CN101760974A - Process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber - Google Patents
Process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber Download PDFInfo
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- CN101760974A CN101760974A CN200810171525A CN200810171525A CN101760974A CN 101760974 A CN101760974 A CN 101760974A CN 200810171525 A CN200810171525 A CN 200810171525A CN 200810171525 A CN200810171525 A CN 200810171525A CN 101760974 A CN101760974 A CN 101760974A
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Abstract
The invention relates to a process for performing ammonium sulfite pulping by using a sulfur-containing flue gas absorber, which comprises the following steps: (1) performing desulphurization on flue gas by using ammonia water, wherein the flue gas is sulfur-containing flue gas; and (2) performing ammonium sulfite pulping during papermaking by using sulfurous acid mixed solution obtained after the desulphurization. In the process, a high-efficiency flue gas absorption system is adopted; the obtained ammonium sulfite is used for ammonium sulfite pulping in papermaking industry; and heavy contaminated condensate produced by pulping can also be used for absorbing sulfur dioxide in the flue gas. The scheme of the invention not only minimally reduces the environmental pollution, but also recycles the resources. The process is particularly suitable to be used in a paper mill with a self-owned power plant.
Description
Technical field
The present invention relates to a kind of circulation technology, particularly utilize the processing method of industrial smoke, in particular, relate to a kind of technology of utilizing the sulfur-containing smoke gas assimilate to carry out pulping with ammonium sulfite method.
Background technology
As everyone knows, coal-burning boiler or thermal power plant produce a large amount of flue gases, contain SO in these flue gases
2, multiple harmful substances such as SO, heavy damage human earth environment of depending on for existence, harm people's health.So various processing absorb the method for coal-fired flue-gas and also just arise at the historic moment, wherein especially more effective with the alkaline process absorption, and the alkaline process absorption has adopted ammonia to absorb more.
For example patent application 200310115522 discloses a kind of method of flue gas being carried out desulfurization with ammonium sulfite, bisulfite ammonium salt solution, this method is by regulating pH value in the desulfurizing tower to certain limit with ammonia, thereby in desulfurizing tower, form equilibrium state solution, the absorption of sulfur dioxide is reached at utmost.At last product ammonium sulfite mixed solution is carried out electron irradiation and be oxidized to ammonium sulfate.And in fact, because the flue gas rate of climb is very fast, the desulfurizing tower of using can not effectivelyly be removed pollutants such as sulfur in smoke at present.If want to use this tower to improve absorption efficiency, then need increase considerably tower height, but will certainly increase cost greatly like this, and bring technical difficulty.
Patent application 200510123488 discloses one and has used ammoniacal liquor and ammonium sulfite mixed liquor to absorb sulfur dioxide in flue gas, thereby obtains the method for ammonium sulfite, and the ammonium sulfite that obtains is used to prepare fertilizer.But what this method obtained must be the product mix of ammonium sulfite and other materials, and it also needs further processing, and must also have loss of material and the generation of other waste pollutants.
Exhaust gas desulphurization method is varied at present, but mostly generates the low-down ammonium sulfate of economic value added and be used to prepare chemical fertilizer.In addition, in the absorption process of flue gas, also there is the lower problem of absorptivity.
In view of this, special proposition the present invention, the present invention has adopted smoke absorption system efficiently, pass through controlled condition, the pulping with ammonium sulfite method that ammonium sulfite is used for paper industry will be obtained, the ammonium sulfite mixture that the present invention obtains can be directly used in the papermaking in the pulping and digesting technology, need not to carry out any special processed again, and can not produce new pollutant again.The present invention program not only has been reduced to bottom line with environmental pollution, and has realized resource reutilization.The present invention is particularly suitable for the paper mill of power plant for self-supply and uses.
Summary of the invention
The object of the invention is to provide a kind of circulation technology that utilizes the sulfur-containing smoke gas assimilate to carry out pulping with ammonium sulfite method.
