CN104556159B - Flue gas desulfurization produces the apparatus and method of magnesium sulfite - Google Patents
Flue gas desulfurization produces the apparatus and method of magnesium sulfite Download PDFInfo
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- CN104556159B CN104556159B CN201410798402.0A CN201410798402A CN104556159B CN 104556159 B CN104556159 B CN 104556159B CN 201410798402 A CN201410798402 A CN 201410798402A CN 104556159 B CN104556159 B CN 104556159B
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- flue gas
- sulfur dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/42—Magnesium sulfites
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Abstract
The invention discloses a kind of flue gas desulfurization and produce the apparatus and method of magnesium sulfite.The inventive system comprises flue gas desulfurization device, serum recycle pond, circulation subsider etc..Assembly of the invention and method are particularly suitable for removing the sulfur dioxide of the few flue gas of the oxygen contents such as fire coal boiler fume, and produce magnesium sulfite.Assembly of the invention and method use the mode that multistage absorption, circulation sedimentation, Sedimentation tank crystallisation by cooling combine, under conditions of completely abolishing oxidation fan power consumption and steam consumption, ensure desulfuration efficiency and side-product quality, and more reduce the operating cost of by-products production system, reduce desulfurization operation expense.
Description
Technical field
The present invention relates to a kind of flue gas desulfurization and produce the apparatus and method of magnesium sulfite, particularly relate to a kind of magnesium oxide method and take off
In sulfur waste liquid tower, direct crystallization produces the apparatus and method of magnesium sulfite.Apparatus and method of the present invention is particularly suited for utilizing combustion
Coal burning boiler flue gas desulfurization glue size is directly produced magnesium sulfite.
Background technology
Magnesium oxide method flue gas desulfurization technique is administered market at fire coal boiler fume and is progressively promoted and applies, the market share
From 2005 less than 1%, to presently more than 6%, wet oxidation magnesium processes desulfurization technology has obtained the accreditation of more and more people.Use
Magnesium oxide method sulfur removal technology and by desulfurization waste liquor preparation generate magnesium sulfate product, solve tradition calcium method desulfurization produce desulfurization stone
Cream processes problem, and magnesium sulfate production marketing income can with the operation and maintenance cost of offset partial desulfurization device, from technology and
Economic angle all has bigger market application advantage than tradition calcium method.
Oxidation fan is used owing to traditional fire coal boiler fume magnesium oxide method desulfurization waste liquor crystallization produces magnesium sulfate technology
Aeration magnesium sulfite is converted into the equipment of the necessary oxidation reaction of magnesium sulfate, and uses steam as evaporation, crystallizes, is dried
Medium, so causing the method using desulfurization waste liquor to produce magnesium sulfate to need to consume more oxidation fan consumption and steam, greatly
Width adds desulfurization operation expense.And using oxidation fan in Ta Nei or the technique of out column aeration oxidation, magnesium sulfite converts
Producing into the inefficient of magnesium sulfate, conversion ratio is the highest, and after limiting magnesium processes desulfurization to a certain extent, waste liquid produces magnesium sulfate
Technology is in the application in coal burning flue gas desulfurization field.Chinese invention patent application such as Publication No. CN1775681A provides
A kind of method: blast air in tower, to desulfurization slurry aeration in tower, make magnesium sulfite be converted into magnesium sulfate, subsequently into
Triple effect evaporation is evaporated concentrating.In this tower, forced aeration oxidation technology technology needs high-power oxidation fan, power consumption
Bigger.
Also have some processes then to use to be decomposed by the technique forcing oxidation, two effects or triple effect evaporation crystallization after desulfurization
Magnesium sulfate or other magnesium compound are made in recovery, and the Chinese invention patent application such as Publication No. CN1544331A provides one
Method: desulfurization waste liquor is forced oxidation, is added the sulphuric acid in magnesium oxide slurry and in waste liquid, is then made by evaporative crystallization
Magnesium compound.This kind of evaporative crystallization technique itself consumes ample resources, relatively costly.Oxidizing process is forced to need by aeration system
System operates, and cannot ensure in slurry that active ingredient converts and give birth under the influence of the factor such as aeration time, how many, the temperature height of oxygen supply
Become magnesium sulfate and the magnesium sulfite mixed liquor of 80% concentrations above.At present from the point of view of actual items effect, mostly running one section
Still return use after time and abandon method to process desulfurizing byproduct.
Summary of the invention
In order to overcome the defect of prior art, the present invention provides device and the side of a kind of flue gas desulfurization production magnesium sulfite
Method, especially provides direct crystallization in a kind of magnesium oxide method desulfurization waste liquor tower to produce the apparatus and method of magnesium sulfite.The present invention's
Device and method is particularly suited for utilizing coal burning flue gas desulfurization waste pulp to produce magnesium sulfite, it is possible to solves current magnesium processes and takes off
After sulfur waste liquid produce magnesium sulfate oxidation fan consume electric power compared with big, steam is more, ton ore deposit production cost is higher and increases desulfurization fortune
The problems such as row expense.
