CN102600903A - Vanadium-based liquid-phase catalyst and preparation method thereof - Google Patents

Vanadium-based liquid-phase catalyst and preparation method thereof Download PDF

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CN102600903A
CN102600903A CN2012100489201A CN201210048920A CN102600903A CN 102600903 A CN102600903 A CN 102600903A CN 2012100489201 A CN2012100489201 A CN 2012100489201A CN 201210048920 A CN201210048920 A CN 201210048920A CN 102600903 A CN102600903 A CN 102600903A
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vanadium
catalyst
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water
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CN102600903B (en
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林晓
曹宏斌
李�杰
张懿
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Institute of Process Engineering of CAS
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Abstract

The invention relates to a vanadium-based liquid-phase catalyst prepared with an extraction reaction of organic amine to oxysalts of metals such as vanadium. Through the controlling over operation conditions, vanadium-containing catalytically active substances and co-catalysts in a water solution are extracted into an organic phase; a curing treatment is carried out, such that the vanadium liquid-phase catalyst is prepared. The catalyst is not sensitive to air, water, or acid, and has good thermal stability. The synthesizing, circulation, and regeneration methods of the catalyst are simple, such that industrialized production can easily be realized. In flue gas denitration, the catalyst shows high contact area and high catalytic activity.

Description

A kind of vanadium base fluid phase catalyst and preparation method thereof
Technical field
The present invention relates to a kind of vanadium base fluid phase catalyst and preparation method thereof, particularly relates to a kind of method that adopts extraction at organic liquid phase load catalytic component based on vanadium.
Background technology
Vanadium sub-group compound is one type and has high catalytic activity catalyst, can be used for catalytic oxidation oxysulfide (SO x), nitrogen oxide (NO x, mainly refer to NO and NO 2), thereby in the processing procedure of industrial smokes such as coal-burning boiler and thermal power plant, be used for synchronized desulfuring and denitrifying, also be widely used in the catalytic oxidation process of sulfuric acid, phthalic anhydride, cis-butenedioic anhydride.
Former study shows, the SO in the gas x, NO xPollutant is the major pollutants in the industrial waste gases such as flue gas, and selective catalytic oxidation is a present domestic and international application treatment technology more widely, and what generally use is with the catalytic component based on vanadium of barium oxide as catalytic active substance, generally loads on TiO 2, Al 2O 3, active carbon, SiO 2(or diatomite etc. contains SiO 2Type material) etc. on the carrier, be prepared as the vanadium base solid catalyst.Through operating conditions such as control reaction temperature, SO 2, gas pollutant such as NO is with after catalytic component based on vanadium contacts, realize catalytic oxidation, remove through selective catalytic oxidation.For example, report is arranged with V 2O 5Be supported on the V that makes on the active carbon (AC) 2O 5/ AC catalyst can remove the SO in the flue gas simultaneously in the time of 200 ℃ 2And NO.
Catalytic component based on vanadium is to the desulfurization and denitrification reaction good catalytic activity; But solid-phase catalyst exists preparation cost higher; Problems such as required capital cost of reactor height, and solid-phase catalyst is after long-time the use, and changes in crystal structure causes the deposition of sintering, ammonium salt and flying dust all can cause specific area to reduce; Make catalytic activity descend, produce catalyst when serious and stop up.Above-mentioned reason has limited the further extensive use of catalytic component based on vanadium.The researcher is in order to solve the problem that catalytic component based on vanadium exists both at home and abroad; Carried out a large amount of research in this field, proposed through improving catalytic activity, improve means reinforcement denitration effects such as carrier specific area and mechanical strength, interpolation co-catalyst, improving catalyst life.
CN1475305A uses active carbon to be carrier, V 2O 5Be active component, be prepared as the desulphurization denitration catalyst of flue gas, cooperate the interior bracing frame of reactor of particular design to use, wherein, the NO conversion ratio is 50%-100%, SO 2Conversion ratio is about 80%.CN1792431 uses Al 2O 3, TiO 2Be carrier, V 2O 5And WO 3Being active component, is framework material with the cordierite honeycomb ceramic, preparation SCR denitrating catalyst, wherein, NO xRemoval efficient be 75-99%.CN102259009A discloses a kind of nano-TiO that promotes based on sulfate radical 2(SO 4 2-/ TiO 2) be carrier, WO 3And CeO 2Be auxiliary agent, V 2O 5Be the vanadium based denitration catalyst of active component, wherein, denitration efficiency is greatly between 68%-98%.