For realizing the object of the invention, the following technical scheme of special employing:
A kind of technology of utilizing the sulfur-containing smoke gas assimilate to carry out pulping with ammonium sulfite method comprises the steps:
(1) flue gas is used the ammoniacal liquor desulfurization, described flue gas is a sulfur-containing smoke gas;
(2) the ammonium sulfite mixed solution that obtains after the desulfurization is used for the papermaking pulping with ammonium sulfite method, and described ammonium sulfite solution concentration is 25%～35%, and purity is 80%～99%, and described percentage is weight percentage.
In general, paper industry waste water and power plant's waste gas are the main sources of present environmental pollution, and adopt the inventive method that the two is carried out combination, the two pollutant is no longer directly discharged, and carry out recycle.Not only environmental pollution is reduced to minimum level, and resource has been carried out regeneration cycle, met the trend of present China and development of world economy.
According to foregoing circulation technology, wherein the described desulfurization of preferred steps (1) is provided with air-introduced machine before desulfurizing tower, and described air-introduced machine flue gas inlet is preferably 200000～400000m
3/ h, more preferably 305000～400000m
3/ h most preferably is 310800m
3/ h.
The flue gas inlet is rationally controlled, can be so that sulfur in smoke be able to sufficient absorption, if it is excessive to enter the flue gas inlet, then sulfur dioxide can not fully be absorbed, the sulfur dioxide in flue gas of discharge is residual too much, still can atmosphere pollution; And if the flue gas inlet is too small, then the ammonium sulfite of Sheng Chenging easily is desulfurized the dioxygen oxidation that dissolves in the mixed solution in the tower and becomes ammonium sulfate, and can not be used for pulping with ammonium sulfite method.We find that through groping repeatedly the flue gas inlet is 200000～400000m at last
3/ h can better address this problem, and is 300000～400000m and advance the flue gas inlet
3/ h, effect is desirable more, when reaching 310800m
3During/h, then hardly can residual sulfur dioxide and that ammonium sulfite takes place is oxidized.
According to foregoing improvement technology, desulfurization is in the described desulfurizing tower of step (1):
(A) with flue gas ash removal after air-introduced machine enter in the desulfurizing tower, spray into ammoniacal liquor and absorb sulfur in smoke, the mixed solution of ammoniacal liquor in the desulfurizing tower and ammonium sulfite, ammonium bisulfite carries out circulated sprinkling by one or more layers spray equipment to flue gas, and described desulfurizing tower top also has a clear water spray equipment;
(B) the ammonium sulfite mixed solution that obtains precipitated, filter and obtain pure ammonium sulfite solution.
Flue gas enters in the desulfurizing tower, by pipeline the ammoniacal liquor in the deposed ammonia jar is sprayed into the absorption sulfur in smoke, in the collecting tank of desulfurizing tower bottom is excess of ammonia water and ammonium sulfite, the mixed solution of ammonium bisulfite, mixed solution is got to the tower middle part by pump, and the flue gas that sprays rising by multilayer carries out circulated sprinkling, thereby residual sulfur dioxide is absorbed, get back to the collecting tank at the bottom of the tower then, also has a clear water spray equipment on desulfurizing tower top, can spray clear water and be used for absorbing the ammonia that sweetening process is overflowed, and flow into the desulfurizing tower bottom downwards and carry out circulated sprinkling absorption sulfur dioxide, the flue gas after the absorption is discharged from cat head.The ammonium sulfite mixed solution that obtains is squeezed in the ammonium sulfite jar by pump, obtains pure ammonium sulfite solution behind process precipitation, the filtration, purification, and is positioned over clean ammonium sulfite storage tank.
In step (A) process the mixed solution of ammonium sulfite, ammonium bisulfite and ammoniacal liquor is sprayed repeatedly sulfur dioxide in flue gas is absorbed repeatedly, can absorb comparatively completely sulfur dioxide in flue gas.
