CN101760975A - Circulation process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber - Google Patents
Circulation process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber Download PDFInfo
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Abstract
The invention relates to a circulation 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; (2) performing ammonium sulfite pulping during papermaking by using sulfurous acid mixed solution obtained after the desulphurization; and (3) performing desulphurization on the flue gas in the step (1) by recycling ammonia-containing contaminated condensate produced during the ammonium sulfite pulping. In the circulation process, a high-efficiency flue gas absorption system is adopted; the obtained ammonium sulfite is used for ammonium sulfite pulping in papermaking industry; and the 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 circulation 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 circulation technology that utilizes the sulfur-containing smoke gas assimilate to carry out pulping with ammonium sulfite method.
Background technology
Along with industrial development, increasing poisonous fume, waste liquid are discharged among the nature, heavy damage human earth environment of depending on for existence.For example coal-burning boiler or thermal power plant produce a large amount of flue gases, contain SO in these flue gases
2, SO
3Etc. multiple harmful substances, caused the generation of acid rain, also brought out human various respiratory tract disease.Also have in addition in the paper industry, especially can produce a large amount of ammonia foul condensates that contain in the digestion process of pulping with ammonium sulfite method, present this foul condensate is all directly dischargings after the chemical treatment generally.This sewage has caused serious destruction to environment equally.
For fear of the generation of above-mentioned pollutant, people have proposed the processing method of various industrial waste gases, waste liquid:
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.
In order further to increase desulfurized effect, patent application 03245106 discloses a kind of desulfurizing tower that has a plurality of Venturi tubes, but this desulfurizing tower and complexity thereof, and Venturi tube occupied desulfurizing tower overwhelming majority spaces, instead had a strong impact on the assimilation effect of sulfur dioxide in flue gas.
In addition, solid pollutant is to the infringement of desulfurizing tower in the flue gas, patent application 200510200308 discloses a kind of scheme that Venturi tube is placed the desulfurizing tower outside, it is provided with spray equipment in Venturi tube, first water carries out dedusting to flue gas before flue gas enters desulfurizing tower, enters the desulfurizing tower absorption that circulates again.This method is compared the process that has only increased a dedusting with patent application 200310115522, and the absorption efficiency of sulfur dioxide be there is no obvious raising.
The ammonium bisulfite that patent application 97103626 disclosed sulfur methods obtain is handled with calcium hydroxide then and is obtained ammonium sulfite, is mixed for absorbing sulfur in smoke with ammoniacal liquor again.This method has produced new solid waste calcium sulfite again after using calcium hydroxide, and it is unsatisfactory to use ammonium sulfite to absorb the sulfur dioxide effect simultaneously.
And in that " ammonium sulfite is administered and to be contained SO
2Flue gas " (Sichuan chemical industry and corrosion control, 2001,4 (5): mention 54-55) and absorb the ammonium sulfite that generates behind the flue gas with sulfur dioxide and can be used for papermaking.But this article does not disclose its detail, and the ammonium sulfite that is used for papermaking at present requires purity higher usually, and absorbs the general complicated component of ammonium sulfite that flue gas obtains, and also needs loaded down with trivial details purification refine link, has increased the production run cost greatly.
In sum, lower to the most efficient of fume desulphurization method at present.And after flue gas carried out desulfurization, generation be the low-down ammonium sulfate of economic value added, and be used to prepare chemical fertilizer, this processing is a kind of great waste equally.
In view of this, special proposition the present invention, the present invention has adopted smoke absorption system efficiently, by controlled condition, will obtain the pulping with ammonium sulfite method that ammonium sulfite is used for paper industry, and the foul condensate that slurrying produces is used to absorb the sulfur dioxide of flue gas.The present invention program not only has been reduced to bottom line with environmental pollution, and resource has been realized recycle.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 circulation technology that utilizes 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, is preferably the industrial coal flue gas;
(2) the ammonium sulfite mixed solution that obtains after the desulfurization is used for the papermaking pulping with ammonium sulfite method;
(3) the foul condensate circulation that contains ammonia that produces in the pulping with ammonium sulfite method process is used for step (1) flue gas is carried out desulfurization.