These optimization means have obtained certain effect, and part has got into commercial Application, but is limited to the characteristics of solid phase catalytic component based on vanadium self, is difficult to make a breakthrough from aspects such as catalytic reaction contact area, anti-fragmentation, anti-water, anti-sulphur property.Therefore, develop a kind of liquid-phase catalyst that is used for the vanadium base, have very important significance.
Summary of the invention
To the deficiency of prior art, high in order to solve existing catalytic component based on vanadium cost, and behind the long reaction since the specific surface area of catalyst that the deposition of sintering of catalyst, ammonium salt and flying dust causes reduce; Catalytic activity descends; Produce the catalyst blocking problem even, the present invention proposes a kind of all insensitive to air, water, acid first, Heat stability is good; Synthetic, circulation, renovation process are simple; Be easy to industrialization, and in denitrating flue gas, demonstrate vanadium base fluid phase catalyst of high contact area, high catalytic activity and preparation method thereof, can be used for the desulphurization denitration of flue gas.
One of the object of the invention is to provide a kind of vanadium base fluid phase catalyst, and the phase of said catalyst is a liquid phase, and the activity of such catalysts material is the organic vanadium compound, and carrier is organic amine and/or is dissolved in the organic amine in the organic solvent.
Said organic vanadium compound is an oxysalt from vanadium preferably, further preferred a kind or at least 2 kinds combination in vanadate, metavanadate, pyrovanadate, vanadate.Vanadium is that the cation of oxysalt can be ammonium ion, alkali metal ion etc., for example sodium vanadate, sodium metavanadate, sodium pyrovanadate, many sodium vanadates, ammonium vanadate, ammonium metavanadate, pyrovanadic acid ammonium, ammonium poly-vanadate, potassium vanadate, potassium metavanadate, many potassium vanadates, pyrovanadic acid potassium etc.
As preferably; It can water-soluble vanadium be oxysalt that the present invention selects for use; Said vanadium is that oxysalt is preferably a kind or at least 2 kinds combination in sodium vanadate, sodium metavanadate, many sodium vanadates, pyrovanadic acid ammonium, ammonium metavanadate, ammonium vanadate, potassium metavanadate, the many potassium vanadates, and said combination is sodium vanadate/ammonium vanadate, pyrovanadic acid ammonium/many potassium vanadates, sodium metavanadate/many sodium vanadates, ammonium metavanadate/potassium vanadate/sodium pyrovanadate etc. for example.Optimal selection of the present invention is a sodium metavanadate.Vanadium of the present invention is that oxysalt all can obtain through consulting prior art for preparing through being purchased acquisition or those skilled in the art.
As preferably, said organic amine is selected from a kind or at least 2 kinds combination in the primary amine, secondary amine, tertiary amine, quaternary ammonium salts of carbon number >=10.Those skilled in the art have the ability to know the organic amine compound that meets said condition.The primary amine that is adopted specific embodiment decyl amine, undecylamine, lauryl amine, octadecylamine etc. are arranged; The embodiment of the secondary amine that adopts has dodecyl methyl secondary amine, pentadecyl ethyl secondary amine etc.; The embodiment of the tertiary amine that adopts has trialkyl tertiary amine, fatty alkyl dimethyl tertiary amine; The embodiment of the quaternary ammonium salt that adopts has chlorination trimethyl alkanamine, chlorination triethyl group alkanamine.1 kind or at least 2 kinds combination in the preferred chlorination trimethyl of the present invention alkanamine class, trialkyl tertiary amines, the fatty alkyl dimethyl tertiary amine class; 1 kind or at least 2 kinds combination in special preferable methyl trioctylphosphine ammonium chloride (N263), aliphatic chain primary amine N1923, tertiary amine TOA, secondary amine 7203, tertiary amine 7301, dodecyl dimethyl tertiary amine (12DMA), the hexadecyldimethyl benzyl ammonium tertiary amine (16DMA), most preferably a kind or at least 2 kinds combination among N263, N1923, TOA, the primary amine Primene JM-T, 7203.Organic amine of the present invention all can be through being purchased acquisition.
As preferably; In the preferred comfortable 200-400 ℃ scope of said organic solvent is liquid; And the organic solvent of boiling point >=350 ℃; Those skilled in the art have the ability to obtain satisfactory organic solvent, typical case but non-limiting instance has solid paraffin, printing ink solvent oil, mineral oil, albolene, silicone oil etc.Organic solvent of the present invention all can obtain through consulting prior art for preparing through being purchased acquisition or those skilled in the art.