Sulfur dioxide and ammoniacal liquor generate ammonium bisulfite and ammonium sulfite in desulfurizing tower, the mixed solution of the ammonium bisulfite in the collecting tank, ammonium sulfite and ammoniacal liquor is reached the tower middle part by pump, and spray by spray equipment, ammonium sulfite has wherein absorbed sulfur in smoke and has generated ammonium bisulfite, and get back to collecting tank, ammonium bisulfite generates ammonium sulfite with the excessive ammonia reaction again.Mixed liquor circulates repeatedly the sulfur dioxide in the desulfurizing tower is absorbed.Following chemical reaction takes place in the desulfurizing tower:
SO
2+2NH
3+H
2O＝(NH
4)
2SO
3
SO
2+(NH
4)
2SO
3+H
2O＝2NH
4HSO
3
NH
3+NH
4HSO
3＝(NH
4)
2SO
3
2NH
3+SO
2+2H
2O＝(NH
4)
2SO
3·H
2O
The absorption technique in above-mentioned desulfurizing tower, the desulfurizing tower of any other prior art also can be used for the present invention, and the realization that is to say circulation technology of the present invention is not subjected to the restriction of this body structure of desulfurizing tower.
Before flue gas enters desulfurizing tower, use air-introduced machine that flue gas is pressurizeed, flue gas is introduced desulfurizing tower.By control air-introduced machine flue gas inlet, can control entering of oxygen, can avoid more sulfite oxidation to become ammonium sulfate like this, thereby product better is used for the paper-making pulping process.It is 200000～400000m that air-introduced machine advances the flue gas inlet
3/ h is preferably 310800m
3/ h.One flue gas memory device perhaps is set before flue gas enters desulfurizing tower, treats to introduce desulfurizing tower with air-introduced machine again when flue gas pressures reaches certain value, and the burning of in the flue gas because front has consumed almost all oxygen, thereby prevented that better ammonium sulfite is oxidized.
According to foregoing technology, the described flue gas of step (A) after discharge at the desulfurizing tower top, also through an ammonia absorber, absorbs ammonia remaining in the flue gas with water purification through desulfurization, forms weak aqua ammonia, and circulation is used to absorb flue gas after the adjusting concentration.
Described weak aqua ammonia can enter in the ammonia water tank, enters the deposed ammonia jar after the adjusting concentration; Perhaps weak aqua ammonia directly enters the deposed ammonia jar, and regulates ammonia concn in the deposed ammonia jar.
According to foregoing technology, preferably in the described desulfurizing tower of step (A), the pH checkout gear is set, regulate by control ammoniacal liquor addition that ammonium sulfite mixed solution pH is 7.2～8.2 in the desulfurizing tower, preferred pH is 7.5.
Yet according to foregoing technology, the described multilayer spray of step (A) is three layers of spray preferably; Temperature is preferably 65～120 ℃ in the desulfurizing tower; Pressure is preferably 100～110kpa, more preferably 106.4kpa; Desulfurizing tower smoke entrance relative pressure is preferably 1000～3000Pa, more preferably 1500～2000Pa.
The pressure differential of described desulfurizing tower smoke entrance relative pressure for importing and exporting by pressure is adjusted, can make under most economical prerequisite that the absorption to sulfur dioxide reaches optimum efficiency.
According to foregoing technology, described ammonia concn is for being preferably 0.8～11%, and more preferably 1～3%.
According to foregoing technology, the described pulping with ammonium sulfite method technology of step (2) is Ammonium Sulfite Method boiling conventional in the prior art or adopts Ammonium Sulfite Method boiling of the present invention.Ammonium Sulfite Method boiling of the present invention can be carried out in batch (-type) ball-type boiling vessel, continuous steamer or vertical digester, and is specific as follows:
1) in batch (-type) ball-type boiling vessel or continuous steamer:
Described Ammonium Sulfite Method boiling is:
1. add cooking liquor at the stalk that is used for slurrying, wherein the ammonium sulfite consumption is the 9-13% to the over dry material quantity, and joining amount of sodium hydroxide is 0～8% of over dry material quantity, and liquor ratio is 1: 2～4;
2. feed steam and heat, heat temperature raising is to 165～173 ℃ of temperature, intensification, little venting, omnidistance 160～210 minutes time of insulation;
2) in vertical digester:
Described Ammonium Sulfite Method boiling is:
The stalk that will be used for slurrying is that 120～140 ℃ hot black liquor is by the packer digester of packing into by temperature, after the dress pot is full, close pot cover, replenishing temperature in the digester is 130～160 ℃ of steaming preparations, discharge the air in the pot simultaneously and boost to 0.6～0.75MPa, the cooking liquor heat cycles pump of open system and tube still heater are that cooking liquor is warming up to 156～173 ℃, heat up, be incubated and be replaced into 180～220 minutes, put with pump at last slurry is delivered to spraying pot; In the described steaming preparation, wherein the ammonium sulfite consumption is to 9～15% of over dry material quantity, and joining amount of sodium hydroxide is 0～8% of over dry material quantity, and liquor ratio is 1: 6～10.
