CN102423622A - Zinc oxide desulfurization process - Google Patents
Zinc oxide desulfurization process Download PDFInfo
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- CN102423622A CN102423622A CN2011103239078A CN201110323907A CN102423622A CN 102423622 A CN102423622 A CN 102423622A CN 2011103239078 A CN2011103239078 A CN 2011103239078A CN 201110323907 A CN201110323907 A CN 201110323907A CN 102423622 A CN102423622 A CN 102423622A
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- zinc oxide
- absorption
- sulfur
- tower
- absorption tower
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 68
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 37
- 230000023556 desulfurization Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 114
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 51
- 239000012535 impurity Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000006228 supernatant Substances 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 22
- 238000003795 desorption Methods 0.000 claims abstract description 21
- 230000002745 absorbent Effects 0.000 claims abstract description 19
- 239000002250 absorbent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims description 30
- 239000000779 smoke Substances 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 239000003500 flue dust Substances 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 abstract description 3
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 230000003009 desulfurizing effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002386 leaching Methods 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a zinc oxide desulfurization process, which comprises the following steps: reversely contacting the sulfur-containing flue gas with absorption liquid containing zinc oxide in an absorption tower to remove sulfur in the sulfur-containing flue gas; conveying the desulfurized absorption liquid to a settling tank for settling to obtain solid impurities and supernatant; stirring and slurrying the supernatant and an absorbent containing zinc oxide in a slurrying tank, and conveying the slurried slurry back to an absorption tower; reacting solid impurities with waste acid solution in an acidification tank to generate SO2And acidifying the slurry; the acidified slurry and air are reversely contacted in a sulfur dioxide desorption tower to desorb SO in the acidified slurry2And desorption SO is obtained2The slurry after the reaction is finished; the generated SO2And (5) preparing acid. According to the zinc oxide desulfurization process provided by the embodiment of the invention, the raw material cost in each system is saved, and the whole system does not discharge any waste gas, waste liquid and waste solids, so that the totally-closed operation is realized, and the requirement of environmental protection is met. In addition, the process is simple, the flow is short, the operation is convenient, and the continuous operation can be realized.
Description
Technical field
The present invention relates to a kind of zinc oxide desulfurization technology.
Background technology
Traditional zinc oxide desulfurization technology is following: contain flue dust or the pure ZnO of zinc oxide (ZnO) and slurries that water is mixed and made into and contain sulfur dioxide (SO
2) the flue gas contact, react, generate zinc sulfite (ZnSO
3), ZnSO
3After the press filtration of deposition process filter press, the filter residue of formation send the roasting workshop; Also have ZnSO
3Under the situation that has oxidation air to blast, oxidation reaction takes place, finally generate ZnSO
4, contain ZnSO
4, ZnSO
3, ZnO and impurity mixed solution, after filtering through filter press, contain a large amount of ZnSO in the filtrating
4, be sent to the leaching section of wet method system.Filter residue is sent to the slag treatment system or the roasting workshop section of zinc smeltery after super-dry.
Total chemical equation is following:
ZnO+SO
2-ZnSO
3
ZnO+SO
2+1/2O
2-ZnSO
4
But conventional oxidation zinc sulfur removal technology does not also have general popularization to open at home, traces it to its cause, roughly have following some:
(1) ZnSO
3Viscosity ratio is bigger, the ZnSO in the circulation fluid
3Be easy in equipment, pipeline, deposit, cause pipeline fouling obstruction, also very bad cleaning after the fouling;
(2) ZnSO
3Be oxidized to ZnSO
4Need a large amount of oxidation airs to carry out oxidation, energy consumption is than higher, and oxidation effectiveness is controlled by several factors, and oxidation efficiency is difficult to control;
(3) owing to there are a large amount of filter residues to filter out; And filter residue is difficult to accomplish that moisture content is very low, if filter badly, often filter residue is as sposh; Make the non-constant of filter press factory building one deck operating environment; And these filter residues can't be accomplished totally-enclosed transportation in the process of outward transport, and plant area is caused secondary pollution;
(4) will be with ZnSO
4Solution and slag are separated, or with the ZnSO in the slurries
3Filter out, all need filter press, and for continued operation; Filter press must the using and the reserved, must arrange the workman to operate and put in order filter cloth like this, and the slag that filters out must be transported; Must build the filter press factory building, the whole system floor space is very big, and operating cost is all very big with investment;
On the whole, because the tail gas desulfurization to enterprise, does not produce any benefit; So general investment is low more, equipment is good more simply more, but conventional oxidation zinc sulfur removal technology, from zinc oxide slurrying; Filter to follow-up filter press, all system scales are all little, but will let a whole set of technology stable and reliable operation, good operational environment, automaticity high; Auxiliary equipment such as this supporting electricity, appearance are all complete, and investment has often all surpassed enterprise's expection.The a lot of equipment of result just can be economized and economize, and just can simplify and simplify, and cause the extraordinary exemplary engineering of zinc oxide desulfurization technology neither one, can't generally promote.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.For this reason, one object of the present invention is to propose a kind of zinc oxide desulfurization technology, has no waste gas, waste liquid and useless solid discharging during said zinc oxide desulfurization technology desulfurization, has realized totally enclosed operation.
