CN103447046A - Stable and efficient wet oxidation catalyst and preparation method thereof - Google Patents
Stable and efficient wet oxidation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a stable and efficient wet oxidation catalyst and a preparation method thereof, belonging to the technical field of water treatment and material preparation. The preparation method of the catalyst comprises the following steps: dropping a mixed salt solution containing copper, zinc, aluminum, iron and lanthanum and a sodium hydroxide solution into a sodium carbonate solution together, and then crystallizing, filtering, washing, drying and roasting to obtain a composite oxide catalyst, wherein a precursor of the catalyst has characteristics of layered hydrotalcite. The catalyst shows an efficient and stable catalytic effect on wet catalytic oxidation of industrial wastewater and analog pollutant phenol. The preparation method improves the activity and stability of a copper-based catalyst and expands the application area of the copper-based catalyst, and the synthesized composite oxide catalyst has important application values and prospects in the field of treatment on high-concentration organic wastewater through wet catalytic oxidation.
Description
Technical field
The invention belongs to water treatment and technical field of material, more particularly, relate to a kind of catalytic wet oxidation that is applied to and process O composite metallic oxide catalyst of high concentrated organic wastewater and preparation method thereof.
Background technology
Development along with world population, industrialization, agricultural and urbanization, a large amount of difficult decomposing organic matters constantly enter water body, not only make the mankind's living environment go from bad to worse, hinder the development of related industries, and make the world can utilize the quality and quantity continuous decrease of freshwater resources.Wastewater treatment has become important society, technology, economy and political issue.The removal of water pollutant has also become important field of research.Chemical industry and petroleum industry produce the of a great variety of hypertoxic debirs.Wherein the phenol wastewater wide material sources, endanger larger.Unsubstituted phenol is studied for wastewater treatment usually used as model compound.For the purified treatment of high-concentration industrial-water, study at present the more wet-air oxidation technology that mainly contains (WAO), catalytic wet oxidation technology (CWO), supercritical Water Oxidation Technology (SCWO) etc. both at home and abroad.Wet type hydrogen peroxide catalytic oxidation (WHPCO) in Wet Catalytic Oxidation Method, as a kind of advanced oxidation process (AOPs), can be effectively and gentle processing toxic wastewater.Transistion metal compound, especially copper-based catalysts are common, the most most economical current catalyst, in the AOPs reaction, demonstrate high catalytic activity.Yet the catalysqt deactivation that in the stripping of transition metal oxide active component in course of reaction and heat treatment process, sintering causes becomes this system problem demanding prompt solution.Selecting suitable method for preparing catalyst is to solve the most direct approach of above-mentioned multi-phase oxidation catalyst stability.
Houghite material (LDHs), claim again anionic clay or layered double hydroxide, is a kind of inorganic functional material with layer structure.But its laminate is arranged and modulation according to certain ratio and order by divalence and trivalent metal cation, and the interlayer anion of balancing charge is commutative.Its topological characteristics of decomposition makes product of roasting have high-specific surface area, high thermal stability, and each metal ion can reach on molecular level and be uniformly distributed.Therefore, can utilize this characteristic of houghite and product of roasting thereof, active component, auxiliary agent and carrier together are incorporated into to the houghite laminate, then through roasting, obtain metal oxide catalyst.
Catalytic wet oxidation is commonly used the copper base oxide catalyst, when producing through roasting with copper base class hydrotalcite precursor, also keep away and unavoidably can supervene a small amount of oxide copper, under the acid reaction condition or be subject to intermediate product affect the easy stripping of copper ion, water body is caused to secondary pollution, and a large amount of composite metal oxides that simultaneously form, copper base spinel oxide for example, because structure is stable than single cupric oxide, under the same conditions, than indissoluble, go out, therefore to oxide, adopt sour pretreatment can obtain stable O composite metallic oxide catalyst, thereby can improve the stability of catalyst.