At this special pulping raw material of grass kind plant fiber, in the method for the invention, the chemical steaming soup has been carried out strict control, its concentration is reduced, reduce degraded and damage to the required composition of slurrying such as cellulose, hemicellulose.Simultaneously, in the process of thermophilic digestion, adopt the method reduce temperature retention time as far as possible in the method for the present invention, the time that makes grass kind plant be in high temperature shortens, thereby has reduced the degraded of cellulose and hemicellulose in the grass kind plant raw material.Therefore; boiling method of the present invention is compared with the prior art boiling method; protected the required composition of slurrying in the grass kind plant raw material to a great extent; shortened simultaneously temperature retention time greatly; significantly reduced energy consumption; and pulping yield is greatly improved, and reached 50-68%, thereby improved production efficiency greatly.Simultaneously, high-hardness pulp of the present invention can be used as the raw material of preparation bleach chemical pulp, because the concentration of used soup reduces during boiling, and the time of boiling and insulation also shortens greatly, thereby on to greatest extent, having reduced the loss and the degraded of needed cellulose and hemicellulose in the paper pulp, the yield and the intensity of paper pulp all is improved.
Technology of the present invention has following advantage:
(1) emission of industrial pollutants is few, and the pollutant chance all consumes and generate the product of economically valuable in inner loop.
(2) realized that resource circulation utilizes again, had high economic worth.
Description of drawings
Fig. 1 is circulation process figure of the present invention.
The specific embodiment
The following examples will be done to explain more specifically to the present invention, but the present invention is not limited only to these embodiment, and these embodiment do not limit the present invention in any way yet equally.
Embodiment 1
Flue gas at first carries out dedusting through electrostatic dust collection equipment, and after the flue gas after the dedusting pressurizeed through air-introduced machine, air-introduced machine flue gas inlet was 310800m
3/ h, flue gas enter in the collecting tank at the bottom of the desulfurizing tower, spray into excess of ammonia water and react with sulfur dioxide and generate ammonium sulfite and ammonium bisulfite.Form the ammonia water mixture of ammonium bisulfite, ammonium sulfite in the collecting tank, this mixed liquor is got to the eminence of tower, and spray downwards, evenly mix, thereby absorb residual sulfur dioxide in the flue gas with the flue gas that makes progress by three layers of spray equipment at tower middle part with pump.Ammonium bisulfite in the mixed liquor obtains ammonium sulfite with the sulfur dioxide reaction and gets back in the collecting tank.Circulate so repeatedly sulfur dioxide in flue gas is absorbed fully.Temperature is 65～120 ℃ in the desulfurizing tower; Pressure is 106.4kpa.Desulfurizing tower smoke entrance relative pressure is 1500～2000Pa.
Cat head also has a clear water spray equipment in addition, is used for absorbing the ammonia that sweetening process is overflowed, and gets back in the collecting tank, joins spray and absorbs in the circulation of sulfur dioxide.
One pH checkout gear is arranged in desulfurizing tower, when pH in the desulfurizing tower reaches 7.5 left and right sides, when promptly ammonium sulfite, ammonium bisulfite reach a poised state in the collecting tank, promptly emit and enter the ammonium sulfite jar.Through entering the ammonium sulfite storage tank of purification behind precipitation, the filtration, purification, be used for pulping with ammonium sulfite method then.The pure ammonium sulfite solution concentration that obtains behind process precipitation, the filtration, purification is 25～35%, and purity is 85～99%.