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.At first flue gas is used the deposed ammonia desulfurization, the ammonium sulfite that obtains can be directly used in the papermaking pulping with ammonium sulfite method, and the deposed ammonia that slurrying produces is used further to absorb sulfur in smoke.
The present invention obtains need not consuming any resource again behind the ammonium sulfite and processes, and the whole circulation flow process also produces the emission of any heavily contaminated hardly, all resource inner loop digestion.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.
Foul condensate according to the described generation of circulation technology step (3) can be introduced into a foul condensate storage tank adjusting ammonia concn, preferably is adjusted to consistent in the deposed ammonia jar, and then is used to absorb sulfur in smoke in the feeding deposed ammonia jar; Perhaps directly enter in the deposed ammonia jar, in the deposed ammonia jar, regulate ammonia concn.
The purpose of regulating ammonia concn is to make the effect that absorbs sulfur in smoke subsequently to reach optimum state.The adjusting of this concentration belongs to the ordinary skill in the art, is conspicuous for those of ordinary skills, need not to make creative work.
In order to make smoke absorption reach optimum efficiency, the adjusting that flue gas advances the flue gas inlet also is one of them factor.According to the difference of ammonia concn, the difference of flue gas sulfur content, the adjusting of flue gas being advanced the flue gas inlet is conspicuous for those of ordinary skills, belongs to the scope of conventional design, need not to make creative work.
Yet preferably, according to foregoing circulation technology, flue gas enters before the desulfurizing tower through an air-introduced machine in the described sweetening process of step (1), and described air-introduced machine advances the flue gas inlet and is preferably 200000～400000m
3/ h, more preferably 305000～400000m
3/ h most preferably is 310800m
3/ h.
According to foregoing circulation technology, the described desulfurization of step (1) is for also being provided with a Venturi tube that is connected the desulfurizing tower bottom before desulfurizing tower.In the described Venturi tube spray equipment is set, makes flue gas at first fully mix with ammoniacal liquor in Venturi tube, mixed solution enters in the desulfurizing tower with flue gas again.
When air-introduced machine and Venturi tube existed simultaneously, general air-introduced machine was arranged on the front of Venturi tube, that is to say flue gas earlier through air-introduced machine, again through Venturi tube and enter in the desulfurizing tower.
This external Venturi tube does not take the space of desulfurizing tower, has further strengthened desulfuration efficiency on the desulfurized effect basis of desulfurizing tower itself greatly.
Preferably, described spray equipment can be arranged on the import reducing pipe place of Venturi tube, bring the trunnion part into by flue gas at a high speed, thereby increase suddenly and form more tiny droplet, thereby increase assimilation effect sulfur dioxide from the outlet increaser back pressure that comes out.
Spray equipment can also be arranged on the trunnion place or the outlet increaser place of Venturi tube, equally also can form the good absorption effect to sulfur dioxide.In addition, injection apparatus is arranged on the different parts of trunnion, as at preceding half section close import reducing pipe place, perhaps at close outlet of second half section increaser place, also assimilation effect is produced Different Effects.Those of ordinary skills make these changes and change the scope that all belongs to conventional design, need not to make creative work.
Preferably by in Venturi tube, flue gas being carried out premixed earlier with ammoniacal liquor, can to sulfur dioxide absorb more abundant, and the mixed effect of Venturi tube is also more better.The following reaction of main generation in the Venturi tube:
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
Reaction mainly obtains ammonium bisulfite in the Venturi tube, and mixed liquor enters in the collecting tank of desulfurizing tower and generates ammonium sulfite with the excessive ammonia reaction, enters among the circulation that absorbs flue gas again.
According to foregoing circulation technology, pH checkout gear and sulfur dioxide checkout gear preferably are set in Venturi tube, N/S amount ratio is 35: 70～45: 60 in the ammoniacal liquor control Venturi tube so that spray into, and is preferably 39: 64.