A kind of zinc oxide desulfurization technology according to the embodiment of the invention may further comprise the steps:
S1, with sulfur-containing smoke gas and the absorption liquid that contains zinc oxide reverse contact in the absorption tower to remove the sulphur of said sulfur-containing smoke gas;
S2, the absorption liquid after the desulfurization is transported to carries out sedimentation in the subsider and obtain solid impurity and supernatant;
S3, carry back in the absorption tower said supernatant and the absorbent that contains zinc oxide stirred pulp in the pulp groove after;
S4, said solid impurity and waste acid liquor reacted in the acidifying groove generate SO
2And acidifying slurries;
S5, with said acidifying slurries and the air reverse SO that inhales in the said acidifying slurries to take off that contacts in the sulfur dioxide desorption tower
2And obtain taking off and inhale SO
2After slurries; And
S6, with the SO that generates among the step S4
2With the SO that generates among the step S5
2Relieving haperacidity.
Zinc oxide desulfurization technology according to the embodiment of the invention; Recycle owing to send in the absorption tower after solid impurity in the end product of this system and the supernatant stirring pulp; Sulfur dioxide gas is sent to the simultaneously final slurries of relieving haperacidity and is sent to the leaching system, has saved the cost of material in each system, and has no waste gas, waste liquid and useless solid discharging in the whole system; Realize totally enclosed operation, satisfied the demand of environmental protection.In addition, technology is simple, is convenient to operation and maintenance, compares the desulfurization of conventional oxidation zinc, and flow process is short and easy to operate, can realize running continuously.
In addition, zinc oxide desulfurization technology according to the present invention also has following additional technical feature:
With said SO
2The liquid-solid ratio of taking off the slurries after the suction is controlled to be 8-10: 1, pH value is controlled to be 5.0-5.2 and leaches to be used for wet method.
The solid content of the said absorption liquid of control is not higher than 8% in step S1, thereby can reduce ZnSO
3Content, and then reduced significantly that equipment stops up and scale problems.Lower solid content can reduce fouling, the blockage problem of equipment, pipeline, reduces wearing and tearing simultaneously, improves service life.
The pH value of the said absorption liquid of control can not have influence on SO greater than 5.2 in step S1
2Absorption efficiency.
Said sulfur-containing smoke gas is transported to from the bottom on absorption tower in the absorption tower and the top of the said absorption liquid that contains zinc oxide from the absorption tower is transported in the absorption tower.
Calcining and/or flue dust that the said absorbent that contains zinc oxide obtains for the zinc concentrate roasting.
Calcining that the said absorption liquid that contains zinc oxide is obtained by the zinc concentrate roasting and/or flue dust and water mix.
Said absorption tower and said sulfur dioxide desorption tower are void tower, and equipment is simple, are convenient to operation and maintenance and cost is low.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize through practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously with easily understanding becoming the description of embodiment in conjunction with figs, wherein:
Fig. 1 is the sketch map according to the desulfurizing zinc oxide system of the zinc oxide desulfurization method employing of the embodiment of the invention; With
Fig. 2 is the process chart according to the zinc oxide desulfurization method of the embodiment of the invention.