Summary of the invention
Purpose of the present invention again with overcome the deficiencies in the prior art, provide wet oxidizing catalyst of a kind of stability and high efficiency and preparation method thereof, for the high concentrated organic wastewater catalytic wet oxidation.This technical scheme not only can improve the activity of catalyst, and can suppress the particularly loss of active component of metal component so that each metal component height of catalyst is dispersed, improves the stability of catalyst.
Technical purpose of the present invention is achieved by following technical proposals:
Catalyst prepared by the present invention is the CuZnAlFeLa composite oxide catalysts, and wherein Cu and Zn are bivalent metal ion M
2+, Al, Fe and La are trivalent metal ion M
3+, its preparation method carries out according to following step:
(1) step 1, the configuration salting liquid, take soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt soluble in water, is mixed with the mixing salt solution that total concentration of metal ions is 0.01～1.50mol/L, wherein divalence and trivalent metal ion mol ratio n[M
2+]: n[M
3+]=(2.0～4.0): 1, cupric and zinc ion mol ratio n[Cu
2+]: n[Zn
2+]=(0.3～3.0): 1, preferably (1～2): 1; The mol ratio n[Al of trivalent aluminium ion and other trivalent ion summation
3+]: n[Fe
3++ La
3+]=(0.1～10.0): 1, preferably (1.5～2.5): 1; The mol ratio n[La of trivalent lanthanum and iron
3+]: n[Fe
3+]=(0.05～2.0): 1, preferably (0.1～1): 1;
In described step 1, described soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt aim to provide corresponding metallic element, select nitrate, sulfate, phosphate, acetate or chloride.
(2) step 2, prepare respectively alkali lye and carbonate solution, selects alkali and carbonate alkali lye and corresponding carbonate solution, the carbonate (CO in wherein said two kinds of solution of being prepared soluble in water respectively
3 2-) and hydroxyl (OH
-), as follows with cation ratio requirement in the mixing salt solution of step 1 preparation: CO
3 2-with trivalent metal ion (being the summation of Al, Fe and La metal ion) mol ratio n[CO
3 2-]/n[M
3+]=(2.0～2.5): 1, OH
-with total metal ion mol ratio n[OH
-]/(2n[M
2+]+3n[M
3+])=(1.6～2.0): 1, preferably (1.6～1.8): 1, (Cu and Zn are bivalent metal ion M to the valence state total electrical charge that wherein said total metal ion is metal ion in mixing salt solution
2+, Al, Fe and La are trivalent metal ion M
3+), said n [CO
3 2-] and n[OH
-] be respectively CO in carbonate and alkali lye
3 2-total mole number and OH
-total mole number
In described step 2, provide alkali hydroxy to select NaOH, potassium hydroxide or ammoniacal liquor; Provide the carbonate of carbonate to select sodium carbonate, potash or ammonium carbonate.When selecting ammoniacal liquor, need hypothesis ammoniacal liquor all to ionize, the addition needed according to the hydroxyl calculating ammoniacal liquor calculated gets final product; In the solution of final preparation, OH in alkali lye
-concentration select 0.01～3.00mol/L, CO in carbonate solution
3 2-concentration select 0.01～3.00mol/L.
(3) step 3, titration, mixing salt solution (pH value presents acidity) in step (1) and the middle alkali lye (the pH value presents alkalescence) of step (2) drip are added in carbonate solution prepared by step (2), and take by the rate of titration of controlling two kinds of solution the pH that keeps whole titration system is 10 ± 0.2
In described step 3, when dripping, stirred, for example 200～500 turn/min, be precipitated thing when dripping.