PH checkout gear and sulfur dioxide checkout gear described in desulfurizing tower can also be set in Venturi tube, be used to control the ammoniacal liquor straying quatity.Come the pH testing result is proofreaied and correct by the content that detects sulfur dioxide in flue gas, thereby the N/S ratio of Venturi tube is controlled, two kinds of checkout equipments are worked simultaneously, can control the straying quatity of ammoniacal liquor more accurately.Usually it is believed that and spray into that ammoniacal liquor is excessive can to absorb sulfur dioxide more completely, and grope through testing repeatedly, find that at last actual is at N/S amount ratio at 35: 70～45: 60 o'clock, can generate more ammonium bisulfite, and ammonium bisulfite absorbs sulfur dioxide effect ideal more in the desulfurizing tower of back, the sulfur dioxide in flue gas residual quantity minimum that makes last discharge, and the ammoniacal liquor surplus also is controlled at minimum degree in the tower.
Described pH detects and the sulfur dioxide checkout gear can be arranged on any position that can accurately detect in the Venturi tube, and this point those skilled in the art normally know and to know.But the pH checkout gear preferably is arranged on the exit in the Venturi tube among the present invention; The sulfur dioxide checkout gear preferably is arranged on the entry site of flue gas in the Venturi tube.
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 circulation technology, the described ammonium sulfite solution concentration of step (2) is 25～35%, and purity is 85～99%.Concentration described here is what obtain divided by liquor capacity with ammonium sulfite weight; And purity is to obtain divided by whole solute gross weights in the solution with the ammonium sulfite weight in the solution.
The ammonium sulfite concentration and the purity content that obtain by technology of the present invention do not need further processed fully, and are directly used in pulping with ammonium sulfite method.The ammonium sulfite of the more energy and raw material production of high purity in next life like this can avoid waste.
According to foregoing circulation technology, the foul condensate that produces in the described pulping process of step (3) is that the black liquor that produces in the pulping process heats generation when concentrating, and the concentrated black liquid that black liquor concentrates the back generation is used to prepare chemical fertilizer.
In papermaking, can produce a large amount of black liquor in the pulping with ammonium sulfite method, directly discharging after the black liquor of common this high pollution all carries out burning disposal or adds the chemicals neutralisation treatment, this way can only reduce the pollution of black liquor to environment a little, and can not eliminate this pollution fully.We heat this black liquor concentrated, and the condensed water that heating process produces has absorbed the ammonia that evaporates in the heating process, forms described foul condensate.This foul condensate that contains ammonia can be used to absorb flue gas again after regulating concentration, and the concentrated black liquid after concentrating can prepare chemical fertilizer owing to be rich in organic principle after the simple processing of process.Processing can produce the pollutant of discharging hardly like this, reasonable use trade waste.
According to foregoing circulation technology, 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 has a clear water spray equipment; Also have a pH checkout gear in the described desulfurizing tower, 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;
(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, it in the collecting tank of desulfurizing tower bottom the mixed solution of excess of ammonia water and ammonium sulfite, 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.
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
Foregoing collecting tank can be the part of desulfurizing tower and the bottom that is arranged on desulfurizing tower; Also can be arranged on the desulfurizing tower outside separately, and be connected with desulfurizing tower with pipeline, and some liquid phase space, desulfurizing tower bottom, it is the mixed solution of ammonium sulfite, ammonium bisulfite, ammoniacal liquor, that is to say that the liquid phase space of desulfurizing tower bottom is identical with the liquid component in the collecting tank.Certainly, as long as can finally obtain ammonium sulfite, can also adopt alternate manner to collect ammonium sulfite solution.This is conspicuous for those of ordinary skills, need not to make creative work.
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 addition, also can add the PVC filler in the tower, with its assimilation effect of further enhancing.The filler shape can be spherical or sheet.This filler has high temperature resistant, and is corrosion-resistant, and specific area is big, characteristics such as resistance is little, ventilation rate height.
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.
According to foregoing circulation technology, preferably, the flue gas of the described discharge of step (A) absorbs ammonia remaining in the flue gas also through an ammonia absorber with water purification, forms weak aqua ammonia, and circulation is used to absorb flue gas after the adjusting concentration.