The specific embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings, and wherein identical from start to finish or similar label is represented identical or similar elements or the element with identical or similar functions.Be exemplary through the embodiment that is described with reference to the drawings below, only be used to explain the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention; It will be appreciated that; Term " on ", the orientation of indications such as D score, " top ", " end ", " interior ", " outward " or position relation be for based on orientation shown in the drawings or position relation; Only be to describe with simplifying for the ease of describing the present invention, rather than the device or the element of indication or hint indication must have specific orientation, with specific azimuth configuration and operation, therefore can not be interpreted as limitation of the present invention.In addition, term " first ", " second " only are used to describe purpose, and can not be interpreted as indication or hint relative importance.
In description of the invention, need to prove that only if clear and definite regulation and qualification are arranged in addition, term " installation ", " linking to each other ", " connection " should be done broad understanding, for example, can be to be fixedly connected, also can be to removably connect, or connect integratedly; Can be directly to link to each other, also can link to each other indirectly through intermediary, can be the connection of two element internals.For those of ordinary skill in the art, can concrete condition understand above-mentioned term concrete implication in the present invention.In addition, in description of the invention, except as otherwise noted, the implication of " a plurality of " is two or more.
The desulfurizing zinc oxide system of at first describing according to a kind of zinc oxide desulfurization process using of the embodiment of the invention below with reference to figure 1.
Desulfurizing zinc oxide system according to the embodiment of the invention comprises: absorption tower 1, subsider 2, pulp groove 3, acidifying groove 4 and sulfur dioxide desorption tower 5.As shown in Figure 1; Limit reaction chamber in the absorption tower 1 and be void tower for absorption tower 1; And the lower sidewall on absorption tower 1 is provided with air inlet 11 so that infeed sulfur-containing smoke gas; The top on absorption tower 1 is provided with gas outlet 12, and the side wall upper part on absorption tower 1 is provided with absorption liquid import 13 and the bottom is provided with absorption liquid outlet 14.Alternatively, absorption liquid import 13 is at least two that are spaced apart from each other, and in each absorption liquid import 13, is connected with a plurality of absorption liquid spouts 15 so that in the reaction chamber on absorption tower 1, spray the absorption liquid that contains zinc oxide (ZnO).Thus; Sulfur-containing smoke gas enters in the absorption tower 1 from air inlet 11; The absorption liquid that contains zinc oxide (ZnO) in absorption liquid import 13 enters into absorption tower 1 motion downwards and with the sulfur-containing smoke gas that upwards flows on the absorption tower 1 reverse the contact to remove the sulphur of sulfur-containing smoke gas; And the solid content of the circulating absorption solution in the control absorption tower 1 is in 8%, and the interior pH value of control absorption tower circulating absorption solution is greater than 5.5.
Subsider 2 and absorption liquid outlet 14 is communicated with to receive the absorption liquid of exporting from absorption liquid outlet 14 and to stir the sedimentation absorption liquid to obtain supernatant and solid impurity, wherein contains ZnSO in the solid impurity
3, the unreacted impurity in ZnO and the absorption liquids of in a large number not participating in reacting completely.Wherein the top of subsider 2 is formed with supernatant outlet 21 so that the supernatant after the sedimentation is overflowed, and the bottom of subsider 2 is formed with the impurity outlet 22 that is used to discharge the solid impurity after the sedimentation.
Pulp groove 3 is communicated with the supernatant that from subsider 2, overflows to receive with subsider 2; Particularly; Above pulp groove 3, be provided with supernatant inlet 32 to receive supernatant; The top of pulp groove 3 is provided with absorbent inlet 31 and contains the absorbent of zinc oxide (ZnO) with adding, sends in the absorption tower 1 after absorbent and the supernatant stirring pulp.Particularly; Be provided with absorbent outlet 33 in the bottom of pulp groove 3; Absorbent and supernatant are discharged and are recycled in the absorption tower 1 through absorbent outlet 33 after stirring pulp, and therefore feasible desulfurizing zinc oxide system according to the embodiment of the invention has no waste solid impurity to discharge.Alternatively, calcining and/or flue dust that the said absorbent that contains zinc oxide obtains for the zinc concentrate roasting, its zinc oxide content all is higher than 50%.Wherein the one of ordinary skilled in the art knows, and zinc calcine is the product of zinc concentrate gained after roasting, mainly contains zinc oxide (ZnO), zinc sulfate (ZnSO
4), zinc sulphide (ZnS) etc.