The waste gas that absorbs through water purification on desulfurizing tower top is discharged from cat head, enters in the ammonia absorber through air-introduced machine then, uses water purification to absorb remaining ammonia in the waste gas in ammonia absorber, forms weak aqua ammonia, enters ammonia water tank, regulates ammonia concn 1～3%.The ammoniacal liquor that to regulate over-richness then is passed in the deposed ammonia jar, recycles the absorption sulfur in smoke.In addition, the deposed ammonia that can also use other industry to produce in the deposed ammonia jar carries out waste gas after adjusting concentration is qualified and absorbs.Toxic emission after the absorption, absorption rate of sulfur dioxide reaches 99.5%.
Foregoing pulping with ammonium sulfite method technology is Ammonium Sulfite Method boiling conventional in the prior art, preferably adopts Ammonium Sulfite Method boiling of the present invention.Ammonium Sulfite Method boiling of the present invention can be carried out in batch (-type) ball-type boiling vessel, continuous steamer or vertical digester, and is specific as follows:
1) in batch (-type) ball-type boiling vessel or continuous steamer:
Described Ammonium Sulfite Method boiling is:
1. add cooking liquor at the stalk that is used for slurrying, wherein the ammonium sulfite consumption is to 9～11% of over dry material quantity, and joining amount of sodium hydroxide is 0～4% of over dry material quantity, and liquor ratio is 1: 2～4;
2. feed steam and heat, heat temperature raising is to 165～170 ℃ of temperature, intensification, little venting, omnidistance 160～180 minutes time of insulation;
2) in vertical digester:
Described Ammonium Sulfite Method boiling is:
The stalk that will be used for slurrying is that 120～130 ℃ hot black liquor is by the packer digester of packing into by temperature, after the dress pot is full, close pot cover, replenishing temperature in the digester is 130～145 ℃ of steaming preparations, discharge the air in the pot simultaneously and boost to 0.6～0.65MPa, the cooking liquor heat cycles pump of open system and tube still heater are that cooking liquor is warming up to 156～163 ℃, heat up, be incubated and be replaced into 180～200 minutes, put with pump at last slurry is delivered to spraying pot; In the described steaming preparation, wherein the ammonium sulfite consumption is to 9～12% of over dry material quantity, and joining amount of sodium hydroxide is 0～4% of over dry material quantity, and liquor ratio is 1: 6～10.
Utilize the ammonium sulfite mixed liquor that produces previously to carry out pulping with ammonium sulfite method, simultaneously also can add other ammonium sulfites, as the useless ammonium sulfite that obtains in the industrial utmost point ammonium sulfite bought or other industry.Pulping with ammonium sulfite method can be with reference to any pulping with ammonium sulfite method technology of prior art.
Embodiment 2
Flue gas at first carries out dedusting through dust removal by filtration equipment, and after the flue gas after the dedusting pressurizeed through air-introduced machine, it was 200000～400000m that air-introduced machine advances the flue gas inlet
3/ h enters in the collecting tank at the bottom of the desulfurizing tower, and spraying into excessive concentration is that 0.8～11% ammoniacal liquor reacts the generation ammonium sulfite with ammonium bisulfite.Form the ammonia water mixture of ammonium bisulfite, ammonium sulfite in the collecting tank, this mixed liquor is got to the eminence of tower, and spray downwards, evenly mix, thereby absorb residual sulfur dioxide in the flue gas with the flue gas that makes progress by two layers of spray equipment at tower middle part with pump.Ammonium bisulfite in the mixed liquor obtains ammonium sulfite with the sulfur dioxide reaction and gets back in the collecting tank.Temperature is 90～120 ℃ in the desulfurizing tower; Pressure is 100～110kpa.Desulfurizing tower smoke entrance relative pressure is 1000～3000Pa.
Cat head also has a clear water spray equipment in addition, is used for absorbing the ammonia that sweetening process is overflowed, and gets back in the collecting tank, joins spray and absorbs in the circulation of sulfur dioxide.
One pH checkout gear is arranged in desulfurizing tower, when pH reaches 7.2～8.2 in the desulfurizing tower, when promptly ammonium sulfite, ammonium bisulfite reach a poised state in the collecting tank, promptly emit and enter the ammonium sulfite jar.Through entering the ammonium sulfite storage tank of purification behind precipitation, the filtration, purification, be used for pulping with ammonium sulfite method then.The pure ammonium sulfite solution concentration that obtains behind process precipitation, the filtration, purification is 25～35%, and purity is 85～90%.