The present invention provides a kind of flue gas desulfurization to produce the device of magnesium sulfite, including:
Flue gas desulfurization device, is internally provided with sulfur dioxide and absorbs spray district, is used for using in magnesium oxide method removing flue gas
Sulfur dioxide, and form absorption serosity；
Serum recycle pond, for receiving the described absorption serosity from flue gas desulfurization device, and will absorb serum recycle extremely
Sulfur dioxide absorbs in spray district and evaporation concentration equipment；
Evaporation concentration equipment, is used for will loop to serosity evaporation and concentration therein, to form enriched product；With
Circulation subsider, for receiving the enriched product from evaporation concentration equipment, and settles enriched product, with
Form sedimentation products；
Wherein, described serum recycle pond, evaporation concentration equipment and circulation subsider are arranged at inside flue gas desulfurization device.
The device of magnesium sulfite is produced, it is preferable that described sulfur dioxide absorbs spray according to flue gas desulfurization of the present invention
Drench district and include that at least two sulfur dioxide absorbs spraying layer；Described evaporation concentration equipment is positioned at sulfur dioxide and absorbs under spray district
Portion.
The device of magnesium sulfite is produced, it is preferable that described device also includes hydrops according to flue gas desulfurization of the present invention
Device, this liquid accumulating device separates out for described evaporation concentration equipment and described sulfur dioxide are absorbed spray.
The device of magnesium sulfite is produced, it is preferable that described device farther includes according to flue gas desulfurization of the present invention:
Crystallizer, for the sedimentation products crystallization of self-loopa subsider in the future, to form crystallized product；
Centrifugation apparatus, for by the crystallized product centrifugation from crystallizer, to form mother solution and magnesium sulfite product
Thing；With
Drying equipment, for being dried the magnesium sulfite product from centrifugation apparatus.
The device of magnesium sulfite is produced, it is preferable that described flue gas meets as follows according to flue gas desulfurization of the present invention
One of condition:
1) flue gas described in is the flue gas from coal-burning boiler；
2) content of sulfur dioxide of described flue gas is 300mg/Nm3～20000mg/Nm3, and oxygen content be 0～
8vt%.
The present invention also provides for a kind of method utilizing said apparatus to produce magnesium sulfite, comprises the steps:
Flue gas desulfurization step: use the sulfur dioxide in magnesium oxide method removing flue gas in flue gas desulfurization device, and formed
Absorb serosity；
Serum recycle step: receive the described absorption serosity from flue gas desulfurization device in serum recycle pond, and will inhale
Receive serum recycle to absorb in spray district and evaporation concentration equipment to sulfur dioxide；
Evaporation-concentration step: will loop to serosity evaporation and concentration therein in evaporation concentration equipment, produces to be formed to concentrate
Thing；With
Circulation precipitation step: receive the enriched product from evaporation concentration equipment in circulation subsider, and concentration is produced
Thing settles, to form sedimentation products.
According to method of the present invention, it is preferable that described method farther includes:
Crystallisation step: the sedimentation products of self-loopa subsider crystallizes, to form crystallized product in the future in crystallizer；
Centrifugation step: by the crystallized product centrifugation from crystallizer in centrifugation apparatus, to form mother solution and Asia
Magnesium sulfate product；With
Drying steps: in drying equipment, the magnesium sulfite product from centrifugation apparatus is dried.
According to method of the present invention, it is preferable that by spilling in circulation subsider in described circulation precipitation step
Serosity is recycled in evaporation concentration equipment after filtering.
According to method of the present invention, it is preferable that in described centrifugation step, isolated Recycling Mother Solution is dense to evaporating
In contracting equipment.
According to method of the present invention, it is preferable that the magnesium sulfite crystal grain in sedimentation products is more than 0.1mm；Crystallization is produced
Magnesium sulfite crystal grain in thing is more than 0.15mm.
Apparatus and method of the present invention uses the mode that multistage absorption, circulation sedimentation, Sedimentation tank crystallisation by cooling combine,
Under conditions of completely abolishing oxidation fan power consumption and steam consumption, it is ensured that desulfuration efficiency and side-product magnesium sulfite quality,
And more reduce the operating cost of by-products production system, reduce desulfurization operation expense.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of the embodiment of the present invention.
In Fig. 1: 1 is desulfurizing tower, 2 is circulation subsider, and 3 is evaporation and concentration spraying layer, and 4 is liquid accumulating device, and 5 is overfall, 6
For circulation subsider outlet, 7 is that two grades of sulfur dioxide absorb spraying layer, and 8 is that three grades of sulfur dioxide absorb spraying layer, and 9 for removing
Day with fog, 10 is exhanst gas outlet, and 11 is serum recycle pond, and 12 is evaporation and concentration circulating pump, and 13 is that two grades of sulfur dioxide absorb spray
Layer circulating pump, 14 is that three grades of sulfur dioxide absorb spraying layer circulating pumps, and 15 meet an urgent need heat sink circulating pump for overtemperature, and 16 coolings are tied
Brilliant Sedimentation tank, 17 is centrifuge, and 18 is exsiccator, and 19 is packer, and 20 return evaporation and concentration spraying layer circulating pump for mother solution, and 21 are
Slurry pool excavationg pump, 22 is filter, and 23 is gas approach, and 24 meet an urgent need heat sink for overtemperature.
