue gas staying space, increases
The time that smoke adding gas is contacted with Superfine Fibre Fabric, while providing the passage of flow of flue gas.
Further, step (2) also increases by two grades of Superfine Fibre Fabric Br2Separator, two grades of Superfine Fibre Fabric Br2
Superfine Fibre Fabric in separator is in Superfine Fibre Fabric Br2The flue gas " adsorbed " in separator carries out two
Secondary " absorption ", reaches Br in more thoroughly separating flue2Purpose.
Further, " strippant " described in step (3) is the high-temperature cleaning air after heating.Br containing high concentration2" solution
Suction " gas is cooled down by depth again, Br therein2Condensation, is reclaimed.Superfine Fibre Fabric after " desorption " is followed
Ring is used；" strippant " or it is clean water.The Br of Superfine Fibre Fabric " absorption "2It is flush with water clean, flushing water and liquid
Bromine mixture can be separated from the water out by gravitational separation, bromine, and bromine (bromine) is finally reclaimed.Rushed
Superfine Fibre Fabric after washing purges drying using forced ventilation, or purges drying with the air after heating, and then circulation makes
With.The flushing water after bromine is separated to recycle.
In above-mentioned steps, solution smokes high-temperature cleaning air, drying hot-air, can be by the gas converting heat of indirect heat exchange
Device is obtained using part high-temperature flue gas energy heats pure air.
Relevant apparatus in above-mentioned step (1), (2), (3) use corrosion-resistant material.
The Br in the separation and recovery flue gas of after-burning zone of the invention2Method, with general adsorbent adsorbing separation adsorbate principle
Difference, by the substantial amounts of small Br of capillarity " absorption " of the micro-pore between fiber in Superfine Fibre Fabric2Drop：
Flue gas is cooled to less than 59 DEG C (temperature is more low better) first.Due to Br in flue gas2Concentration is higher, temperature is low, portion
Divide Br2The condensation on the part fiber fines of fabric, and fine droplet can continue " growing up " thereon, that is, exist
The Br that a large amount of condensations form larger drop is difficult under simple flue gas cooler environment2(not by means of other materials or method, only
Work as Br2Concentration is far above thousands of mg/Nm3When, Br in flue gas2Condensation amount can be only achieved considerable degree) super
Fine fiber surface condensation is adhered to and is assembled, and is separated from flue gas.Due to capillarity, " absorption " is relatively outer in fabric
The drop on surface is by " suction " fabric.Because the pore of fabric enriches very much, Superfine Fibre Fabric can be with " suction
It is attached " larger amount of Br2, so as to by Br2Efficiently separated from flue gas and be enriched with.
The present invention has the advantage that and effect compared with prior art：
(1) separative efficiency is high：Superfine Fibre Fabric can be with the Br of " absorption "2Weight exceeds well over own wt 30%；Point
Carried out at low temperature from operation, the Br in flue gas2It is more easy to separate out (micro channel for blocking adsorbent without having to worry about drop).
(2) micro HBr, the HCl and flue gas depth of " absorption " material (Superfine Fibre Fabric) to possible remaining in flue gas
The corrosivity resistance of hydrobromic acid, hypobromous acid, the acid of oxysulfide formation that degree cooling procedure is likely to form etc. is strong, thus
Long lifespan, the discarded object produced using process are few, discarded Superfine Fibre Fabric can incineration disposal, reclaim heat energy.
(3) operation operating cost is low：Superfine Fibre Fabric relative low price；Superfine Fibre Fabric own wt is light,
Filling, cleaning process are easy to operate, and running drag losses is small, energy consumption is low.
(4) it is easy to compatible with other fume treatment technologies, process unit.
In a word, the present invention is creatively using the Br in Superfine Fibre Fabric separation, recovered flue gas2, separating mechanism with pass
The adsorbing separation of system is different, and operation operating cost is low and does not produce newborn discarded object substantially, realizes environmental benefit, economy
The unification of benefit.
Brief description of the drawings
Fig. 1 is process flow diagram of the invention.