The impurity outlet 22 of acidifying groove 4 and subsider 2 links to each other, particularly, is provided with impurity at the top of acidifying groove 4 and enters the mouth and 44 contain a large amount of ZnSO with reception
3With the unreacted solid impurity of ZnO completely.The top of acidifying groove 4 is provided with the waste acid liquor inlet 41 that is used to infeed sulfur waste acid, and sulfur waste acid is for producing the spent acid that produces in the sulfate system and wherein being mixed with materials such as flue dust, arsenic, mercury, fluorine, chlorine.The top of acidifying groove 4 also is provided with the gas vent 42 that is used to discharge sulfur dioxide gas, and the lower sidewall of acidifying groove 4 is provided with acidifying slurries outlet 43, and thus, sulfur waste acid react generation SO with solid impurity in acidifying groove 4
2Gas and contain ZnSO
4The acidifying slurries of solution.In acidifying groove 4, regulate the pH value of acidifying slurries, and liquid-solid ratio, the requirement that makes these slurries can satisfy the system that leaches in the wet method is that liquid-solid ratio is 8-10: the 1PH value is 5.0-5.2.
Sulfur dioxide desorption tower 5 links to each other with acidifying groove 4; Particularly; Be provided with acidifying slurries inlet 54 on the top of sulfur dioxide desorption tower 5 to receive the acidifying slurries that flow out behind acidifying groove 4 internal reactions; The top of sulfur dioxide desorption tower 5 is provided with sulfur dioxide outlet 51, the bottom is provided with slurries outlet 52 and sidewall is provided with air intake 53, with acidifying slurries and air reverse SO that inhales in the acidifying slurries to take off that contacts in sulfur dioxide desorption tower 5
2And obtain taking off and inhale SO
2After slurries, these slurries are sent to the leaching system.The sulfur dioxide gas of discharging in groove 4 of acidifying simultaneously and the sulfur dioxide desorption tower 5 is fed to and carries out relieving haperacidity in the sulfate system.
According to the desulfurizing zinc oxide system of the embodiment of the invention, the solid content of the absorption liquid through the circulation in the control absorption tower 1 is in 8%, to reduce ZnSO
3Content, equipment stops up and scale problems thereby reduced significantly.Lower solid content can reduce fouling, the blockage problem of equipment, pipeline, reduces wearing and tearing simultaneously, improves service life.And after the solid content reduction, as long as the pH value of the absorption liquid in the control absorption tower 1 greater than 5.2, then can not have influence on SO
2Absorption efficiency.In addition; Recycle owing to send in the absorption tower 1 after solid impurity in the end product of this system and the supernatant stirring pulp; Sulfur dioxide gas is sent to the simultaneously final slurries of relieving haperacidity and is sent to the leaching system, has saved the cost of material in each system, and has no waste gas, waste liquid and useless solid discharging in the whole system; Realize totally enclosed operation, satisfied the demand of environmental protection.In addition, equipment is simple, is convenient to operation and maintenance and cost is low, compares the desulfurization of conventional oxidation zinc, and flow process is short and easy to operate, can realize continuous the running.
As shown in Figure 1; According to one embodiment of present invention; Desulfurizing zinc oxide system further comprises first mixing component 61; First mixing component 61 comprises first stirring parts 611 and first drive unit 612, and it is interior so that the absorption liquids in the subsider 2 are stirred sedimentation that wherein first stirring parts 611 rotatably is located at subsider 2, and it is rotatable that first drive unit 612 drives first stirring parts 611.
Alternatively; As shown in fig. 1, subsider 2 comprises column section 20a and taper section 20b, and taper section 20b is connected the below of column section 20a and forms the inverted cone shape; Thereby make solid impurity be more convenient for sedimentation and discharge, wherein impurity outlet 22 is formed on the bottom of taper section 20b.
In further embodiment of the present invention, desulfurizing zinc oxide system also comprises between impurity outlet 22 that first valve, 71, the first valves 71 are located at subsider 2 and the acidifying groove 4 to control the flow that solid impurity is discharged from subsider 2, and is as shown in Figure 1.
According to one embodiment of present invention, desulfurizing zinc oxide system also further comprises second mixing component 62 and the 3rd mixing component 63.Second mixing component 62 comprises second stirring parts 621 and second drive unit 622; It is interior so that absorbent and supernatants in the pulp groove 3 are stirred that wherein second stirring parts 621 rotatably is located at pulp groove 3, and it is rotatable that second drive unit 622 drives second stirring parts 621.