(4) step 4, the sediment that step (3) is obtained, under 40～90 ℃ of conditions, stirs crystallization 4～72h, preferably, under 50～80 ℃ of conditions, stirs crystallization 24～60h, turn/min of mixing speed 100～300; Then by the slurry that obtains repeatedly filtered water be washed till neutrality, after drying, grind to form fine powder under 40～150 ℃, obtain catalyst precarsor
In described step 4, by the slurry that obtains repeatedly filtered water be washed till in neutral process, aqueous temperature is controlled at 20～60 ℃; Preferably 50～120 ℃ of bake out temperatures, select baking oven to be dried, selection of time 12～24h.
(5) step 5, roasting: the catalyst precarsor (powder) that step (4) is obtained is placed in Muffle furnace, with 1～10 ℃ of min
-1heating rate is warming up to 400～800 ℃ of roasting 1～10h from 20 ℃ of room temperatures, then cools to room temperature with the furnace and obtains catalyst, preferably 500～700 ℃ of roasting 2～6h.
(6) step 6, acid treatment: the diluted acid diafiltration of 0.10～1.00mol/L for the oxide powder that step (5) is obtained, until can't detect metal ion in filtrate, then use the clear water diafiltration 4 times, then the condition of repeating step (5), by sample roasting 2h, obtains catalyst.
In step 6, described diluted acid is selected hydrochloric acid, sulfuric acid or nitric acid.
In above-mentioned preparation method, the resulting precursor of step (5) be take hydrotalcite-like compound as main, and resulting catalyst is composite metal oxide after step (5) roasting.
But technical scheme of the present invention is uniformly distributed characteristics based on houghite laminate element modulation and element, by the catalyst activity component, each element of auxiliary agent and carrier is introduced laminate simultaneously, prepare the houghite precursor, then the characteristics of utilizing stratiform houghite material topology to decompose, obtain the O composite metallic oxide catalyst material by roasting and acid treatment, realize the performance of stability and high efficiency under high-concentration waste water wet oxidation condition: the catalyst of preparation is mixed to use with hydrogen peroxide, for phenolic waste water, saccharin sodium is produced the comprehensive wastewater (chemical oxygen demand COD of measuring with potassium dichromate method
cr=17339.32mg/l, ammonia-nitrogen content NH
3-N=6439.22mg/l, pH=8.17, black) wet oxidation catalysis in.
Method of the present invention has been widened the applying working condition of houghite based composite metal oxidate, can in acid or alkali environment, stablize use.Composite oxide catalytic thing catalyst prepared by the method is processed the high concentrated organic wastewater field at catalytic wet oxidation and is had good using value and prospect.Compared with prior art, the present invention be take houghite as precursor prepares composite metal oxide, is conducive to the uniform and stable distribution of active component, improves the utilization ratio of active component; The introducing of component Fe and La, be conducive to control activation and decomposition, the dispersion of active component and the activity of composite oxides Surface Oxygen and Lattice Oxygen of hydrogen peroxide; The preparation low cost of raw materials, simple to operate, be easy to large-scale production.
The accompanying drawing explanation
Fig. 1 is the XRD spectra of catalyst and precursor thereof before and after acid treatment in embodiment 1, in figure, and a: embodiment 1 gained catalyst precarsor, b: embodiment 1 gained catalyst precarsor product of roasting, gained O composite metallic oxide catalyst after c: embodiment 1 acid treatment.
The XRD spectra that Fig. 2 is acid treatment procatalyst and precursor thereof in embodiment 2, in figure, a: embodiment 2 gained catalyst precarsors, b: embodiment 2 gained catalyst precarsor product of roastings.
The specific embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.The ammoniacal liquor used, purchased from the ammoniacal liquor of the pure mass percent 25% of analysis of Tianjin Ke Wei company, is mixed with the weak aqua ammonia of mass percent 7.0% by dilution.
