CN102732730A - Recovery method for vanadium component in selective catalytic reduction denitration catalyst - Google Patents

Recovery method for vanadium component in selective catalytic reduction denitration catalyst Download PDF

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CN102732730A
CN102732730A CN2012102202969A CN201210220296A CN102732730A CN 102732730 A CN102732730 A CN 102732730A CN 2012102202969 A CN2012102202969 A CN 2012102202969A CN 201210220296 A CN201210220296 A CN 201210220296A CN 102732730 A CN102732730 A CN 102732730A
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vanadium
electrolysis
solution
catalyst
electrolyzer
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CN102732730B (en
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肖雨亭
赵建新
汪德志
彭光军
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Guoneng Longyuan catalyst Jiangsu Co.,Ltd.
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Jiangsu Longyuan Catalyst Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a recovery method for the component of vanadium in a selective catalytic reduction denitration catalyst, which belongs to the technical field of catalyst recovery. The method comprises the following steps: smashing a waste vanadium-tungsten-titanium based catalyst, adding the smashed catalyst into an electrolytic bath for electrolysis so as to obtain negative electrode mixed liquor in the electrolytic bath, and carrying out filtration and separation on the negative electrode mixed liquor to obtain a vanadium-containing mixed solution; subjecting the vanadium-containing mixed solution to secondary electrolysis so as to obtain secondary electrolysis positive electrode mixed liquor; and adjusting the pH value of the positive electrode mixed liquor with an alkali solution, then reacting an ammonium salt solution with the positive electrode mixed liquor overnight so as to allow vanadium to be precipitated, carrying out filtration to obtain a white solid, and firing the white solid to obtain a recovered product, i.e., a pale yellow solid containing vanadium. The recovery method provided in the invention has the following advantages: the method can be carried out at normal temperature, reaction conditions are mild, an electrolytic reaction has good chemical reaction selectivity, and complete recovery of the component of vanadium can be realized substantially.

Description

The method that denitrifying catalyst with selective catalytic reduction vanadium component reclaims
Technical field
The present invention relates to the method that a kind of denitrifying catalyst with selective catalytic reduction vanadium component reclaims, belong to the catalyst recovery technical field.
Background technology
Along with the control of national team's discharged nitrous oxides during " 12 " is more and more stricter, SCR (SCR) technology is widely used in the denitrating system of coal-burning power plant because of its efficient and reliable denitration performance.The cardinal principle of SCR technology is in the boiler emission flue gas, to spray into NH 3Deng reductive agent, under the effect of catalyzer, with the harmless N of NOx generation in the flue gas 2And H 2O.
The technological core of SCR technology is a vanadium tungsten Ti-base catalyst, in operational process, exists the active problem that descends.Cause the reason of catalyst deactivation to have a lot; The influence of existing operation condition; Such as dust in flue gas and temperature fluctuation meeting catalyzer macroscopic view result is caused damage; The effect of various poisonous and harmful chemical ingredientss in the flue gas is also arranged, and the toxic action that wherein arsenic element, basic metal, earth alkali metal and MOX had is the most obvious.
The processing of spent catalyst can be divided into regeneration and reclaim two portions.Catalyst regeneration mainly is can recover the catalyzer of denitration performance to some; For can't the regenerated spent catalyst, the processing mode that has economic benefit most be exactly the metallic element that reclaims wherein, comprises the recovery of vanadium, tungsten, titanium elements.Metallic element way of recycling at present commonly used is to add alkaline matter to carry out high-temperature calcination and separate through operations such as water logging depositions then and obtain various metallic elements.
Summary of the invention
The purpose of this invention is to provide the method that a kind of brand-new denitrifying catalyst with selective catalytic reduction vanadium component reclaims,, in the vanadium component reclaims, have the advantage of certain saving energy not through the high temperature sodium roasting.