The 3rd mixing component 63 comprises the 3rd stirring parts 631 and the 3rd drive unit 632; Wherein the 3rd stirring parts 631 rotatably is located in the acidifying groove 4 so that solid impurity in the acidifying groove 4 and waste acid liquor are stirred and reaction, and the 3rd drive unit 632 drivings the 3rd stirring parts 631 is rotatable.
Desulfurizing zinc oxide system further comprises: first pump 81, second pump 82 and the 3rd pump 83; The downstream that first pump 81 is connected absorption tower 1 are to be conveyed into a part of absorption liquid in the absorption tower 1 in the subsider 2 and another part absorption liquid is sent in the absorption tower 1 through absorption liquid import 13 circulations; Second pump 82 is connected between pulp groove 3 and the absorption tower 1, and the 3rd pump 83 is connected between acidifying groove 4 and the sulfur dioxide desorption tower 5.
Alternatively, as shown in Figure 1, between first pump 81 and subsider 2, also be provided with second valve 72, from absorption tower 1, be pumped into the flow of the absorption liquid in the subsider 2 with control.
As shown in Figure 1, desulfurizing zinc oxide system can comprise that also the 4th pump 84, the four pumps 84 are connected to be suitable for that the slurries that flow out in the sulfur dioxide desorption tower 5 are sent to next step operation with the slurries outlet 52 of sulfur dioxide desorption tower 5 be that wet method leaches system.
With reference to figure 1 and Fig. 2 the zinc oxide desulfurization technology according to the embodiment of the invention is described below.
A kind of zinc oxide desulfurization technology may further comprise the steps:
S1, with sulfur-containing smoke gas and the absorption liquid that contains zinc oxide reverse contact in absorption tower 1 to remove the sulphur in the sulfur-containing smoke gas.
S2, the absorption liquid after the desulfurization is transported to carries out sedimentation in the subsider 2 and obtain solid impurity and supernatant, wherein contain ZnSO in the solid impurity
3, the unreacted impurity in ZnO and the absorption liquids of in a large number not participating in reacting completely.
S3, carry back in the absorption tower 1 supernatant and the absorbent that contains zinc oxide stirred pulp in pulp groove 3 after, alternatively, calcining and/or flue dust that the said absorbent that contains zinc oxide obtains for the zinc concentrate roasting.
S4, solid impurity and waste acid liquor reacted in acidifying groove 4 generate SO
2And the acidifying slurries, contain zinc sulfate ZnSO in the acidifying slurries
4Solution.
S5, with acidifying slurries and the air reverse SO that inhales in the acidifying slurries to take off that contacts in sulfur dioxide desorption tower 5
2And obtain taking off and inhale SO
2After slurries.
S6, with the SO that generates among the step S4
2With the SO that generates among the step S5
2Relieving haperacidity.
Zinc oxide desulfurization technology according to the embodiment of the invention; Recycle owing to send in the absorption tower 1 after solid impurity in the end product of this system and the supernatant stirring pulp; Sulfur dioxide gas is sent to the simultaneously final slurries of relieving haperacidity and is sent to the leaching system, has saved the cost of material in each system, and has no waste gas, waste liquid and useless solid discharging in the whole system; Realize totally enclosed operation, satisfied the demand of environmental protection.In addition, technology is simple, is convenient to operation and maintenance, compares the desulfurization of conventional oxidation zinc, and flow process is short and easy to operate, can realize running continuously.
Wherein, will take off suction SO
2After the liquid-solid ratio of slurries be controlled to be 8-10: 1, pH value is controlled to be 5.0-5.2 and leaches to be used for wet method, for example can inhale SO through being controlled at the liquid-solid ratio and the pH value of the acidifying slurries in the acidifying groove among the step S4, reaching to take off
2After the liquid-solid ratio of slurries be controlled to be 8-10: 1, pH value is controlled to be 5.0-5.2.
The solid content of the said absorption liquid of control is not higher than 8% in step S1, thereby can reduce ZnSO
3Content, and then reduced significantly that equipment stops up and scale problems.Lower solid content can reduce fouling, the blockage problem of equipment, pipeline, reduces wearing and tearing simultaneously, improves service life.Further, after solid content reduced in step S1, the pH value of control absorption liquid then can not have influence on SO greater than 5.5
2Absorption efficiency.