Embodiment 1
8.46g copper nitrate, 9.52g zinc nitrate, 9.38g aluminum nitrate, 3.23g ferric nitrate and 0.15g lanthanum nitrate are dissolved in 100ml water, are mixed with mixing salt solution.Respectively 11.20g potassium hydroxide and 6.30g sodium carbonate are dissolved in 100ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and potassium hydroxide solution slowly are added drop-wise in the sodium carbonate liquor of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, salting liquid to be mixed runs out of, stop dripping, sediment, under 60 ℃ of water bath condition, is stirred to crystallization 24h, the slurries filtration obtained is washed to neutrality, and, by filter cake dried overnight in the baking oven of 60 ℃, in Fig. 1, a is known, the gained powder is houghite, by precursor powder in Muffle furnace, with 2 ℃ of min
-1heating rate is warming up to 550 ℃ of roasting 4h from room temperature, obtain product of roasting, and b is known in Fig. 1, its product of roasting is mainly composite metal oxide, rare nitric acid diafiltration to it with 1mol/l, until can't detect metal ion in filtrate, then use the clear water diafiltration 4 times, and then in Muffle furnace with 2 ℃ of min
-1heating rate is warming up to 550 ℃ of roasting 2h from room temperature, and its XRD spectra is as shown in c in Fig. 1, and the catalyst sample after known processing is complex metal.
Taking the above-mentioned catalyst of 1g puts in the phenolic waste water that 100ml concentration is 500mg/l, add 5ml(30% under stirring condition) hydrogen peroxide, vigorous stirring 1h in the normal temperature and pressure enclosed system, adopting the conversion ratio of high-performance liquid chromatogram determination phenol is 91%, and inductively coupled plasma spectrophotometer reactant liquor does not detect metal ion.
Take the above-mentioned catalyst of 7.5g and put into 100ml saccharin sodium production comprehensive wastewater (COD
cr=17339.32mg/l, NH
3-N=6439.22mg/l, pH=8.17, black) in, add 20ml(30% under stirring condition in batches) hydrogen peroxide, vigorous stirring 24h in the normal temperature and pressure enclosed system, COD
crbe down to 4832.33mg/l, NH
3-N is down to 3530.62mg/l, and pH is 7.50, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.2mg/l.
Embodiment 2
9.38g copper nitrate, 14.87g zinc nitrate, 13.13g aluminum nitrate, 5.05g ferric nitrate and 1.08g lanthanum nitrate are dissolved in 150ml water, are mixed with mixing salt solution.Respectively 16.20g NaOH and 5.30g sodium carbonate are dissolved in 100ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and sodium hydroxide solution slowly are added drop-wise in the sodium carbonate liquor of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, salting liquid to be mixed runs out of, stop dripping, sediment, under 60 ℃ of water bath condition, is stirred to crystallization 48h, the slurries filtration obtained is washed to neutrality, and, by filter cake dried overnight in the baking oven of 60 ℃, in Fig. 2, a is known, the gained powder is houghite, by precursor powder in Muffle furnace, with 5 ℃ of min
-1heating rate is warming up to 500 ℃ of roasting 4h from room temperature, obtain product of roasting, and b is known in Fig. 2, its product of roasting is mainly composite metal oxide, finally use the watery hydrochloric acid diafiltration of 0.1mol/l, until can't detect metal ion in filtrate, then use the clear water diafiltration 4 times, and then in Muffle furnace with 5 ℃ of min
-1heating rate is warming up to 500 ℃ of roasting 2h from room temperature, obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 98%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 1330.77mg/l, NH
3-N is down to 530.04mg/l, and pH is 7.53, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.1mg/l.