As preferably, vanadium base fluid phase catalyst of the present invention contains co-catalyst.Co-catalyst is through the chemical composition that changes catalyst, ionic valence condition, Acidity of Aikalinity, surface texture, grain size etc., thereby makes the additive of activity of such catalysts, selectivity, mithridatism or the stable one type of catalyst that is improved.Preferably, co-catalyst according to the invention is preferably molybdate and/or tungstates.
Molybdate is the positive molybdate of series of stable, and chemical general formula is M 2MoO 4Or MMoO (wherein M is monovalence metal or divalent metal).The preferred water-soluble molybdate of molybdate according to the invention; For example ammonium molybdate, sodium molybdate, potassium molybdate, molybdic acid thallium, magnesium molybdate etc.; 1 kind or at least 2 kinds combination in ammonium salt, alkali metal salt, magnesium salts and the thallium salt of further preferred molybdic acid; Said combination is sodium molybdate/potassium molybdate, magnesium molybdate/potassium molybdate, ammonium molybdate/sodium molybdate etc. for example, a kind or at least 2 kinds combination in further preferred ammonium molybdate, sodium molybdate, potassium molybdate, the magnesium molybdate, preferred especially sodium molybdate.Molybdate of the present invention all can obtain through consulting prior art for preparing through being purchased acquisition or those skilled in the art.
The anion of tungstates contains tungstate radicle (WO 4 2-) or gather the salt of tungstate radicle.The preferred water-soluble tungstates of tungstates according to the invention; The ammonium salt of preferred wolframic acid and a kind or at least 2 kinds combination in the alkali metal salt; 1 kind or at least 2 kinds combination in further preferred ammonium tungstate, sodium tungstate, potassium tungstate, the tungstate lithium; Said combination is ammonium tungstate/sodium tungstate, potassium tungstate/tungstate lithium, potassium tungstate/sodium tungstate etc. for example, preferred especially sodium tungstate.Tungstates of the present invention all can obtain through consulting prior art for preparing through being purchased acquisition or those skilled in the art.
Two of the object of the invention is to provide a kind of preparation method of vanadium base fluid phase catalyst.
The preparation method of said vanadium base fluid phase catalyst is a load vfanadium compound on organic amine.With the vanadate is catalytic active substance, and ammonium molybdate is that co-catalyst is an example, and the principle of organic extractant phase is following among the preparation method of explanation vanadium base fluid phase catalyst:
With the aqueous solution that is dissolved with vanadate, co-catalyst raw material, mix with the organic solvent that contains organic amine, inorganic salts such as organic amine and vanadium, molybdenum are combined into organo-metallic compound:
Wherein M is represented as vanadium or molybdenum.
After organic extractant phase finishes, after the washing of the organic facies after the extraction, slaking, prepare vanadium base fluid phase catalyst, said vanadium base fluid phase catalyst load Mo co-catalyst.
Because above-mentioned extraction process control pH is between 3-9; Make inorganic salts such as vanadate, molybdate, tungstates combine with organic amine with solvation extraction mechanism; Active high, the load cocatalyst simultaneously of vfanadium compound in the organic extracted species of this metal, and the water-insoluble organic solvent system can not absorb water, arsenic etc. to the virulent material of catalyst.
The present invention utilizes organic amine to this catalyst of the extractive reaction of metal oxygen-containing hydrochlorates such as vanadium preparation, through the control operation condition with in the aqueous solution contain the vanadium catalytic active substance, co-catalyst is extracted in the organic facies, is prepared as the vanadium liquid-phase catalyst after the maturation process.
Preferably, the preparation method of said vanadium base fluid phase catalyst comprises the steps:
(1) is in oxysalt, molybdate, the water-soluble solution of tungstates with vanadium, obtains containing the vanadium aqueous solution;
(2) organic amine is dissolved in the organic solvent, obtains containing the organic solution of organic amine;
(3) organic solution that contains organic amine that the vanadium aqueous solution and step (2) obtain that contains that step (1) is obtained is fully mixed, and regulates the pH value, and the extracting vanadium compound is to the organic facies that contains organic amine;
(4) will contain the vanadium organic facies after washing, dehydration, slaking, promptly get vanadium base fluid phase catalyst.