The absorption of ammonia all is arranged on the desulfurizing tower top in the prior art, and this part is highly very little, and the non-constant of assimilation effect still has a large amount of ammonias to be discharged in the atmosphere like this.And the present invention has adopted independent absorption tower, and is then that this absorption of amino in the flue gas is complete.And the ammoniacal liquor that obtains reusable edible after overregulating concentration is used to absorb flue gas.
According to foregoing circulation technology, preferably, the described multilayer spray of step (A) is three layers of spray; Temperature is 65～120 ℃ in the desulfurizing tower; Pressure is that pressure is 100～110kpa, is preferably 106.4kpa; Desulfurizing tower smoke entrance relative pressure is 1000～3000Pa, is 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 circulation technology, preferred described ammonia concn is 0.8～11%, wherein more preferably 1～3%.
According to foregoing circulation technology, the described pulping with ammonium sulfite method technology of step (3) 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.
According to foregoing circulation technology, the foul condensate that produces in the described pulping process of step (3) is that the black liquor that produces in the pulping process produces when concentrating, and black liquor concentrates the concentrated black liquid that the back produces and is used to prepare chemical fertilizer.
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.
(3) the improved smoke absorption of employing system, sulfur dioxide absorption efficiency height.
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 at first enters Venturi tube, and the deposed ammonia jar is connected with Venturi tube, sprays into 1～3% ammoniacal liquor and sulfur in smoke is absorbed obtain the ammonium bisulfite mixed liquor in Venturi tube.And regulating the ammoniacal liquor straying quatity by pH checkout gear and sulfur dioxide checkout gear, to control N/S amount ratio be 39: 64.
The flue gas mixed liquor that comes out from Venturi tube enters the collecting tank at the bottom of the desulfurizing tower, sprays into excess of ammonia water and 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 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 65～90 ℃ 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 reaches 7.5 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 85～99%.
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%.
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 technical grade 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 foul condensate that contains ammonia when carrying out boiling, the perhaps this foul condensate that produces in other processes of pulping with ammonium sulfite method, enter the 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.Perhaps the foul condensate of collecting directly is passed in the deposed ammonia jar, in the deposed ammonia jar, regulates ammonia concentration 1～3%.
The concentrated black liquid that produces after the black liquor boiling of front is used to prepare chemical fertilizer.
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.
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 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 foul condensate that contains ammonia when carrying out boiling, the perhaps this foul condensate that produces in other processes of pulping with ammonium sulfite method, enter the 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.Perhaps the foul condensate of collecting directly is passed in the deposed ammonia jar, in the deposed ammonia jar, regulates ammonia concentration 0.8～11%.
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 at first enters Venturi tube, and the deposed ammonia jar is connected with Venturi tube, sprays into 1～3% ammoniacal liquor and sulfur in smoke is absorbed obtain the ammonium bisulfite mixed liquor in Venturi tube.And it is 35: 70～45: 60 by pH checkout gear and sulfur dioxide checkout gear control N/S amount ratio.
The flue gas mixed liquor that comes out from Venturi tube enters the collecting tank at the bottom of the desulfurizing tower, sprays into excess of ammonia water and 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 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 80～100 ℃ in the desulfurizing tower; Pressure is 106.4kpa.Desulfurizing tower smoke entrance relative pressure is 1300～1800Pa.
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 reaches 7.6～8.0 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 28～32%, 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 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%.
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 technical grade 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 foul condensate that contains ammonia when carrying out boiling, the perhaps this foul condensate that produces in other processes of pulping with ammonium sulfite method, enter the 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.Perhaps the foul condensate of collecting directly is passed in the deposed ammonia jar, in the deposed ammonia jar, regulates ammonia concentration 1～3%.
The concentrated black liquid that produces after the black liquor boiling of front is used to prepare chemical fertilizer.
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.
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, the ammoniacal liquor that produces in the pulping process circulates again and is used for the process of smoke absorption.But the present invention simultaneously is not limited to field of papermaking again, and any industrial production that may utilize this ammonium sulfite all can be with reference to the present invention, especially utilizes this ammonium sulfite and can produce the industrial production of the waste water that contains ammonia simultaneously, all within protection domain of the present invention.