Detailed description of the invention
" % " of the present invention, if no special instructions, is percent by volume." vt% " of the present invention represents body
Long-pending percentage ratio." device " of the present invention is a kind of product, the system set of the most each device.In the present invention, entrance with enter
Mouth has identical implication, and the two can be replaced.
According to an embodiment of the invention, the flue gas of the present invention can be the flue gas from coal-burning boiler, coal-fired pot
In kiln gas, oxygen content is less than 8%.According to another implementation of the invention, described flue gas can also be any dioxy
Change sulfur content is 300mg/Nm3～20000mg/Nm3Between and oxygen content be the flue gas between 0～8vt%.In flue gas
Content of sulfur dioxide is preferably 500mg/Nm3～10000mg/Nm3, more preferably 1000mg/Nm3～5000mg/Nm3.In flue gas
Oxygen content be preferably 2～6vt%, more preferably 3～5vt%.Reduce oxygen content as far as possible, can improve in absorption serosity
The ratio of magnesium sulfite.
The magnesium oxide method flue gas desulfurization of the present invention refers to magnesium oxide for desulfurizing agent Main Ingredients and Appearance, but is not limited to add other
The flue gas desulfurization technique of arbitrary composition (such as calcium oxide, quick lime etc.).In magnesium oxide method sulfur removal technology, the structure of desulfurizing agent
May be varied from composition, its formula or change be to those skilled in the art known to.
<device of flue gas desulfurization production magnesium sulfite>
The flue gas desulfurization of the present invention produces the device of magnesium sulfite and includes following equipment: flue gas desulfurization device, serum recycle
Pond, evaporation concentration equipment, circulates subsider.Preferably, described device farther includes filter plant, drying equipment.Optionally,
Assembly of the invention also includes packaging facilities.According to assembly of the invention, described serum recycle pond, evaporation concentration equipment and circulation
Subsider is arranged at inside flue gas desulfurization device.Assembly of the invention can not contain oxygen-increasing device and/oxidation unit.
The flue gas of the present invention is oxygen content flue gas within 8%, the oxygen content in flue gas reach 2～8vt% it
Between, preferably 2～6vt%, more preferably 3～5vt%.So can improve the ratio of flue gas desulfurization glue size sulfite magnesium.
The flue gas desulfurization device of the present invention, its internal top is provided with sulfur dioxide and absorbs spray district, is used for using oxidation
Sulfur dioxide in magnesium processes removing flue gas, and form absorption serosity.The flue gas desulfurization device of the present invention can be flue gas desulfurization device
Or fume desulfurizing tower.Say from the angle of commercial Application, preferably fume desulfurizing tower.Described sulfur dioxide absorbs spray district bag
Include at least one sulfur dioxide and absorb spraying layer；Preferably include at least two sulfur dioxide absorb spraying layer, more preferably two
Or three sulfur dioxide absorb spraying layer.
The preparation that inventive desulfurization is used can be used by magnesium oxide method removing flue gas commonly used in the art those
Desulfurizer slurry, the magnesium hydroxide such as high-temperature condensation water adding industrial tap water or vaporising device in magnesia powder made
Serosity.
The evaporation concentration equipment of the present invention, is used for will loop to serosity therein (magnesium sulfite serosity) and is circulated evaporation
Concentrate and form enriched product.According to an embodiment of the invention, described evaporation concentration equipment is arranged on flue gas desulfurization and sets
Standby internal, and it is arranged on the bottom in sulfur dioxide absorption spray district.According to another implementation of the invention, described evaporation is dense
Contracting equipment is evaporation and concentration spraying layer.According to yet further embodiment of the invention, (such as, the evaporation of described evaporation concentration equipment
Concentrate spraying layer) and described sulfur dioxide absorb spray district separated by liquid accumulating device.The material of described liquid accumulating device can be fiber
Strengthen composite plastic FRP, preferably its temperature resistant range at 50～95 DEG C；But it is not limited to above-mentioned material, can play and serosity is gathered up
The facility of the effect come can.
The circulation subsider of the present invention, for receiving from the enriched product in evaporation concentration equipment, and makes enriched product
Sedimentation forms sedimentation products (including initial crystallization process).Preferably, described circulation subsider is arranged on flue gas desulfurization and sets
Standby internal, and it is positioned at the bottom of evaporation concentration equipment.According to operating mode, described circulation subsider can be set to monolayer sedimentation or double-deck
Sedimentation or multilamellar sedimentation.Its material can be fiberglass, it is also possible to be special steel, or ordinary steel material adds preservative treatment.According to
An embodiment of the invention, circulation subsider is arranged on below gas approach.The middle and upper part of circulation subsider is provided with excessive
Head piece, overfall is connected with filter through slurry pool excavationg pump, so that the serosity overflowed is recycled to evaporation and concentration after filtering
In equipment.Circulation subsider bottom is provided with circulation subsider outlet.