Step (1) is described, and to contain vanadium in the vanadium aqueous solution be that the concentration of oxysalt, molybdate, tungstates can be selected according to actual conditions and the professional knowledge grasped by those skilled in the art; The preferred vanadium of the present invention is that oxysalt, molybdate, tungstates concentration independently are selected from 0.08-10mol/L respectively; For example 0.08mol/L, 0.09mol/L, 9.5mol/L, 0.50mol/L, 8.9mol/L, 0.70mol/L, 1.2mol/L, 7.0mol/L, 7.4mol/L, 1.95mol/L, 2.04mol/L, 2.87mol/L, 3.5mol/L, 4.0mol/L, 4.2mol/L, 4.3mol/L, 5.3mol/L, 6.0mol/L, 10mol/L etc.; Further preferred 0.08-1mol/L, preferred especially 0.1-0.2mol/L.
The described well-mixed mixed proportion of the organic solution that contains organic amine that the vanadium aqueous solution and step (2) obtain that contains that step (1) is obtained of step (3) does not have particular determination; Those skilled in the art have the ability to know proper mixture ratio example, for example mixed proportion can make 1: 1,2: 1,1: 5,1: 10 etc.
The described pH value of step (3) preferably is controlled between the 3-9; Purpose is for inorganic salts such as vanadate, molybdate, tungstates are combined with organic amine with solvation extraction mechanism; Thereby make in the catalyst active high, the load cocatalyst simultaneously of vfanadium compound; And the water-insoluble organic solvent system can not absorb water, arsenic etc. to the virulent material of catalyst, improves the mithridatism and the stability of catalyst.Regulating the reagent that the pH value selects for use is prior art, and those skilled in the art have the ability to know, typical case but non-limiting instance has H 2SO 4, HCl, HNO 3, NaOH etc.
The said washing of step (4) is that water fully mixes with organic facies, and purpose is to clean through water is fully mixed with organic facies, is entrained in the aqueous solution residual on the organic facies to remove.Preferably, dewater after the washing, said dehydration can be accomplished through modes such as centrifugal layering dehydration and/or standing demix dehydrations.The organic facies that contains catalytic component based on vanadium should guarantee no longer to contain moisture through after the washing-dehydration.
The said slaking of step (4) is stand at low temperature slaking or quiescence in high temperature slaking.The temperature of said stand at low temperature slaking is 1-10 ℃; Preferably, the temperature of said quiescence in high temperature slaking is 85-105 ℃, for example 85 ℃, 86 ℃, 88 ℃, 90 ℃, 95 ℃, 99 ℃, 100 ℃, 103 ℃, 104 ℃, 105 ℃ etc.; Further preferably, the said curing time is >=30 hours, for example 30h, 37h, 42h, 59h, 68h, 79h etc., preferred 30-60 hour especially, most preferably 48 hours.
Used water in the method for the invention all is selected from a kind or at least 2 kinds combination in running water, deionized water, distilled water, redistilled water or the ultra-pure water, preferred deionized water.For example used water all is independently selected from a kind or at least 2 kinds combination in running water, deionized water, distilled water, redistilled water or the ultra-pure water in step (1) and (4), preferably uses deionized water.
Three of the object of the invention is to provide a kind of method of flue gas desulfurization and denitrification, and said method is used vanadium base fluid phase catalyst of the present invention.Said method is reacted for directly feeding reaction gas to vanadium base fluid phase catalyst.
The method of said flue gas desulfurization and denitrification comprises the steps:
(1) vanadium base fluid phase catalyst is fed inert gas at a certain temperature;
(2) in vanadium base fluid phase catalyst, feed reaction gas;
(3) carry out catalytic oxidation, reach the purpose of desulphurization denitration.
The said uniform temperature of step (1) is 80 ℃-200 ℃, for example 80 ℃, 85 ℃, 92 ℃, 99 ℃, 103 ℃, 130 ℃, 170 ℃, 178 ℃, 183 ℃, 190 ℃, 197 ℃, 200 ℃, and preferred 90 ℃-150 ℃, most preferably 100 ℃.
Said inert gas is a kind or at least 2 kinds combination in helium, neon, argon gas, krypton gas, the xenon, preferred argon gas; Time >=the 20min of said feeding inert gas, for example 20min, 25min, 30min, 50min, 70min etc.The purpose that feeds inert gas is to get rid of the active gases in the vanadium base fluid phase catalyst and be purchased the volatile organic matter impurity that possibly exist in organic amine, the organic solvent, improves the reactivity of desulfurization and denitrification reaction.