Fig. 2 is equipment flowsheet schematic diagram of the invention.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Process flow diagram of the invention is as shown in figure 1, equipment flowsheet schematic diagram of the invention is as shown in Figure 2.From height
(about 1000~1400 DEG C of warm combustion chamber and dual firing chamber brominated high-temperature flue gas out；6.5wt% containing Br in raw material, flue gas
In inorganic Br contents about 11g/Nm3) into two sections of cooling devices 1 of water-cooled of indirect heat exchange, be cooled in two stages
200 DEG C or so (HBr that 80% is there are about in flue gas is converted into Br2), remove flue gas subsequently into smoke eliminator 2
In flying dust, NOx etc., the flue gas depth cooling device 3 that the flue gas after purification is exchanged heat by indirect water-cooling, temperature is down to
28 DEG C or so (, more than 6 minutes, there are about 93% HBr conversions flue gas residence time in depth cooling device in flue gas
It is Br2, Br in flue gas2Concentration about 5.2g/Nm3)。
The flue gas cooled down by depth enters Superfine Fibre Fabric Br2Separator 4, overwhelming majority Br in flue gas2By by
Superfine Fibre Fabric internal void gradually " is adsorbed " and entered, is attached to inside Superfine Fibre Fabric.De- Br2Flue gas afterwards leads to
Cross CaO reactors 5 remove it is final through air-introduced machine, smoke stack emission after the HBr of remaining.A small amount of rinse water is store by rinse water
Case 11 is deposited through pump with certain pressure feeding Superfine Fibre Fabric Br2Separator 4, backwashes to it.Flushing water is taken
Band bromine flows into bromine, water separation tank 6.After standing a period of time in knockout drum, heavy bromine is sunk automatically,
Bromine storage tank 7 is flowed into, is finally separated and recovered.And dissolve a small amount of Br2Water then float on tank internal upper part, by means of overflow
Intermediate water tank 12 is flowed back in stream effect, finally returns that rinse water container 11 is recycled.Superfine Fibre Fabric Br2Separate
After fabric cleaning is clean in device 4, high-temperature cleaning air enters from bottom, is discharged through blower fan from top, and fabric is done
It is dry.After the completion of cleaning, drying, Superfine Fibre Fabric Br2Separator 4 reenters " absorption " working condition.
Two sections of cooling devices 1 are provided with water by cooling water water tank 8, be pumped up into.The steam of generation is sent outside and supplies user
Use.Cooling water used by depth cooling device 3 is provided by depth cooling water container 9, be pumped up into.Cooling is produced
Hot water flow into cooling water intermediate water tank 10.The water that cooling water intermediate water tank 10 is collected is after natural cooling or pressure cooling
Depth cooling water container 9 can be sent into recycle.
High-temperature cleaning air needed for drying Superfine Fibre Fabric, can be clear by flue gas indirectly heat by air preheater
Clean air is obtained, it is also possible to obtained by the steam heating clean air that two sections of cooling devices are produced by indirect heat exchanger.
Claims (7)
1. one kind after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that comprise the following steps：
(1) 1000~1400 DEG C of high-temperature flue gas from combustion chamber or/and dual firing chamber out first pass through preliminary cooling, purification
Afterwards into the flue gas depth cooling device of indirect heat exchange, it is gradually cooled as it passes through the cooler to less than 59 DEG C, and flue gas is cooled down in depth and filled
Middle mean residence time is put more than 5 minutes；
Less than (2) 59 DEG C flue gases enter Superfine Fibre Fabric Br2Separator, the Br in flue gas2It is ultra-fine in by device
Fabric " absorption ", separates from flue gas, then, fume emission or enters device for deep cleaning；
(3) after Superfine Fibre Fabric " absorption " saturation, desorbed with " strippant ", the Superfine Fibre Fabric after desorption
Recycle.
2. it is according to claim 1 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：Step
(1) flue gas depth cooling device described in is indirect water-cooling formula heat exchanger, the cooling medium for being used for running water,
Any one in deionized water, industrial circulating water；Or be indirect air cooling formula heat exchanger, the cooling medium for being used is for empty
Gas；Or be indirect refrigeration formula heat exchanger, indirect heat exchange mode is first passed through by cooling water temperature needed for depth cooling device, so
Depth cooling, the cooling that cooling water temperature is used are carried out to flue gas by indirect heat exchange mode with the cooling water after cooling afterwards
Medium is any one in liquefied ammonia, lithium bromide refrigerating agent.
3. it is according to claim 1 and 2 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：
Superfine Fibre Fabric Br described in step (2)2Separator is chemical industry vessels not under pressure storage tank equipment, is filled out inside device
Superfine Fibre Fabric is filled, Superfine Fibre Fabric layering filling is provided with insulating frame in a device and between every layer.