The serum recycle pond of the present invention is for receiving the absorption serosity formed in flue gas desulfurization device, and will absorb serosity
(magnesium sulfite serosity) is recycled to sulfur dioxide and absorbs in spray district and/or evaporation concentration equipment.As preferably, by described sulfurous
Acid magnesium serosity absorbs in spray district and/or evaporation concentration equipment to sulfur dioxide through filtering Posterior circle.As it is further preferred that by institute
State magnesium sulfite serosity in filtration Posterior circle to evaporation concentration equipment.Preferably, described serum recycle pond is arranged on flue gas
Desulphurization plant inner bottom part, is recycled to sulfur dioxide by circulating pump respectively by magnesium sulfite serosity and absorbs spray district and evaporation and concentration
In equipment.It is highly preferred that described magnesium sulfite serosity is sent into filter plant from serum recycle pond by excavationg pump, leach after filtration
Solid material send into centrifuge, filtrate recycles in circulating pump enters back into flue gas desulfurization device.Described filter plant can
Think plate filter or vacuum belt filter, preferably plate filter；Preferably, described filter plant comprises and is not less than
300 mesh, preferably not less than 400 mesh filter mediums.
The crystallizer of the present invention for receive circulation subsider in sedimentation products (after initial crystallization discharge crystal with
The mixture of serosity) and its further crystallization is obtained magma；Enter the sedimentation products of crystallizer, pass through in crystallizer
The mode of cooling forms magma further, and magma sulfite magnesium crystal grain is more than 0.15mm, preferably greater than 0.2mm.For anti-crystal grain
Sedimentation, can be provided with agitating device in crystallizer, and agitating device can use air stirrer or electric stirring dress
Put.According to an embodiment of the invention, the crystallizer of the present invention can be crystallisation by cooling Sedimentation tank, it is preferable that institute
State crystallisation by cooling Sedimentation tank and there is the automatic cooling system of band water-cooling ring device.Its low-temperature receiver can be that normal-temperature water may also be freezing
Water.Also the heat sinks such as water tower can be separately provided.
The centrifugation apparatus of the present invention is used for receiving the magma (crystallized product) that crystallizer is discharged, and by its centrifugation shape
Become magnesium sulfite product.Centrifugation apparatus can use known in the art those.
(preliminary product magnesium sulfite is brilliant for the magnesium sulfite product that the drying equipment of the present invention is discharged for receiving centrifugation apparatus
Body), and be dried to finished product.The drying equipment of the present invention is preferably drying apparatus of vibrating fluidized bed, and this device is particularly suitable for
The dry run of magnesium sulfite crystal.Present invention preferably employs the drying apparatus of vibrating fluidized bed of configuration hot air apparatus.Pressure fan
Air input air heater after filtering, through the hot-air of heating, enters in the lower box of main frame, then by fluidisation
The dispersion plate of bed is the most vertically blown into the material being dried, and making material is fluidized state.Material enters from charging aperture,
Main frame produces well-balanced vibration under the exciting force effect of vibrating motor, makes material along horizontal throwing, and the material being dried is above-mentioned
Thermal current and machine vibration comprehensive function under, form fluidized state, thus make material and hot air time long,
Area is big, thus obtains high efficiency drying effect.The temperature that assembly of the invention can utilize calorific value relatively low is 120～133
DEG C, pressure is 0.2～0.3MPa saturated vapor by air heating send into vibrated fluidized bed and the effect of mechanical vibration under realize
Magnesium sulfite crystal is fully dried into magnesium sulfite material.May be used for from the steam of fluid bed output, it not only saves the energy,
Also reduce operation cost.
The packaging facilities of the present invention is for by dried finished product packing.Packaging facilities can use known in the art
Those.
Heretofore described " discharge " (such as discharges the mixture of crystal and serosity, from crystallization from circulation subsider
Equipment is discharged magma, from centrifugation apparatus, discharges magnesium sulfite crystal etc.) device for transferring can be used, specifically obtain at one
In embodiment, described device for transferring is excavationg pump.
The present invention can also arrange overtemperature and meet an urgent need heat sink in the gas approach position of flue gas desulfurization device, other to solve
The appearance of flue-gas temperature overtemperature situation after smoke uptake cancellation.When temperature exceedes limiting temperature, the serosity on top, serum recycle pond
Send into overtemperature through circulating pump to meet an urgent need the emergency area that heat sink determines, for the emergent cooling of flue gas desulfurization device.Above-mentioned restriction
Temperature can be 160～200 DEG C, preferably greater than or equal to 180 DEG C.
<flue gas desulfurization produces the method for magnesium sulfite>
The said apparatus utilizing the present invention can produce magnesium sulfite, comprises the steps: that flue gas desulfurization step, serosity follow
Ring step, evaporation-concentration step, circulation precipitation step.Preferably, this method farther include crystallisation step, centrifugation step and
Drying steps, optionally, it is also possible to include packaging step.