The component of the said reaction gas of step (2) comprises the pending SO that contains x, NO xThe flue gas of pollutant and carrier gas, said reaction gas also can contain O 2, NH 3Deng gas, said carrier gas is preferably the combination of nitrogen, inert gas, airborne a kind or at least 2 kinds, and for example reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Composition, reaction gas are by NH 3, NO, SO 2And carrier gas air composition etc.The air speed of said feeding reaction gas is 5000-30000h -1, 5000h for example -1, 5500h -1, 6200h -1, 7300h -1, 8000h -1, 10000h -1, 12000h -1, 20000h -1, 26000h -1, 28000h -1, 30000h -1, preferred 8000-15000h -1, 10000h most preferably -1
The said catalytic oxidation process of step (3) is that reaction gas is in catalyst, stopping certain hour under the uniform temperature.Preferably; In the catalytic oxidation process; Described uniform temperature is 200 ℃-400 ℃; For example 200 ℃, 201 ℃, 205 ℃, 210 ℃, 222 ℃, 250 ℃, 280 ℃, 302 ℃, 330 ℃, 370 ℃, 390 ℃, 400 ℃, 263 ℃, 399 ℃ etc., preferred 250 ℃-350 ℃, most preferably 300 ℃.Preferably, in the catalytic oxidation process, described certain hour >=0.5s, for example 0.5s, 1s, 5s, 15s, 40s, 1min, 5min etc., the preferred time of staying is 1s.
When using vanadium base fluid phase catalyst to carry out flue gas desulfurization and denitrification; The flow velocity of reaction gas, with ratio, the reaction temperature of catalytic oxidation and the reaction conditions such as time that in catalyst, stop of carrier gas; Those skilled in the art should select according to specific circumstances, such as containing SO in the pending flue gas x, NO xThe content of pollutant and ratio etc.
Vanadium base fluid phase catalyst according to the invention can be realized recycling utilization, realizes that recycling utilization is the state of the art, and those skilled in the art have the ability to know.Preferably, step (3) is carried out back extraction realization recycling utilization to catalyst carrier afterwards.The present invention is through the method for extractive reaction, with the vanadium base fluid phase catalyst regeneration of load, particularly, can be through back extraction, removal of impurities, extract load once more and realize recycling utilization.
The present invention has the following advantages:
(1) catalyst according to the invention is water-insoluble organic liquid phase, has good water-resistance, and is all insensitive to air, water, acid simultaneously; Heat stability is good; Synthetic, circulation, renovation process are simple, are easy to industrialization, and in flue gas desulfurization and denitrification, demonstrate high contact area and high catalytic activity.
(2) the liquid-phase catalysis system substitutes the solid catalysis system, has improved the catalytic reaction contact area greatly, thereby improves the catalytic efficiency of per volume of catalyst, reduces reactor volume, catalyst amount, significantly reduces investment and operating cost.
(3) vanadium base fluid phase catalyst of the present invention can be through back extraction, removal of impurities, extract load once more and realize recycling utilization.
(4) use vanadium base fluid phase catalyst according to the invention to carry out the desulphurization denitration of flue gas, reaction speed is the shortest to be 0.5s, the SO of catalysis simultaneously 2And NO, and the high (SO of catalytic efficiency 2Conversion ratio be up to 89%, the removal efficiency of NO is up to 99.8%), and equipment investment is little, operating cost is low, circular regeneration is simple.
Description of drawings
Fig. 1 is the preparation-use-circular regeneration flow chart of vanadium base fluid phase catalyst according to the invention.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment one
The sodium metavanadate aqueous solution of preparation 0.2mol/L; With obtained aqueous solution and aliphatic chain primary amine N1923 by comparing mixing in 1: 1, through replenishing 1: 1 H 2SO 4The aqueous solution, the balance pH behind the conditioned reaction is at 6-8.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.Organic facies after the washing through behind the centrifuge dewatering of 2000rpm, is placed under 4 ℃ of environment and left standstill slaking 48 hours, be prepared as vanadium base fluid phase catalyst.
Get the catalyst 50ml of above-mentioned preparation, logical argon gas feeds reaction gas after 30 minutes under 100 ℃, and reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 1000ppm, SO 2Be 500ppm, O 2Be 5%.Control air speed 10000h -1, reaction temperature is 200 ℃, the time of staying is 1s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 80%, and the removal efficiency of NO is 81.2%.
Above-mentioned vanadium base fluid phase catalyst recycles 15 times, and removal efficiency is constant basically, during the 15th use, and SO 2Conversion ratio reaches 80%, and the removal efficiency of NO is 81.6%.