Alternatively, the absorption liquid that is transported to absorption tower in from the bottom on absorption tower sulfur-containing smoke gas and will contains zinc oxide is transported in the absorption tower from the top on absorption tower.Wherein, the calcining that obtained by the zinc concentrate roasting of the said absorption liquid that contains zinc oxide and/or flue dust and water mix.
In examples more of the present invention, absorption tower 1 is void tower with sulfur dioxide desorption tower 5, and equipment is simple, is convenient to operation and maintenance and cost is low.
Below with reference to Fig. 1 and Fig. 2 the sweetening process according to the zinc oxide desulfurization technology of the embodiment of the invention is described.
Sulfur-containing smoke gas enters in the absorption tower 1 from air inlet 11; The absorption liquid that contains zinc oxide (ZnO) in absorption liquid import 13 enters into absorption tower 1 motion downwards and with the sulfur-containing smoke gas that upwards flows on the absorption tower 1 reverse the contact; Sulfur dioxide and zinc oxide (ZnO) that absorption liquid is drawn in the sulfur-containing smoke gas react, and generate ZnSO
3Or zine hydrosulfite Zn (HSO
3)
2, in order to prevent ZnSO
3Scale problems, the solid content of the circulating absorption solution in the control absorption tower 1 makes solid content not be higher than 8%, and the interior pH value of control absorption tower circulating absorption solution is greater than 5.5.After reacting completely, absorption liquid exports 14 discharge absorption towers 1 from absorption liquid, and wherein a part of absorption liquid is admitted in the subsider 2 through first pump 81 and stirs sedimentation, and another part circulates again through absorption liquid import 13 and absorbs in the absorption tower 1.
Be sent to a part of absorption liquid in the subsider 2, through the stirring settlement action of first mixing component 61, with ZnSO
3, ZnO and the calcining impurity of in a large number not participating in reacting settle down unreacted in the lump completely; The underflow solid content of subsider 2 is controlled at 30～40%; Solid impurity can export 22 through impurity and flows automatically in the acidifying groove 4 thus, and supernatant flows out through the supernatant outlet 22 of subsider 2 and the supernatant inlet through pulp groove 3 flow in the pulp groove 3.
The absorbent that contains zinc oxide (ZnO) is input to the absorbent inlet 31 of pulp groove 3 through charging system (scheming not shown) and then joins in the pulp groove 3; After pulp groove 3 inner absorbents and supernatant stirring pulp, be sent in the absorption tower 1 to form the absorption liquid of circulation through second pump 82.
Export a large amount of ZnSO that contain of 22 outflows from the impurity of subsider 2
3, ZnO etc. solid impurity enter in the acidifying groove 4, the sulfur waste acid that is mixed with materials such as flue dust, arsenic, mercury, fluorine, chlorine enters in the acidifying groove 4 through waste acid liquor inlet 41, solid impurity and sulfur waste acid are reacted, generation SO
2And contain ZnSO
4The slurries of solution wherein stir accelerated reaction through the 3rd mixing component 63.In acidifying groove 4, regulate the pH value and the liquid-solid ratio of acidifying slurries, the requirement that makes final slurries can satisfy the system that leaches in the wet method is that liquid-solid ratio is 8-10: 1, pH value is 5.0-5.2.
The acidifying slurries of discharging from the acidifying slurries outlet 43 of acidifying groove 4 enter into sulfur dioxide desorption tower 5 through acidifying slurries inlet 54; Air enters into sulfur dioxide desorption tower 5 from air intake 53, thus acidifying slurries and air reverse SO that inhales in the acidifying slurries to take off that contacts in sulfur dioxide desorption tower 5
2And obtain taking off and inhale SO
2After slurries, these slurries are sent to the leaching system.The sulfur dioxide gas of discharging in groove 4 of acidifying simultaneously and the sulfur dioxide desorption tower 5 is fed to and carries out relieving haperacidity in the sulfate system.
Zinc oxide desulfurization technology according to the embodiment of the invention; As absorbent, end product can be got back to wet method again and leach system, has realized having no waste discharge with calcining or zinc calcination fume; And the solid content in the absorption liquid is low, can solve pipeline and equipment and stop up and scale problems.In addition, compare the equipment in the conventional oxidation zinc sulfur removal technology, saved large equipments such as oxidation fan, absorption tower side agitator, filter press in the zinc oxide desulfurization technology according to the embodiment of the invention; And have no waste residue to produce, and not needing again the arrangement personnel to go operation and muck haulage, power consumption, maintenance cost, operating cost are lower; Equipment is simple, and flow process is short, and is easy to operate; Can realize continuous running; In acidization, can carry out comprehensive reutilization to the sulfur waste acid of full factory again, make integrated artistic power consumption, operating cost, overall investment lower.