According to technical scheme provided by the invention, the method that a kind of denitrifying catalyst with selective catalytic reduction vanadium component reclaims, step is following:
(1) pulverizes: get waste and old vanadium tungsten Ti-base catalyst and be crushed to 200 ~ 300 orders;
(2) electrolysis: get electrolyzer, all add the anti-reductive strong electrolyte solution of 2 ~ 10mol/L in the positive and negative polarities electrolyzer, the waste and old vanadium tungsten Ti-base catalyst of getting step (1) pulverizing adds in the electrolyzer negative pole, and the control electrolytic current density is 60 ~ 100mA/cm 2Carrying out constant-current electrolysis or controlling electrolysis voltage is that 2 ~ 6V carries out constant-potential electrolysis;
(3) separate: power taking separates that the negative pole mixed solution carries out filtering separation with B in the electrolyzer of back, obtains containing the mixing solutions of vanadium mass concentration 10% ~ 18%;
(4) re-electrolysis: get another electrolyzer again, electrolyzer anodal add step (3) separate obtain contain the vanadium mixing solutions, negative pole adds the anti-reductive strong electrolyte solution of 2 ~ 10mol/L, the control electrolytic current density is 60 ~ 100mA/cm 2Carrying out constant-current electrolysis or controlling electrolysis voltage is that 2 ~ 6V carries out constant-potential electrolysis;
(5) aftertreatment: getting the anodal mixed solution of gained after step (4) re-electrolysis, to be adjusted to pH with the basic soln of mass concentration 10% ~ 50% be 10 ~ 12; Use the precipitation of spending the night of the ammonium salt solution of 120 ~ 300g/L then; Filtration obtains white solid; Behind 450 ~ 690 ℃ of calcination 1 ~ 5h, the product after obtaining reclaiming contains the faint yellow solid of vanadium.
Required electrolysis electricity Q (Ah) calculates according to the amount that contains vanadium in the waste and old vanadium tungsten Ti-base catalyst that adds during step (2) electrolysis, and calculating formula is following:
Q(Ah)=0.32×m×V 2O 5%(Ah);
Wherein, m is the quality of waste and old vanadium tungsten Ti-base catalyst, and unit is g; V 2O 5% contains V in the spent catalyst 2O 5Mass percentage content, unit is 1.
Electrolytic chemical equation is as follows:
Anodal: 2H 2O-4e —>4H ++ O 2↑;
Negative pole: V 2O 5+ 6H ++ 2e —>2VO 2++ 3H 2O, VO 2++ 2H ++ e —>V 3++ H 2O.
The required electrolysis electricity Q of step (4) re-electrolysis (Ah) obtains according to the cubage of vanadium in the positive solution in the electrolyzer (IV), and calculating formula is following:
Q(Ah)=0.58×m×V(IV)%(Ah);
Wherein, m is the quality of electrolyzer positive solution, and unit is g; V (IV) % is the mass percentage content of V in the electrolyzer positive solution (IV), and unit is 1.
Electrolytic chemical equation is as follows:
Anodal: 2VO 2++ 3H 2O-2e —>V 2O 5+ 6H +, V 3++ H 2O-e —>VO 2++ 2H +
Negative pole: 2H ++ 2e —>H 2↑.
The concentration of said anti-reductive strong electrolyte solution is 3 ~ 5mol/L.Said anti-reductive strong electrolyte solution is Na 2SO 4, K 2SO 4, NaNO 3, KNO 3, NaCl, KCl or H 2SO 4Solution.
The said basic soln mass concentration of step (5) is 10% ~ 50%.Said basic soln is ammoniacal liquor, KOH, RbOH, CsOH or NaOH solution.
The said ammonium salt solution concentration of step (5) is 120 ~ 300g/L.Said ammonium salt solution is NH 4Cl, NH 4NO 3Or (NH 4) 2SO 4Solution.
The present invention has following advantage: the present invention can operate at normal temperatures, and reaction conditions is comparatively gentle, and electrolytic reaction has the better chemical reaction preference, and can accomplish the recovery fully of vanadium component basically.