The circular regeneration of catalyst: 15 times catalyst and the deionized water of will circulating carries out back extraction regeneration by after comparing 1: 1 and mixing, wash, clarify.The back extraction regenerative agent is the NaOH aqueous solution of 2mol/L, back extraction time of staying 50min, catalyst and back washing agent be in a ratio of 35 ℃ of balance pH value 10-11, temperature behind 1: 4, back extraction.After the back extraction, vanadium gets into the back washing agent aqueous solution with sodium metavanadate, and organic amine N1923 is in organic facies.The sodium metavanadate aqueous solution can repeat to extract the load vanadium with the organic amine solvent after regulating pH, realizes the circular regeneration of catalyst.
Vanadium base fluid phase catalyst behind the circular regeneration carries out catalytic oxidation, SO 2Conversion ratio reaches 80%, and the removal efficiency of NO is 82.1%.
Embodiment two
The preparation question response aqueous solution wherein contains the sodium metavanadate of 0.1mol/L, the sodium molybdate of 0.2mol/L, the sodium tungstate of 0.2mol/L; With the gained question response aqueous solution and quaternary amine N263 by comparing mixing in 2: 1, through replenishing 1: 1 H 2SO 4The aqueous solution, the balance pH behind the conditioned reaction is at 6-8.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.Organic facies after the washing through behind the centrifuge dewatering of 2000rpm, is placed under 100 ℃ of environment and left standstill slaking 48 hours, be prepared as the vanadium base fluid phase catalyst that contains Mo, W.
Get the catalyst 50ml of above-mentioned preparation, logical argon gas feeds reaction gas after 30 minutes under 100 ℃, and reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 1000ppm, SO 2Be 500ppm, O 2Be 5%.Control air speed 10000h -1, reaction temperature is 400 ℃, the time of staying is 1s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 82%, and the removal efficiency of NO is 99.3%.
Embodiment three
The preparation question response aqueous solution wherein contains the sodium metavanadate of 0.1mol/L, the sodium molybdate of 0.2mol/L, the sodium tungstate of 0.2mol/L; The organic facies that preparation tertiary amine TOA, primary amine Primene JM-T, secondary amine 7203 mixed in 1: 1: 1 by volume; With organic facies and the aqueous solution by comparing mixing in 1: 1, through replenishing 1: 1 H 2SO 4The aqueous solution, the balance pH behind the conditioned reaction is at 6-8.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.With the organic facies after the washing through behind the centrifuge dewatering of 2000rpm, place 100 ℃ of environment under with melissane just mixed in 1: 1 by volume complete after, left standstill slaking 48 hours, be prepared as the vanadium base fluid phase catalyst that contains Mo, W.
Get the catalyst 50ml of above-mentioned preparation, logical argon gas feeds reaction gas after 30 minutes under 100 ℃, and reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 1000ppm, SO 2Be 500ppm, O 2Be 5%.Control air speed 10000h-1, reaction temperature is 270 ℃, the time of staying is 1s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 86%, and the removal efficiency of NO is 96.6%.
Embodiment four
The preparation question response aqueous solution wherein contains the ammonium vanadate of 0.07mol/L, the sodium molybdate of 0.01mol/L, drips 1: 1 HSO 4The aqueous solution to ammonium vanadate all dissolves; The organic facies that preparation quaternary amine N263, TOA, silicone oil mixed in 1: 1: 2 by volume; The resulting aqueous solution mixed by 2: 1 with organic facies, through additional 1: 1 HSO 4The aqueous solution, the balance pH behind the conditioned reaction is at 3-7.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.After the centrifuge layering dehydration of the organic facies after the washing through 2000rpm, place under 1 ℃ of environment and left standstill slaking 30 hours, be prepared as the vanadium base fluid phase catalyst that contains Mo, W.
Get the catalyst 50ml of above-mentioned preparation, feed reaction gas at 80 ℃ of following helium injection gas after 50 minutes, reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 2000ppm, SO 2Be 800ppm, O 2Be 7%.Control air speed 30000h -1, reaction temperature is 400 ℃, the time of staying is 10s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 89%, and the removal efficiency of NO is 99.8%.
Embodiment five
The preparation question response aqueous solution wherein contains the pyrovanadic acid potassium of 7mol/L, the ammonium molybdate of 1mol/L, the sodium tungstate of 2mol/L; The organic facies that preparation 16DMA, N1923, paraffin mixed in 1: 1: 3 by volume, by comparing mixings in 1: 3, through additional 1: 1 the HCl aqueous solution, the balance pH behind the conditioned reaction was at 5-9 with the resulting aqueous solution and organic facies.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.After the centrifuge layering dehydration of the organic facies after the washing through 2000rpm, place under 10 ℃ of environment and left standstill slaking 30 hours, be prepared as the vanadium base fluid phase catalyst that contains Mo, W.