The flue gas desulfurization step of the present invention is to use the titanium dioxide in magnesium oxide method removing flue gas in flue gas desulfurization device
Sulfur, and form absorption serosity.According to an embodiment of the invention, the described top within flue gas desulfurization device is provided with two
Absorption of sulfur oxides spray district.Flue gas is inside the gas approach access arrangement of flue gas desulfurization device, through two in uphill process
Absorption of sulfur oxides spray district carries out desulfurization and absorbs reaction, and the sulfur dioxide in flue gas is absorbed, and the flue gas after purification takes off from flue gas
The top of sulfur equipment is discharged.The preparation that inventive desulfurization is used is as previously mentioned.Flue gas is at the gas approach of flue gas desulfurization device
The flow velocity at place is 2.5～4.5m/s, and preferably 3～4m/s, input gas temperature is 110～180 DEG C, preferably 120～160 DEG C.
The serum recycle step of the present invention is the magnesium sulfite serosity received in serum recycle pond to be recycled to flue gas take off
Sulfur dioxide in sulfur equipment absorbs in spray district and evaporation concentration equipment.Described circulation can be carried out by circulating pump.As
Preferably, described magnesium sulfite serosity is recycled to sulfur dioxide after filtering absorb in spray district and/or evaporation concentration equipment.Make
For it is further preferred that by described magnesium sulfite serosity after filtering in evaporation concentration equipment.It is highly preferred that by described magnesium sulfite
Serosity is sent into filter plant from serum recycle pond by excavationg pump, enters evaporation and concentration absorbed layer by circulating pump again and carry out after filtration
Evaporation and concentration.Described filter plant is as described above.It is recycled to the serosity of evaporation concentration equipment to preferably comprise output (i.e. serosity follows
Cisterna ambiens circulation output total amount) 30～45vt%, preferably 35～40vt%；It is recycled to sulfur dioxide and absorbs the serosity in spray district
Each sulfur dioxide can be respectively fed to by least two circulating pump and absorb spraying layer, be recycled to sulfur dioxide and absorb spray district
Serosity preferably comprise the 40～50vt% of output, preferably 45～50vt%.PH value in serum recycle pond is preferably controlled in 5.5
～between 7.
The evaporation-concentration step of the present invention is that the serosity (magnesium sulfite serosity) that will loop to evaporation concentration equipment follows
Ring evaporation and concentration also forms enriched product.According to an embodiment of the invention, described evaporation concentration equipment is arranged on flue gas
Inside desulphurization plant, and it is arranged on the bottom in sulfur dioxide absorption spray district.The flue gas of the present invention first passes through in uphill process
Evaporation and concentration spraying layer (has one-level sulfur dioxide absorption function), after cooling and initial absorption, then inhales through sulfur dioxide
Receive spray district and carry out desulfurization absorption reaction.Flue gas after desulfurization the most directly can be arranged after carrying out dehydrating demisting by demister further
Put.
The circulation precipitation step of the present invention is to receive from the enriched product in evaporation concentration equipment in circulation subsider,
And enriched product is settled, to form sedimentation products (crystal discharged after initial crystallization and the mixture of serosity).Sedimentation
Magnesium sulfite crystal grain in product is more than 0.1mm；Preferably, sedimentation products (crystal and the serosity that circulation precipitation step is discharged
Mixture) in solid content more than 30wt%.Circulation subsider temperature general control at 55～70 DEG C, preferably 60～65 DEG C.Excellent
Selection of land, (crystal and the mixture of serosity, crystal grain is more than 0.1mm to the sedimentation products that circulation precipitation step is discharged, and solid content is more than
30wt%) enter in crystallizer crystallize further via the outlet being positioned at bottom.The serosity overflowed by circulation subsider
It is recycled in evaporation concentration equipment be circulated evaporation and concentration；Preferably, after first passing through the filtration of filter equipment, then enter through circulating pump
Enter evaporation and concentration spraying layer and carry out recirculation.Described filter plant is as described above.
Crystallisation step of the present invention is for the sedimentation products (crystal will discharged in circulation precipitation step in crystallizer
Mixture with serosity) further crystallization obtain magma；Enter the sedimentation products of crystallizer, by cooling in crystallizer
Mode realize magnesium sulfite hypersaturated state decrease temperature crystalline, form magma further, crystallization temperature general control is 20～30
DEG C, preferably 20～25 DEG C；The crystal grain formed in crystallisation step is more than 0.15mm, more preferably greater than 0.2mm.The granularity of the present invention is adopted
(seeing GB/T21524-2008) is measured with sieve method.For anti-crystal granula sedimentation, in crystallizer, it is provided with agitating device, sulfurous
Acid magnesium crystal in crystallizer gradually grow up disengaging agitator disturbance be deposited in bottom crystallizer, by excavationg pump by magma
Discharge, and send in centrifugation apparatus.The solid content of the magma discharged is more than 40wt%.
The centrifugation step of the present invention be in centrifugation apparatus by crystallisation step discharge magma centrifugation formed mother solution and
Magnesium sulfite product (preliminary product magnesium sulfite crystal)；In order to ensure centrifugal fully, centrifugal speed control 1500～
2000rpm, preferably 1600～1800rpm.For intermittent operation, the centrifugation time of every batch materials controls at 5～30 minutes,
It is preferably 5～10 minutes.For continuous way operate, the centrifugation time of every batch materials controls at 10～30 minutes, preferably 10～
15 minutes.The water content of the magnesium sulfite product (preliminary product magnesium sulfite crystal) obtained in centrifugation step is less than 2wt%.From
In heart step, isolated mother solution is recycled in evaporation concentration equipment, such as, can be recycled to evaporation and concentration by circulating pump and set
In Bei.