In the description of this specification, the description of reference term " embodiment ", " some embodiment ", " illustrative examples ", " example ", " concrete example " or " some examples " etc. means the concrete characteristic, structure, material or the characteristics that combine this embodiment or example to describe and is contained at least one embodiment of the present invention or the example.In this manual, the schematic statement to above-mentioned term not necessarily refers to identical embodiment or example.And concrete characteristic, structure, material or the characteristics of description can combine with suitable manner in any one or more embodiment or example.
Although illustrated and described embodiments of the invention; Those having ordinary skill in the art will appreciate that: under the situation that does not break away from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited claim and equivalent thereof.
Claims (8)
1. a zinc oxide desulfurization technology is characterized in that, may further comprise the steps:
S1, with sulfur-containing smoke gas and the absorption liquid that contains zinc oxide reverse contact in the absorption tower to remove the sulphur of said sulfur-containing smoke gas;
S2, the absorption liquid after the desulfurization is transported to carries out sedimentation in the subsider and obtain solid impurity and supernatant;
S3, carry back in the absorption tower said supernatant and the absorbent that contains zinc oxide stirred pulp in the pulp groove after;
S4, said solid impurity and waste acid liquor reacted in the acidifying groove generate SO
2And acidifying slurries;
S5, with said acidifying slurries and the air reverse SO that inhales in the said acidifying slurries to take off that contacts in the sulfur dioxide desorption tower
2And obtain taking off and inhale SO
2After slurries; And
S6, with the SO that generates among the step S4
2With the SO that generates among the step S5
2Relieving haperacidity.
2. zinc oxide desulfurization technology according to claim 1 is characterized in that, with said SO
2The liquid-solid ratio of taking off the slurries after the suction is controlled to be 8-10: 1, pH value is controlled to be 5.0-5.2 and leaches to be used for wet method.
3. zinc oxide desulfurization technology according to claim 1 is characterized in that, the solid content of the said absorption liquid of control is not higher than 8% in step S1.
4. zinc oxide desulfurization technology according to claim 3 is characterized in that, the pH value of the said absorption liquid of control is greater than 5.2 in step S1.
5. zinc oxide desulfurization technology according to claim 1 is characterized in that, said sulfur-containing smoke gas is transported to from the bottom on absorption tower in the absorption tower and the top of the said absorption liquid that contains zinc oxide from the absorption tower is transported in the absorption tower.
6. zinc oxide desulfurization technology according to claim 1 is characterized in that, calcining and/or flue dust that the said absorbent that contains zinc oxide obtains for the zinc concentrate roasting.
7. zinc oxide desulfurization technology according to claim 1 is characterized in that, calcining that the said absorption liquid that contains zinc oxide is obtained by the zinc concentrate roasting and/or flue dust and water mix.
8. zinc oxide desulfurization technology according to claim 1 is characterized in that, said absorption tower and said sulfur dioxide desorption tower are void tower.
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| CN2011103239078A CN102423622A (en) | 2011-10-21 | 2011-10-21 | Zinc oxide desulfurization process |
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| CN2011103239078A CN102423622A (en) | 2011-10-21 | 2011-10-21 | Zinc oxide desulfurization process |
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| CN106731632A (en) * | 2016-12-30 | 2017-05-31 | 云南雄冶科技有限公司 | The device and its technique of a kind of zinc oxide removing sulfur dioxide in flue gas |
| CN107983136A (en) * | 2017-12-21 | 2018-05-04 | 双盾环境科技有限公司 | A kind of technique of ash-laden gas recycling Sulphur ressource using after zinc calcine or zinc roasting |
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| CN107983136A (en) * | 2017-12-21 | 2018-05-04 | 双盾环境科技有限公司 | A kind of technique of ash-laden gas recycling Sulphur ressource using after zinc calcine or zinc roasting |
| CN107998864A (en) * | 2017-12-21 | 2018-05-08 | 双盾环境科技有限公司 | A kind of zinc oxide desulfurization forces oxidation technology |
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Application publication date: 20120425 |