Claims (11)
1. a circulation technology that utilizes 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;
(3) the foul condensate circulation that contains ammonia that produces in the pulping with ammonium sulfite method process is used for step (1) flue gas is carried out desulfurization.
2. circulation technology according to claim 1 is characterized in that, the described desulfurization of step (1) is for to be provided with an air-introduced machine before desulfurizing tower, and it is 200000～400000m that described air-introduced machine advances the flue gas inlet
3/ h is preferably 305000～400000m
3/ h, more preferably 310800m
3/ h.
3. circulation technology according to claim 1, it is characterized in that, the described desulfurization of step (1) is for also being provided with a Venturi tube that is connected the desulfurizing tower bottom before desulfurizing tower, in the described Venturi tube spray equipment is set, make flue gas at first fully mix with ammoniacal liquor in Venturi tube, mixed solution enters in the desulfurizing tower with flue gas again then.
4. circulation technology according to claim 3 is characterized in that, pH checkout gear and sulfur dioxide checkout gear are set in Venturi tube, sprays into that N/S amount ratio is 35: 70～45: 60 in the ammoniacal liquor control Venturi tube, is preferably 39: 64.
5. circulation technology according to claim 1 is characterized in that, the described ammonium sulfite solution concentration of step (2) is 25～35%, and purity is 85～99%.
6. circulation technology according to claim 1 is characterized in that, the foul condensate that produces in the described pulping process of step (3) is that the black liquor that produces in the pulping process heats generation when concentrating, and the concentrated black liquid that black liquor concentrates the back generation is used to prepare chemical fertilizer.
7. circulation 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 has a clear water spray equipment; Also have a pH checkout gear in the described desulfurizing tower, 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;
(B) the ammonium sulfite mixed solution that obtains precipitated, filter and obtain pure ammonium sulfite solution.
8. circulation technology according to claim 7 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.
9. circulation technology according to claim 7 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; Desulfurizing tower smoke entrance relative pressure is 1000～3000Pa, is preferably 1500～2000Pa.
10. according to any described circulation technology of claim 1～9, it is characterized in that described ammonia concn is 0.8～11%, is preferably 1～3%.
11. circulation technology according to claim 1, it is characterized in that, the described pulping with ammonium sulfite method technology of step (3) 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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|---|---|---|---|
| CN2008101715260A CN101760975B (en) | 2008-10-17 | 2008-10-17 | Circulation process for performing ammonium sulfite pulping by using sulfur-containing flue gas absorber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011113329A1 (en) * | 2010-03-17 | 2011-09-22 | 山东泉林纸业有限责任公司 | Circular utilization method of straw in pulping and papermaking process |
| CN102512937A (en) * | 2011-12-30 | 2012-06-27 | 宜宾海丝特纤维有限责任公司 | Method for recycling hydrogen sulfide waste gas |
| CN105833704A (en) * | 2016-05-14 | 2016-08-10 | 张波 | System and technology of restraining ammonium sulfite oxidation through ammonia desulphurization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334238A (en) * | 2000-07-14 | 2002-02-06 | 沈阳博斯腾新技术开发有限公司 | Ecological process preparation method of ammonium sulfite |
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2008
- 2008-10-17 CN CN2008101715260A patent/CN101760975B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011113329A1 (en) * | 2010-03-17 | 2011-09-22 | 山东泉林纸业有限责任公司 | Circular utilization method of straw in pulping and papermaking process |
| US8778135B2 (en) | 2010-03-17 | 2014-07-15 | Shandong Tralin Paper Co., Ltd. | Circular utilization method in pulping and papermaking processes with straw |
| CN102512937A (en) * | 2011-12-30 | 2012-06-27 | 宜宾海丝特纤维有限责任公司 | Method for recycling hydrogen sulfide waste gas |
| CN105833704A (en) * | 2016-05-14 | 2016-08-10 | 张波 | System and technology of restraining ammonium sulfite oxidation through ammonia desulphurization |
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