The drying steps of the present invention is for be dried magnesium sulfite product to finished product in drying equipment.The dry step of the present invention
Suddenly can carry out by the way of being vacuum dried or be passed through and adding hot-air.Baking temperature is 90～150 DEG C, preferably 100～
130 DEG C, more preferably 110～120 DEG C；Drying pressure is 0.01～0.5MPa, preferably 0.05～0.2MPa.By dry step
Suddenly, the moisture of dried precipitation is less than 1wt%, preferably smaller than 0.5wt%, more preferably less than 0.1wt%.At a tool
In body embodiment, by temperature be 120 DEG C of pressure be that air heating is sent into vibrated fluidized bed and existed by the saturated vapor of 0.2MPa
And realize magnesium sulfite crystal under the effect of mechanical vibration and be fully dried into magnesium sulfite finished product.
Below in conjunction with accompanying drawing, the present invention will be described in more detail.
<embodiment 1>
Fig. 1 is the device schematic diagram of the present embodiment 1, and this device includes a desulfurizing tower 1.The middle and lower part of desulfurizing tower 1 is provided with
Gas approach 23, top are provided with exhanst gas outlet 10.Gas approach 23 is provided above overtemperature and meets an urgent need heat sink 24, other to solve
The appearance of flue-gas temperature overtemperature situation after smoke uptake cancellation.When temperature exceedes limiting temperature 180 DEG C, top, serum recycle pond 11
Serosity deliver to be met an urgent need the emergency area that heat sink 24 determines, for desulfurization by overtemperature through overtemperature heat sink circulating pump 15 of meeting an urgent need
The emergent cooling of tower 1.It is provided above evaporation and concentration spraying layer 3, on evaporation and concentration spraying layer at overtemperature heat sink 24 of meeting an urgent need
Side is provided with liquid accumulating device 4；Liquid accumulating device 4 is provided above two grades of sulfur dioxide and absorbs spraying layer 7 and three grades of sulfur dioxide absorption sprays
Drench layer 8；Three grades of sulfur dioxide absorb spraying layer 8 and are provided above demister 9；Circulation sedimentation it is provided with below gas approach 23
Groove 2, the middle and upper part of circulation subsider 2 is provided with overfall 5, and overfall 5 is connected with filter 22 through slurry pool excavationg pump 21；Follow
Ring subsider 2 bottom is provided with circulation subsider outlet 6；Serum recycle pond 11 is arranged on the bottom of desulfurizing tower 1, its outlet
Road is divided into four tunnels, and a road is connected with filter 22 via slurry pool excavationg pump 21 from the bottom in serum recycle pond 11, filter 22
It is connected to evaporation and concentration spraying layer 3 through evaporation and concentration circulating pump 12, makes the clear liquid that filter 22 is filtrated to get via evaporation and concentration
Circulating pump 12 is delivered to evaporation and concentration spraying layer 3 and is carried out condensing crystallizing；Another two-way from the top in serum recycle pond 11 respectively through two grades
Sulfur dioxide absorbs spraying layer circulating pump 13 and three grades of sulfur dioxide absorb spraying layer circulating pump 14 and two grades of sulfur dioxide absorptions
Spraying layer 7 and three grades of sulfur dioxide absorb spraying layer 8 and connect；Meet an urgent need through overtemperature from the top in serum recycle pond 11 and lower the temperature in 4th tunnel
Device circulating pump 15 emergency area determined by heat sink 24 of meeting an urgent need with overtemperature is connected, with the serosity by top, serum recycle pond 11
Deliver to be met an urgent need the emergency area that heat sink 24 determines by overtemperature through overtemperature heat sink circulating pump 15 of meeting an urgent need.Circulation subsider is discharged
Mouth 6, crystallisation by cooling Sedimentation tank 16, centrifuge 17, exsiccator 18 and packer 19 are sequentially connected with；And centrifuge 17 also via
Mother solution returns evaporation and concentration layer circulating pump 20 and is connected with evaporation and concentration circulating pump 12, delivers to evaporation and concentration with the mother solution by centrifugal generation
Spraying layer 3 is circulated crystallization.