Get the catalyst 50ml of above-mentioned preparation, logical argon gas feeds reaction gas after 50 minutes under 200 ℃, and reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 1500ppm, SO 2Be 400ppm, O 2Be 5%.Control air speed 5000h -1, reaction temperature is 400 ℃, the time of staying is 0.5s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 84%, and the removal efficiency of NO is 89.8%.
Embodiment six
The preparation question response aqueous solution wherein contains many sodium vanadates of 0.4mol/L, the sodium molybdate of 0.3mol/L, the tungstate lithium of 0.2mol/L; By comparing mixing in 1: 2, through replenishing 1: 1 the HCl aqueous solution, the balance pH behind the conditioned reaction is at 4-8 with the resulting aqueous solution and quaternary amine N263.Get reacted organic facies and fully mix, wash organic facies by comparing 1: 10 with deionized water.After the centrifuge layering dehydration of the organic facies after the washing through 2000rpm, place under 85 ℃ of environment and left standstill slaking 60 hours, be prepared as the vanadium base fluid phase catalyst that contains Mo, W.
Get the catalyst 50ml of above-mentioned preparation, logical argon gas feeds reaction gas after 20 minutes under 130 ℃, and reaction gas is by NH 3, NO, SO 2, O 2And carrier gas N 2Form, wherein NH 3, NO is 1300ppm, SO 2Be 700ppm, O 2Be 4%.Control air speed 5000h -1, reaction temperature is 300 ℃, the time of staying is 1s in liquid-phase catalyst.After the reaction, SO 2Conversion ratio reaches 83%, and the removal efficiency of NO is 95.8%.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.

Claims (10)

1. a vanadium base fluid phase catalyst is characterized in that, said activity of such catalysts material is the organic vanadium compound, and said catalyst carrier is organic amine and/or is dissolved in the organic amine in the organic solvent that the phase of said catalyst is a liquid phase.
2. catalyst as claimed in claim 1; It is characterized in that; It is oxysalt that said organic vanadium compound is selected from vanadium; 1 kind or at least 2 kinds combination in preferred vanadate, metavanadate, pyrovanadate, the vanadate, preferred water-soluble vanadium is a kind or at least 2 kinds combination in the oxysalt, further preferred vanadium is the ammonium salt of oxyacid, a kind or at least 2 kinds combination in the alkali metal salt; 1 kind or at least 2 kinds combination, most preferably sodium metavanadate in preferred especially sodium vanadate, sodium metavanadate, many sodium vanadates, pyrovanadic acid ammonium, ammonium metavanadate, ammonium vanadate, potassium metavanadate, the many potassium vanadates;
Preferably; Said organic amine is selected from a kind or at least 2 kinds combination in the primary amine, secondary amine, tertiary amine, quaternary ammonium salts of carbon number >=10; 1 kind or at least 2 kinds combination in preferred chlorination trimethyl alkanamine class, trialkyl tertiary amines, the fatty alkyl dimethyl tertiary amine class; 1 kind or at least 2 kinds combination among preferred especially N263, N1923, TOA, 7203,7301,12DMA, the 16DMA, most preferably a kind or at least 2 kinds combination among N263, N1923, TOA, the Primene JM-T, 7203; In the preferred comfortable 200-400 ℃ scope of said organic solvent is liquid, and the organic solvent of boiling point >=350 ℃.
3. according to claim 1 or claim 2 catalyst is characterized in that said catalyst contains co-catalyst, and said co-catalyst is molybdate and/or tungstates;
Preferably; The preferred water-soluble molybdate of said molybdate; 1 kind or at least 2 kinds combination in ammonium salt, alkali metal salt, magnesium salts and the thallium salt of preferred molybdic acid, a kind or at least 2 kinds combination in further preferred ammonium molybdate, sodium molybdate, potassium molybdate, the magnesium molybdate, preferred especially sodium molybdate;
Preferably; The preferred water-soluble tungstates of said tungstates; The ammonium salt of preferred wolframic acid and a kind or at least 2 kinds combination in the alkali metal salt, a kind or at least 2 kinds combination in further preferred ammonium tungstate, sodium tungstate, potassium tungstate, the tungstate lithium, preferred especially sodium tungstate.
4. the preparation method like each described vanadium base fluid phase catalyst of claim 1-3 is characterized in that, comprises the steps:
(1) is in oxysalt, molybdate, the water-soluble solution of tungstates with vanadium, obtains containing the vanadium aqueous solution;
(2) organic amine is dissolved in the organic solvent, obtains containing the organic solution of organic amine;
(3) organic solution that contains organic amine that the vanadium aqueous solution and step (2) obtain that contains that step (1) is obtained is fully mixed, adjustment pH value, and the extracting vanadium compound is to the organic facies that contains organic amine;
(4) will contain the vanadium organic facies after washing, dehydration, slaking, promptly get vanadium base fluid phase catalyst.