Embodiment
Embodiment 1
(1) pulverizes: get waste and old vanadium tungsten Ti-base catalyst and be crushed to 200 ~ 300 orders;
(2) electrolysis: get electrolyzer, all add the H of 4mol/L in the positive and negative polarities electrolyzer 2SO 4Solution, the waste and old vanadium tungsten Ti-base catalyst of getting step (1) pulverizing adds in the electrolyzer negative pole, and the control electrolytic current density is 80mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2H 2O-4e —>4H ++ O 2↑;
Negative pole: V 2O 5+ 6H ++ 2e>2VO 2++ 3H 2O, VO 2++ 2H ++ e>V 3++ H 2O;
Electrolysis electricity can calculate according to vanadium (V) content in the electrolyzer negative pole mixed solution, calculates electrolysis electricity Q (Ah)=32Ah through following formula:
Q (Ah)=0.32 * m * V 2O 5% (Ah), wherein, m=10000g; V 2O 5%=1%;
(3) separate: negative pole mixed solution filtering separation in the electrolyzer of back is separated in power taking, obtains containing the mixing solutions of vanadium mass concentration 12%;
(4) re-electrolysis: get another electrolyzer again, electrolyzer anodal add step (3) separate obtain contain the vanadium mixing solutions, negative pole adds the H of 4mol/L 2SO 4Solution, the control electrolytic current density is 80mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2VO 2++ 3H 2O-2e —>V 2O 5+ 6H +, V 3++ H 2O-e —>VO 2++ 2H +
Negative pole: 2H ++ 2e —>H 2↑;
Electrolysis electricity can calculate according to vanadium (IV) content in the electrolyzer positive solution, calculates electrolysis electricity Q (Ah)=55.68Ah through following formula:
Q (Ah)=0.58 * m * V (IV) % (Ah), wherein, m=800g; V (IV) %=12%;
(5) aftertreatment: get and use 120g/LNH after the anodal mixed solution 10%NaOH of gained solution is regulated pH to 11 after step (4) re-electrolysis 4The precipitation of spending the night of Cl solution is filtered and is obtained white solid, and after 450 ℃ of calcinations, the product after obtaining reclaiming contains the faint yellow solid of vanadium, wherein contains 58% vanadium (V) component.
Embodiment 2
(1) pulverizes: get waste and old vanadium tungsten Ti-base catalyst and be crushed to 200 ~ 300 orders;
(2) electrolysis: get electrolyzer, all add the NaNO of 5mol/L in the positive and negative polarities electrolyzer 3Solution, the waste and old vanadium tungsten Ti-base catalyst of getting step (1) pulverizing adds in the electrolyzer negative pole, and the control electrolytic current density is 100mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2H 2O-4e —>4H ++ O 2↑;
Negative pole: V 2O 5+ 6H ++ 2e —>2VO 2++ 3H 2O, VO 2++ 2H ++ e —>V 3++ H 2O;
Electrolysis electricity can calculate according to vanadium (V) content in the electrolyzer negative pole mixed solution, calculates electrolysis electricity Q (Ah)=48Ah through following formula:
Q (Ah)=0.32 * m * V 2O 5% (Ah), wherein, m=10000g; V 2O 5%=1.5%;
(3) separate: negative pole mixed solution filtering separation in the electrolyzer of back is separated in power taking, obtains containing the mixing solutions of vanadium mass concentration 18%;
(4) re-electrolysis: get another electrolyzer again, electrolyzer anodal add step (3) separate obtain contain the vanadium mixing solutions, negative pole adds the NaNO of 5mol/L 3Solution, the control electrolytic current density is 100mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2VO 2++ 3H 2O-2e —>V 2O 5+ 6H +, V 3++ H 2O-e —>VO 2++ 2H +
Negative pole: 2H ++ 2e —>H 2↑;
Electrolysis electricity can calculate according to vanadium (IV) content in the electrolyzer positive solution, calculates electrolysis electricity Q (Ah)=83.52Ah through following formula:
Q(Ah)=0.58×m×V(IV)%(Ah),m=800g;V(IV)%=18%;
(5) aftertreatment: get and use 120g/LNH after the anodal mixed solution 10%KOH of gained solution is regulated pH to 11 after step (4) re-electrolysis 4NO 3The solution precipitation of spending the night is filtered and is obtained white solid, and after 450 ℃ of calcinations, the product after obtaining reclaiming contains the faint yellow solid of vanadium, wherein contains 58% vanadium (V) component.