The technological process of the present embodiment is as follows:
A. flue gas enters into desulfurizing tower 1 from the gas approach 23 of desulfurizing tower 1, enters after overtemperature meets an urgent need heat sink 24
Evaporation and concentration spraying layer 3 carries out lowering the temperature and initial absorption；
B. the flue gas after cooling and initial absorption sequentially enters two grades of sulfur dioxide and absorbs spraying layers 7 and three grades of sulfur dioxide
Absorb spraying layer 8 to carry out desulfurization and absorb reaction, finally enter demister 9 and carry out after dehydrating demisting the exhanst gas outlet through top chimney
Directly discharge in 10；
C. two grades of sulfur dioxide absorption spraying layers 7 and three grades of sulfur dioxide absorb what spraying layer 8 sulfur dioxide absorption was formed
Absorb serosity and enter serum recycle pond 11；
D. the serosity of bottom, serum recycle pond 11 is discharged through slurry pool excavationg pump 21, is then passed through delivering to after filter 22 filters
Evaporation and concentration spraying layer 3 is evaporated concentrating, and its circulating load accounts for the 35vt% of serum recycle pond serosity output total amount；Serum recycle
The serosity on top, pond 11 absorbs 13, three grades of sulfur dioxide of spraying layer circulating pump by two grades of sulfur dioxide and absorbs spraying layer circulating pump
14 deliver to two grades of sulfur dioxide respectively absorbs spraying layer 7 and three grades of sulfur dioxide absorption spraying layers 8, and the circulating load of the two accounts for output
The 50vt% of total amount, the two volume ratio is 1: 1；
E. the serosity overflowed by the overfall 5 of circulation subsider 2 enters filter 22 through slurry pool excavationg pump 21, through filtering
After deliver to evaporation and concentration spraying layer 3 and carry out recirculation crystallization；
F. the crystal grain that the circulation subsider outlet 6 bottom circulation subsider 2 the is discharged sedimentation products more than 0.1mm is (sub-
Magnesium sulfate crystals and the mixture of serosity, solid content are more than 30wt%) enter crystallisation by cooling Sedimentation tank 16 in carry out decrease temperature crystalline,
Form the crystal grain magnesium sulfite magma (solid content is more than 40wt%) more than 0.15mm further；Settle for anti-crystal, in cooling
Being provided with agitating device in crystallization Sedimentation tank 16, agitating device is electric mixing device；
G. the magma (solid content is more than 40wt%) that crystallisation by cooling Sedimentation tank 16 is formed is sent into centrifuge 17 and is separated, from
The mother solution of scheming 17 isolated is delivered to evaporation and concentration spraying layer 3 and is circulated evaporation and concentration, containing of centrifuge 17 isolated
The water yield is delivered to exsiccator 18 less than the magnesium sulfite product of 2wt% and is further dried to finished product, and delivers to packer 19 and wrap
Dress.
In the technological process of the present embodiment:
1) make magnesium hydroxide slurry by magnesia powder adds tap water, be pumped to desulfurizing tower 1 as desulfurizing agent；
2) flue gas (oxygen content is 3vt%) that coal-burning boiler produces enters into desulfurization from the gas approach 23 of desulfurizing tower 1
Tower 1, is discharged by exhanst gas outlet 10.
3) pH value in the serum recycle pond 11 bottom desulfurizing tower 1 controls between 6～7；
4) filter 22 has 300 mesh filter mediums, to realize the magnesium sulfite serosity (serosity of bottom, serum recycle pond 11
With overfall 5 overflow serosity) fine straining.
5) temperature of circulation subsider 2 controls at 60 DEG C, and the solid content sedimentation products more than 30wt% is via circulation sedimentation
The circulation subsider outlet 6 of groove 2 enters the further decrease temperature crystalline of crystallisation by cooling Sedimentation tank 16；
6) temperature stabilization is passed through at 20～30 DEG C of recirculated cooling waters to the magnesium sulfite solution in crystallisation by cooling Sedimentation tank 16
Cooling realizes magnesium sulfite hypersaturated state decrease temperature crystalline；
7) by temperature be 120 DEG C, pressure be that air heating is sent into exsiccator 18 and (i.e. vibrated by the saturated vapor of 0.2MPa
Fluid bed), and under the effect of mechanical vibration, magnesium sulfite crystal fully dried as magnesium sulfite finished product and be delivered to automatically
Packer is packed, and finally gives the magnesium sulfite product that quality is more than industry certified products；
Other parameter of above-mentioned technique refers to table 1, the present embodiment fume emission situation and the situation of gained magnesium sulfite
See table 2 and table 3.
Table 1 200t/h coal burning flue gas desulfurization project duty parameter table
| Sequence number | Project | Quantity | Unit |
| 1 | Desulfurizing tower inlet flue gas amount (operating mode) | 380000 | m3/h |
| 2 | Mark state exhaust gas volumn | 277863 | Nm3/h |
| 3 | Desulfurizing tower entrance flue gas temperature | 120 | ℃ |
| 4 | SO2Entrance concentration | 4000 | mg/Nm3 |
| 5 | Magnesium sulfur ratio | 1.02 | Mg/S |
| 6 | Magnesium oxide purity | 70～85 | % mass percent |
| 7 | Humidity of flue gas | 5.2 | % mass percent |
The discharge of table 2 desulfurizing item and magnesium sulfite output situation
| Sequence number | Project | Quantity | Unit |
| 1 | Desulfurizer exiting flue gas amount (operating mode) | 346085 | m3/h |
| 2 | Exhaust gas temperature | 51 | ℃ |
| 3 | SO2Concentration of emission | ＜ 100 | mg/Nm3 |
| 4 | Magnesium sulfite quantum of output | 3.6 | t/h |
| 5 | Magnesium sulfite quality | ＞ 98 | % mass percent |
Table 3 desulfurizing item output magnesium sulfite quality
| Sequence number | Project | Quantity | Unit |
| 1 | Main content is (with MgSO3Meter) | 98 | % mass percent |
| 2 | Ferrum (in terms of Fe) content | 0.0042 | % mass percent |
| 3 | Chloride (in terms of Cl) content | 0.02 | % mass percent |
| 4 | Content of beary metal | 0.0015 | % mass percent |
| 5 | Water insoluble matter content | 0.06 | % mass percent |
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the flesh and blood of the present invention, and this area skill
Art personnel it is contemplated that any deformation, improve, replace and each fall within the scope of the present invention.