5. method as claimed in claim 4 is characterized in that, the mode of the said mixing of step (3) is selected from a kind or at least 2 kinds the combination in mixing of stirring, concussion, ultrasonic, jet, preferably stirs and/or shakes mixing;
Preferably, the described balance pH value of step (3) is controlled between the 3-9.
6. like claim 4 or 5 described methods, it is characterized in that the said washing of step (4) is that water fully mixes with organic facies; Said dehydration is the water layer of removing in the organic facies system, preferably adopts the dehydration of centrifugal layering dehydration and/or standing demix;
The said slaking of step (4) is stand at low temperature slaking or quiescence in high temperature slaking; Preferably, the temperature of said stand at low temperature slaking is 1-10 ℃; Preferably, the temperature of said quiescence in high temperature slaking is 85-105 ℃; Further preferably, the said curing time is >=30 hours, preferred 30-60 hour especially, and most preferably 48 hours;
Preferably, institute of the present invention water all is independently selected from a kind or at least 2 kinds combination in running water, deionized water, distilled water, redistilled water or the ultra-pure water, preferred deionized water.
7. the method for a flue gas desulfurization and denitrification, said method is used like each described vanadium base fluid phase catalyst of claim 1-3.
8. method as claimed in claim 7 is characterized in that, said method is reacted for directly feeding reaction gas to vanadium base fluid phase catalyst;
Preferably, said method comprises the steps:
(1) vanadium base fluid phase catalyst is fed inert gas at a certain temperature;
(2) in vanadium base fluid phase catalyst, feed reaction gas;
(3) carry out catalytic oxidation, reach the purpose of desulphurization denitration.
9. like claim 7 or 8 described methods, it is characterized in that the said uniform temperature of step (1) is 80 ℃-200 ℃, preferred 90 ℃-150 ℃, most preferably 100 ℃; Said inert gas is a kind or at least 2 kinds combination in helium, neon, argon gas, krypton gas, the xenon, preferred argon gas; Time >=the 20min of said feeding inert gas;
The component of the said reaction gas of step (2) comprises the pending SO that contains x, NO xThe flue gas of pollutant and carrier gas, said carrier gas are preferably the combination of nitrogen, inert gas, airborne a kind or at least 2 kinds; The air speed of said feeding reaction gas is 5000-30000h -1, preferred 8000-15000h -1, 10000h most preferably -1
The said catalytic oxidation process of step (3) is that reaction gas is in catalyst, stopping certain hour under the uniform temperature; Preferably, in the catalytic oxidation process, described uniform temperature is 200 ℃-400 ℃, preferred 250 ℃-350 ℃, and most preferably 300 ℃; Preferably, in the catalytic oxidation process, described certain hour >=0.5s.
10. like each described method of claim 7-9, it is characterized in that step (3) is carried out back extraction to catalyst carrier afterwards and realized recycling utilization.
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CN104419446A (en) * 2013-09-02 2015-03-18 中国科学院大连化学物理研究所 Ultra-deep oxidation desulfurization method of diesel oil
WO2015086424A1 (en) * 2013-12-11 2015-06-18 Evonik Industries Ag A catalyst for oxidation reactions, a method for its preparation and the use thereof
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US10052620B2 (en) 2013-12-11 2018-08-21 Evonik Degussa Gmbh Catalyst for oxidation reactions, a method for its preparation and the use thereof
CN105828939B (en) * 2013-12-11 2019-07-16 赢创德固赛有限公司 For the catalyst of oxidation reaction, Its Preparation Method And Use
CN103923245A (en) * 2014-05-04 2014-07-16 中国科学院长春应用化学研究所 Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof
CN103923244A (en) * 2014-05-04 2014-07-16 中国科学院长春应用化学研究所 Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof
CN103923244B (en) * 2014-05-04 2016-09-28 中国科学院长春应用化学研究所 Preparation method, vanadium catalyst composition and the application thereof of a kind of catalyst containing trivalent vanadium
CN104263946A (en) * 2014-10-10 2015-01-07 武汉凯迪电力环保有限公司 Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst
CN104762475A (en) * 2014-12-03 2015-07-08 核工业北京化工冶金研究院 Vanadium extracting method capable of dynamically adjusting acid
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