The waste gas that absorbs through water purification on desulfurizing tower top is discharged from cat head, enters in the ammonia absorber through air-introduced machine then, uses water purification to absorb remaining ammonia in the waste gas in ammonia absorber, forms weak aqua ammonia, enters ammonia water tank, regulates ammonia concn 0.8～11%.The ammoniacal liquor that to regulate over-richness then is passed in the deposed ammonia jar, recycles the absorption sulfur in smoke.In addition, the deposed ammonia that can also use other industry to produce in the deposed ammonia jar carries out waste gas after adjusting concentration is qualified and absorbs.
Utilize the ammonium sulfite mixed liquor that produces previously to carry out pulping with ammonium sulfite method, simultaneously also can add other ammonium sulfites, as the useless ammonium sulfite that obtains in the industrial utmost point ammonium sulfite bought or other industry.Pulping with ammonium sulfite method can be with reference to any pulping with ammonium sulfite method technology of prior art, the black liquor that pulping with ammonium sulfite method produces has produced the heavy foul condensate that contains ammonia when carrying out boiling, the perhaps this heavy foul condensate that produces in other processes of pulping with ammonium sulfite method, enter heavy foul condensate storage tank after the collection, it is consistent with deposed ammonia to regulate ammonia concentration, is passed into then in the deposed ammonia jar to be used for smoke absorption.The heavy foul condensate that perhaps will collect directly is passed in the deposed ammonia jar, regulates ammonia concentration 0.8～11% in the deposed ammonia jar.
Described pulping with ammonium sulfite method technology is Ammonium Sulfite Method boiling conventional in the prior art or adopts Ammonium Sulfite Method boiling of the present invention.Ammonium Sulfite Method boiling of the present invention can be carried out in batch (-type) ball-type boiling vessel, continuous steamer or vertical digester, and is specific as follows:
1) in batch (-type) ball-type boiling vessel or continuous steamer:
Described Ammonium Sulfite Method boiling is:
1. add cooking liquor at the stalk that is used for slurrying, wherein the ammonium sulfite consumption is the 11-13% to the over dry material quantity, and joining amount of sodium hydroxide is 4～8% of over dry material quantity, and liquor ratio is 1: 2～4;
2. feed steam and heat, heat temperature raising is to 170～173 ℃ of temperature, intensification, little venting, omnidistance 180～210 minutes time of insulation;
2) in vertical digester:
Described Ammonium Sulfite Method boiling is:
The stalk that will be used for slurrying is that 130～140 ℃ hot black liquor is by the packer digester of packing into by temperature, after the dress pot is full, close pot cover, replenishing temperature in the digester is 145～160 ℃ of steaming preparations, discharge the air in the pot simultaneously and boost to 0.65～0.75MPa, the cooking liquor heat cycles pump of open system and tube still heater are that cooking liquor is warming up to 163～173 ℃, heat up, be incubated and be replaced into 200～220 minutes, put with pump at last slurry is delivered to spraying pot; In the described steaming preparation, wherein the ammonium sulfite consumption is to 12～15% of over dry material quantity, and joining amount of sodium hydroxide is 4～8% of over dry material quantity, and liquor ratio is 1: 6～10.
Embodiment 3
Flue gas at first carries out dedusting through electrostatic dust collection equipment, and after the flue gas after the dedusting pressurizeed through air-introduced machine, air-introduced machine flue gas inlet was 305000～400000m
3/ h, flue gas enter in the collecting tank at the bottom of the desulfurizing tower, spray into excess of ammonia water and react with sulfur dioxide and generate ammonium sulfite and ammonium bisulfite.Form the ammonia water mixture of ammonium bisulfite, ammonium sulfite in the collecting tank, this mixed liquor is got to the eminence of tower, and spray downwards, evenly mix, thereby absorb residual sulfur dioxide in the flue gas with the flue gas that makes progress by three layers of spray equipment at tower middle part with pump.Ammonium bisulfite in the mixed liquor obtains ammonium sulfite with the sulfur dioxide reaction and gets back in the collecting tank.Circulate so repeatedly sulfur dioxide in flue gas is absorbed fully.Temperature is 100～110 ℃ in the desulfurizing tower; Pressure is 106.4kpa.Desulfurizing tower smoke entrance relative pressure is 1500～1800Pa.