Embodiment 3
(1) pulverizes: get waste and old vanadium tungsten Ti-base catalyst and be crushed to 200 ~ 300 orders;
(2) electrolysis: get electrolyzer, all add the NaCl solution of 3mol/L in the positive and negative polarities electrolyzer, the waste and old vanadium tungsten Ti-base catalyst of getting step (1) pulverizing adds in the electrolyzer negative pole, and the control electrolytic current density is 60mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2H 2O-4e —>4H ++ O 2↑;
Negative pole: V 2O 5+ 6H ++ 2e —>2VO 2++ 3H 2O, VO 2++ 2H ++ e —>V 3++ H 2O;
Electrolysis electricity can calculate according to vanadium (V) content in the electrolyzer negative pole mixed solution, calculates electrolysis electricity Q (Ah)=16Ah through following formula:
Q (Ah)=0.32 * m * V 2O 5% (Ah), wherein, m=10000g; V 2O 5%=0.5%;
(3) separate: negative pole mixed solution filtering separation in the electrolyzer of back is separated in power taking, obtains containing the mixing solutions of vanadium mass concentration 10%;
(4) re-electrolysis: get another electrolyzer again, electrolyzer anodal add step (3) separate obtain contain the vanadium mixing solutions, negative pole adds the NaCl solution of 3mol/L, the control electrolytic current density is 60mA/cm 2Carry out constant-current electrolysis;
Electrolytic chemical equation is as follows:
Anodal: 2VO 2++ 3H 2O-2e —>V 2O 5+ 6H +, V 3++ H 2O-e —>VO 2++ 2H +
Negative pole: 2H ++ 2e —>H 2↑;
Electrolysis electricity can calculate according to vanadium (IV) content in the electrolyzer positive solution, calculates electrolysis electricity Q (Ah)=46.4Ah through following formula:
Q(Ah)=0.58×m×V(IV)%(Ah),m=800g;V(IV)%=10%;
(5) aftertreatment: the anodal mixed solution of gained is regulated pH to 11 back with 120g/L (NH with strong aqua after getting step (4) re-electrolysis 4) 2SO 4The solution precipitation of spending the night is filtered and is obtained white solid, and after 450 ℃ of calcinations, the product after obtaining reclaiming contains the faint yellow solid of vanadium, wherein contains 45% vanadium (V) component.

Claims (9)

1. the method that reclaims of a denitrifying catalyst with selective catalytic reduction vanadium component is characterized in that step is following:
(1) pulverizes: get waste and old vanadium tungsten Ti-base catalyst and be crushed to 200 ~ 300 orders;
(2) electrolysis: get electrolyzer, all add the anti-reductive strong electrolyte solution of 2 ~ 10mol/L in the positive and negative polarities electrolyzer, the waste and old vanadium tungsten Ti-base catalyst of getting step (1) pulverizing adds in the electrolyzer negative pole, and the control electrolytic current density is 60 ~ 100mA/cm 2Carrying out constant-current electrolysis or controlling electrolysis voltage is that 2 ~ 6V carries out constant-potential electrolysis;
(3) separate: power taking separates that the negative pole mixed solution carries out filtering separation with B in the electrolyzer of back, obtains containing the mixing solutions of vanadium mass concentration 10% ~ 18%;
(4) re-electrolysis: get another electrolyzer again, electrolyzer anodal add step (3) separate obtain contain the vanadium mixing solutions, negative pole adds the anti-reductive strong electrolyte solution of 2 ~ 10mol/L, the control electrolytic current density is 60 ~ 100mA/cm 2Carrying out constant-current electrolysis or controlling electrolysis voltage is that 2 ~ 6V carries out constant-potential electrolysis;
(5) aftertreatment: getting the anodal mixed solution of gained after step (4) re-electrolysis, to be adjusted to pH with the basic soln of mass concentration 10% ~ 50% be 10 ~ 12; Use the precipitation of spending the night of the ammonium salt solution of 120 ~ 300g/L then; Filtration obtains white solid; Behind 450 ~ 690 ℃ of calcination 1 ~ 5h, the product after obtaining reclaiming contains the faint yellow solid of vanadium.
2. the method that reclaims of denitrifying catalyst with selective catalytic reduction vanadium component according to claim 1, it is characterized in that: required electrolysis electricity Q (Ah) calculates according to the amount that contains vanadium in the waste and old vanadium tungsten Ti-base catalyst that adds during step (2) electrolysis, and calculating formula is following:
Q(Ah)=0.32×m×V 2O 5%(Ah);
Wherein, m is the quality of waste and old vanadium tungsten Ti-base catalyst, and unit is g; V 2O 5% contains V in the spent catalyst 2O 5Mass percentage content, unit is 1.