Claims (8)
1. the method that the device utilizing flue gas desulfurization to produce magnesium sulfite produces magnesium sulfite, it is characterised in that described
Device includes:
Flue gas desulfurization device, is internally provided with sulfur dioxide and absorbs spray district, for using two in magnesium oxide method removing flue gas
Sulfur oxide, and form absorption serosity；
Serum recycle pond, for receiving the described absorption serosity from flue gas desulfurization device, and will absorb serum recycle to dioxy
Change sulfur to absorb in spray district and evaporation concentration equipment；
Evaporation concentration equipment, is used for will loop to serosity evaporation and concentration therein, to form enriched product；With
Circulation subsider, for receiving the enriched product from evaporation concentration equipment, and settles enriched product, to be formed
Sedimentation products；
Wherein, described serum recycle pond, evaporation concentration equipment and circulation subsider are arranged at inside flue gas desulfurization device；
Described device also includes liquid accumulating device, and this liquid accumulating device is for absorbing spray by described evaporation concentration equipment and described sulfur dioxide
Separate out；
Described method comprises the steps:
Flue gas desulfurization step: use the sulfur dioxide in magnesium oxide method removing flue gas in flue gas desulfurization device, and form absorption
Serosity；
Serum recycle step: receive the described absorption serosity from flue gas desulfurization device in serum recycle pond, and absorption is starched
Liquid is recycled to sulfur dioxide and absorbs in spray district and evaporation concentration equipment；
Evaporation-concentration step: will loop to serosity evaporation and concentration therein in evaporation concentration equipment, to form enriched product；With
Circulation precipitation step: receive the enriched product from evaporation concentration equipment in circulation subsider, and enriched product is entered
Row sedimentation, to form sedimentation products.
Method the most according to claim 1, it is characterised in that in the device, described sulfur dioxide absorbs spray
District includes that at least two sulfur dioxide absorbs spraying layer；Described evaporation concentration equipment is positioned at sulfur dioxide and absorbs under spray district
Portion.
Method the most according to claim 1 and 2, it is characterised in that described device farther includes:
Crystallizer, for the sedimentation products crystallization of self-loopa subsider in the future, to form crystallized product；
Centrifugation apparatus, for by the crystallized product centrifugation from crystallizer, to form mother solution and magnesium sulfite product；With
Drying equipment, for being dried the magnesium sulfite product from centrifugation apparatus.
Method the most according to claim 1 and 2, it is characterised in that described flue gas meets one of following condition:
1) flue gas described in is the flue gas from coal-burning boiler；
2) content of sulfur dioxide of described flue gas is 300mg/Nm3～20000mg/Nm3, and oxygen content be 0～8vt%.
Method the most according to claim 3, it is characterised in that described method farther includes:
Crystallisation step: the sedimentation products of self-loopa subsider crystallizes, to form crystallized product in the future in crystallizer；
Centrifugation step: by the crystallized product centrifugation from crystallizer in centrifugation apparatus, to form mother solution and sulfurous acid
Magnesium product；With
Drying steps: in drying equipment, the magnesium sulfite product from centrifugation apparatus is dried.
Method the most according to claim 5, it is characterised in that overflow by circulation subsider in described circulation precipitation step
The serosity gone out is recycled in evaporation concentration equipment after filtering.
Method the most according to claim 5, it is characterised in that isolated Recycling Mother Solution is to steaming in described centrifugation step
Send out in concentrator.
Method the most according to claim 5, it is characterised in that the magnesium sulfite crystal grain in sedimentation products is more than 0.1mm；Knot
Magnesium sulfite crystal grain in brilliant product is more than 0.15mm.
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| CN106467313B (en) * | 2015-08-19 | 2017-12-08 | 中晶环境科技股份有限公司 | A kind of device and technique of coal burning flue gas desulfurization production magnesium sulfate |
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| JPH10109013A (en) * | 1996-10-04 | 1998-04-28 | Hisaji Koyama | Magnesium oxide and regenerated sulfuric acid recovering type flue gas desulfurization apparatus |
| JP3573950B2 (en) * | 1997-06-24 | 2004-10-06 | 東洋エンジニアリング株式会社 | Exhaust gas desulfurization method |
| CN1207083C (en) * | 2003-04-11 | 2005-06-22 | 清华大学 | Technology for magnesia wet method stack gas desulfurization and recovering the products |
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