Cat head also has a clear water spray equipment in addition, is used for absorbing the ammonia that sweetening process is overflowed, and gets back in the collecting tank, joins spray and absorbs in the circulation of sulfur dioxide.
One pH checkout gear is arranged in desulfurizing tower, when pH in the desulfurizing tower reaches 7.8～8.0 left and right sides, when promptly ammonium sulfite, ammonium bisulfite reach a poised state in the collecting tank, promptly emit and enter the ammonium sulfite jar.Through entering the ammonium sulfite storage tank of purification behind precipitation, the filtration, purification, be used for pulping with ammonium sulfite method then.The pure ammonium sulfite solution concentration that obtains behind process precipitation, the filtration, purification is 30～35%, and purity is 90～95%.
The waste gas that absorbs through water purification on desulfurizing tower top is discharged from cat head, enters in the ammonia absorber through air-introduced machine then, uses water purification to absorb remaining ammonia in the waste gas in ammonia absorber, forms weak aqua ammonia, enters ammonia water tank, regulates ammonia concn 1～3%.The ammoniacal liquor that to regulate over-richness then is passed in the deposed ammonia jar, recycles the absorption sulfur in smoke.In addition, the deposed ammonia that can also use other industry to produce in the deposed ammonia jar carries out waste gas after adjusting concentration is qualified and absorbs.Toxic emission after the absorption, absorption rate of sulfur dioxide reaches 99.9%.
Foregoing pulping with ammonium sulfite method technology is Ammonium Sulfite Method boiling conventional in the prior art, preferably adopts Ammonium Sulfite Method boiling of the present invention.Ammonium Sulfite Method boiling of the present invention can be carried out in batch (-type) ball-type boiling vessel, continuous steamer or vertical digester, and is specific as follows:
1) in batch (-type) ball-type boiling vessel or continuous steamer:
Described Ammonium Sulfite Method boiling is:
1. add cooking liquor at the stalk that is used for slurrying, wherein the ammonium sulfite consumption is to 9～11% of over dry material quantity, and joining amount of sodium hydroxide is 0～4% of over dry material quantity, and liquor ratio is 1: 2～4;
2. feed steam and heat, heat temperature raising is to 165～170 ℃ of temperature, intensification, little venting, omnidistance 160～180 minutes time of insulation;
2) in vertical digester:
Described Ammonium Sulfite Method boiling is:
The stalk that will be used for slurrying is that 120～130 ℃ hot black liquor is by the packer digester of packing into by temperature, after the dress pot is full, close pot cover, replenishing temperature in the digester is 130～145 ℃ of steaming preparations, discharge the air in the pot simultaneously and boost to 0.6～0.65MPa, the cooking liquor heat cycles pump of open system and tube still heater are that cooking liquor is warming up to 156～163 ℃, heat up, be incubated and be replaced into 180～200 minutes, put with pump at last slurry is delivered to spraying pot; In the described steaming preparation, wherein the ammonium sulfite consumption is to 9～12% of over dry material quantity, and joining amount of sodium hydroxide is 0～4% of over dry material quantity, and liquor ratio is 1: 6～10.
Utilize the ammonium sulfite mixed liquor that produces previously to carry out pulping with ammonium sulfite method, simultaneously also can add other ammonium sulfites, as the useless ammonium sulfite that obtains in the industrial utmost point ammonium sulfite bought or other industry.Pulping with ammonium sulfite method can be with reference to any pulping with ammonium sulfite method technology of prior art.
Above-mentioned for the present invention absorbs sulfur dioxide in flue gas generation ammonium sulfite with reclaiming deposed ammonia, and be used for the pulping and digesting of papermaking.But the present invention simultaneously is not limited to field of papermaking again, and any industrial production of this ammonium sulfite of may utilizing all can be with reference to the present invention.