3. the method that reclaims of denitrifying catalyst with selective catalytic reduction vanadium component according to claim 1, it is characterized in that: the required electrolysis electricity Q of step (4) re-electrolysis (Ah) obtains according to the cubage of vanadium in the positive solution in the electrolyzer (IV), and calculating formula is following:
Q(Ah)=0.58×m×V(IV)%(Ah);
Wherein, m is the quality of electrolyzer positive solution, and unit is g; V (IV) % is the mass percentage content of V in the electrolyzer positive solution (IV), and unit is 1.
4. the method that reclaims of denitrifying catalyst with selective catalytic reduction vanadium component according to claim 1, it is characterized in that: the concentration of said anti-reductive strong electrolyte solution is 3 ~ 5mol/L.
5. the method that reclaims like the said denitrifying catalyst with selective catalytic reduction vanadium of claim 4 component is characterized in that: said anti-reductive strong electrolyte solution and be Na 2SO 4, K 2SO 4, NaNO 3, KNO 3, NaCl, KCl or H 2SO 4Solution.
6. the method that reclaims of denitrifying catalyst with selective catalytic reduction vanadium component according to claim 1, it is characterized in that: the said basic soln mass concentration of step (5) is 10% ~ 50%.
7. the method that reclaims like the said denitrifying catalyst with selective catalytic reduction vanadium of claim 7 component, it is characterized in that: said basic soln is ammoniacal liquor, KOH, RbOH, CsOH or NaOH solution.
8. the method that reclaims of denitrifying catalyst with selective catalytic reduction vanadium component according to claim 1, it is characterized in that: the said ammonium salt solution concentration of step (5) is 120 ~ 300g/L.
9. the method that reclaims like the said denitrifying catalyst with selective catalytic reduction vanadium of claim 8 component, it is characterized in that: said ammonium salt solution is NH 4Cl, NH 4NO 3Or (NH 4) 2SO 4Solution.
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CN103966447A (en) * 2014-05-20 2014-08-06 漯河兴茂钛业股份有限公司 Comprehensive utilization method of waste denitration catalyst
CN105177298A (en) * 2015-10-19 2015-12-23 宁波大学 Method for recovering vanadium oxide from failed denitration catalyst
CN107419104A (en) * 2017-07-24 2017-12-01 航天龙源(北京)环保科技发展有限公司 The comprehensive recovering process of useless SCR denitration
CN107758940A (en) * 2017-11-03 2018-03-06 无锡华光新动力环保科技股份有限公司 A kind of recovery and treatment method of laboratory vanadium-containing waste liquid
CN107970910A (en) * 2016-10-25 2018-05-01 中国石油化工股份有限公司 A kind of method that spent vanadium catalyst recycles

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CN103966447A (en) * 2014-05-20 2014-08-06 漯河兴茂钛业股份有限公司 Comprehensive utilization method of waste denitration catalyst
CN103966447B (en) * 2014-05-20 2015-12-02 漯河兴茂钛业股份有限公司 A kind of method of waste denitration catalyst comprehensive utilization
CN105177298A (en) * 2015-10-19 2015-12-23 宁波大学 Method for recovering vanadium oxide from failed denitration catalyst
CN107970910A (en) * 2016-10-25 2018-05-01 中国石油化工股份有限公司 A kind of method that spent vanadium catalyst recycles
CN107419104A (en) * 2017-07-24 2017-12-01 航天龙源(北京)环保科技发展有限公司 The comprehensive recovering process of useless SCR denitration
CN107419104B (en) * 2017-07-24 2019-03-29 航天龙源(北京)环保科技发展有限公司 The comprehensive recovering process of useless SCR denitration
CN107758940A (en) * 2017-11-03 2018-03-06 无锡华光新动力环保科技股份有限公司 A kind of recovery and treatment method of laboratory vanadium-containing waste liquid
CN107758940B (en) * 2017-11-03 2021-03-12 无锡华光新动力环保科技股份有限公司 Recovery treatment method of laboratory vanadium-containing waste liquid

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