4. it is according to claim 1 and 2 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：
Step (2) also increases by two grades of Superfine Fibre Fabric Br2Separator, two grades of described Superfine Fibre Fabric Br2Separate dress
Superfine Fibre Fabric in putting is in Superfine Fibre Fabric Br2Secondary " suction is carried out by the flue gas that " absorption " is crossed in separator
It is attached ".
5. it is according to claim 1 and 2 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：
" strippant " described in step (3), is the high-temperature cleaning air after heating, or clean water.
6. it is according to claim 1 and 2 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：
Preliminary cooling described in step (1), the device for being used is two sections of cooling devices, and cooling medium is running water, goes
Any one in ionized water, industrial circulating water.
7. it is according to claim 5 after-burning zone separation and recovery flue gas in Br2Method, it is characterised in that：" solution
When vapor " is the high-temperature cleaning air after heating, Br containing high concentration2" desorption " gas by depth again cool down, condensation
Separate out Br2, so that Br2Reclaimed；When " strippant " is clean water, the Br of Superfine Fibre Fabric " absorption "2By water
Rinse well, by gravitational separation, bromine is separated from the water out so that bromine is returned for flushing water and bromine mixture
Receive.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510944067.5A CN106881003B (en) | 2015-12-15 | 2015-12-15 | One kind Br in the separation and recovery flue gas of after-burning zone2Method |
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| CN201510944067.5A CN106881003B (en) | 2015-12-15 | 2015-12-15 | One kind Br in the separation and recovery flue gas of after-burning zone2Method |
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| CN106881003A true CN106881003A (en) | 2017-06-23 |
| CN106881003B CN106881003B (en) | 2019-09-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579324A (en) * | 2018-07-11 | 2018-09-28 | 湖南科技大学 | It is a kind of to recycle Br in brominated flue gas2Device and method |
| CN108579332A (en) * | 2018-07-11 | 2018-09-28 | 湖南科技大学 | Higher boiling can coagulate the adsorptive reactor and method of component in a kind of separation mixed gas |
| CN111841066A (en) * | 2020-08-14 | 2020-10-30 | 中国华能集团清洁能源技术研究院有限公司 | System and method for removing acid gas in flue gas |
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| CN102974169A (en) * | 2012-12-28 | 2013-03-20 | 苏州大学 | Filtering material and preparation method thereof |
| CN103292339A (en) * | 2013-06-24 | 2013-09-11 | 湖南科技大学 | Comprehensive processing recycling process and device of bromine-contained high temperature flue gas |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102974169A (en) * | 2012-12-28 | 2013-03-20 | 苏州大学 | Filtering material and preparation method thereof |
| CN103292339A (en) * | 2013-06-24 | 2013-09-11 | 湖南科技大学 | Comprehensive processing recycling process and device of bromine-contained high temperature flue gas |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579324A (en) * | 2018-07-11 | 2018-09-28 | 湖南科技大学 | It is a kind of to recycle Br in brominated flue gas2Device and method |
| CN108579332A (en) * | 2018-07-11 | 2018-09-28 | 湖南科技大学 | Higher boiling can coagulate the adsorptive reactor and method of component in a kind of separation mixed gas |
| WO2020011151A1 (en) * | 2018-07-11 | 2020-01-16 | 遵义师范学院 | Device and method for recovering br2 in bromine-containing fumes |
| JP2021527568A (en) * | 2018-07-11 | 2021-10-14 | 遵義師範学院Ｚｕｎｙｉ Ｎｏｒｍａｌ Ｕｎｉｖｅｒｓｉｔｙ | Equipment and method for recovering Br2 in bromine-containing fume |
| JP7162935B2 (en) | 2018-07-11 | 2022-10-31 | 遵義師範学院 | Apparatus and method for recovering Br2 in bromine-containing fumes |
| CN108579324B (en) * | 2018-07-11 | 2023-05-09 | 遵义师范学院 | Br in recovered bromine-containing flue gas 2 Apparatus and method of (a) |
| CN108579332B (en) * | 2018-07-11 | 2024-01-19 | 遵义师范学院 | Adsorption reactor and method for separating high-boiling-point condensable components in mixed gas |
| CN111841066A (en) * | 2020-08-14 | 2020-10-30 | 中国华能集团清洁能源技术研究院有限公司 | System and method for removing acid gas in flue gas |
| CN111841066B (en) * | 2020-08-14 | 2024-06-11 | 中国华能集团清洁能源技术研究院有限公司 | System and method for removing acid gas in flue gas |
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