Claims (8)
1. a technology of utilizing the sulfur-containing smoke gas assimilate to carry out pulping with ammonium sulfite method comprises the steps:
(1) flue gas is used the ammoniacal liquor desulfurization, described flue gas is a sulfur-containing smoke gas;
(2) the ammonium sulfite mixed solution that obtains after the desulfurization is used for the papermaking pulping with ammonium sulfite method, and described ammonium sulfite solution concentration is 25%～35%, and purity is 80%～99%.
2. circulation technology according to claim 1 is characterized in that, the described desulfurization of step (1) is provided with air-introduced machine before desulfurizing tower, and described air-introduced machine flue gas inlet is 200000～400000m
3/ h is preferably 305000～400000m
3/ h, more preferably 310800m
3/ h.
3. technology according to claim 1 is characterized in that, step (1) is described to be made of with the ammoniacal liquor desulfurization flue gas following step:
(A) with flue gas ash removal after air-introduced machine enter in the desulfurizing tower, spray into ammoniacal liquor and absorb sulfur in smoke, the mixed solution of ammoniacal liquor in the desulfurizing tower and ammonium sulfite, ammonium bisulfite carries out circulated sprinkling by one or more layers spray equipment to flue gas, and described desulfurizing tower top also is provided with a clear water spray equipment;
(B) the ammonium sulfite mixed solution that obtains precipitated, filter and obtain pure ammonium sulfite solution.
4. technology according to claim 3 is characterized in that, the described flue gas of step (A) is after desulfurization is discharged at the desulfurizing tower top, also through an ammonia absorber, absorb ammonia remaining in the flue gas with water purification, form weak aqua ammonia, circulation is used to absorb flue gas after the adjusting concentration.
5. technology according to claim 3 is characterized in that, in the described desulfurizing tower of step (A) the pH checkout gear is set also, regulates ammonium sulfite mixed solution pH7.2～8.2 in the desulfurizing tower by control ammoniacal liquor addition, and preferred pH is 7.5.
6. technology according to claim 3 is characterized in that, the described multilayer spray of step (A) is three layers of spray; Temperature is 65～120 ℃ in the desulfurizing tower; Pressure is 100～110kpa, is preferably 106.4kpa.
7. according to any described technology of claim 1～6, it is characterized in that described ammonia concn is 0.8～11%, is preferably 1～3%.
8. technology according to claim 1, it is characterized in that, the described pulping with ammonium sulfite method technology of step (2) is Ammonium Sulfite Method boiling conventional in the prior art or adopts Ammonium Sulfite Method boiling of the present invention, described Ammonium Sulfite Method boiling can be carried out in batch (-type) ball-type boiling vessel, continuous steamer or vertical digester, and is specific as follows:
1) in batch (-type) ball-type boiling vessel or continuous steamer:
Described Ammonium Sulfite Method boiling is:
1. add cooking liquor at the stalk that is used for slurrying, wherein the ammonium sulfite consumption is the 9-13% to the over dry material quantity, and joining amount of sodium hydroxide is 0～8% of over dry material quantity, and liquor ratio is 1: 2～4;
2. feed steam and heat, heat temperature raising is to 165～173 ℃ of temperature, intensification, little venting, omnidistance 160～210 minutes time of insulation;
2) in vertical digester:
Described Ammonium Sulfite Method boiling is:
The stalk that will be used for slurrying is that 120～140 ℃ hot black liquor is by the packer digester of packing into by temperature, after the dress pot is full, close pot cover, replenishing temperature in the digester is 130～160 ℃ of steaming preparations, discharge the air in the pot simultaneously and boost to 0.6～0.75MPa, the cooking liquor heat cycles pump of open system and tube still heater are that cooking liquor is warming up to 156～173 ℃, heat up, be incubated and be replaced into 180～220 minutes, put with pump at last slurry is delivered to spraying pot; In the described steaming preparation, wherein the ammonium sulfite consumption is to 9～15% of over dry material quantity, and joining amount of sodium hydroxide is 0～8% of over dry material quantity, and liquor ratio is 1: 6～10.
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