Embodiment 3
6.25g copper nitrate, 6.11g zinc acetate, 7.99g aluminum sulfate, 2.00g ferric sulfate and 2.17g lanthanum nitrate are dissolved in 100ml water, are mixed with mixing salt solution.The weak aqua ammonia 100ml of preparation 7.0%, and the 4.80g ammonium carbonate is dissolved in 100ml water, be mixed with aqueous slkali and carbonate solution.Mixing salt solution and weak aqua ammonia slowly are added drop-wise in the sal volatile of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 60 ℃ of water bath condition, stir crystallization 20h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 80 ℃, then by precursor powder in Muffle furnace, with 10 ℃ of min
-1heating rate is warming up to 650 ℃ of roasting 2h from room temperature, obtains product of roasting, and it with the watery hydrochloric acid diafiltration of 0.5mol/l, until can't detect metal ion in filtrate, then is used to the clear water diafiltration 4 times, and then in Muffle furnace with 10 ℃ of min
-1heating rate is warming up to 650 ℃ of roasting 2h from room temperature, obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 95%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 3346.15mg/l, NH
3-N is down to 1440.21mg/l, and pH is 7.71, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.2mg/l.
Embodiment 4
12.50g copper sulphate, 8.05g zinc sulfate, 11.89g aluminum phosphate, 6.00g ferric sulfate and 0.75g lanthanum chloride are dissolved in 150ml water, are mixed with mixing salt solution.Respectively 6.40g NaOH and 6.30g sodium carbonate are dissolved in 100ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and sodium hydroxide solution slowly are added drop-wise in the sodium carbonate liquor of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 50 ℃ of water bath condition, stir crystallization 30h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 100 ℃, by precursor powder in Muffle furnace, with 5 ℃ of min
-1heating rate is warming up to 450 ℃ of roasting 4h from room temperature, obtains product of roasting, and it with the dilute sulfuric acid diafiltration of 0.5mol/l, until can't detect metal ion in filtrate, then is used to the clear water diafiltration 4 times, and then in Muffle furnace with 5 ℃ of min
-1heating rate is warming up to 450 ℃ of roasting 2h from room temperature, obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 96%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 2038.46mg/l, NH
3-N is down to 2238.17mg/l, and pH is 7.56, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.3mg/l.
Embodiment 5
8.52g copper chloride, 6.82g zinc chloride, 4.00g aluminium chloride, 4.05g iron chloride and 1.50g lanthanum chloride are dissolved in 150ml water, are mixed with mixing salt solution.Respectively 34.08g potassium hydroxide and 10.36g potash are dissolved in 150ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and potassium hydroxide solution slowly are added drop-wise in the solution of potassium carbonate of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 50 ℃ of water bath condition, stir crystallization 72h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 120 ℃, by the gained powder in Muffle furnace, with 5 ℃ of min
-1heating rate is warming up to 750 ℃ of roasting 2h from room temperature, obtains product of roasting, and it with the watery hydrochloric acid diafiltration of 1.5mol/l, until can't detect metal ion in filtrate, then is used to the clear water diafiltration 4 times, and then in Muffle furnace with 5 ℃ of min
-1heating rate is warming up to 750 ℃ of roasting 2h from room temperature, obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 92%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 4769.23mg/l, NH
3-N is down to 3314.73mg/l, and pH is 7.53, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.3mg/l.
Embodiment 6
8.46g copper nitrate, 9.52g zinc nitrate, 10.27g aluminum sulfate, 4.05g iron chloride and 1.58g lanthanum acetate are dissolved in 150ml water, are mixed with mixing salt solution.Respectively 34.08g potassium hydroxide and 10.36g potash are dissolved in 150ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and potassium hydroxide solution slowly are added drop-wise in the solution of potassium carbonate of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 70 ℃ of water bath condition, stir crystallization 48h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 90 ℃, after powder in Muffle furnace, with 1 ℃ of min
-1heating rate is warming up to 600 ℃ of roasting 3h from room temperature, obtains product of roasting, and it with rare nitric acid diafiltration of 1.0mol/l, until can't detect metal ion in filtrate, then is used to the clear water diafiltration 4 times, and then in Muffle furnace with 5 ℃ of min
-1heating rate is warming up to 600 ℃ of roasting 3h from room temperature, obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 93%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 4230.76mg/l, NH
3-N is down to 2769.82mg/l, and pH is 7.98, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.2mg/l.
Embodiment 7
5.00g copper sulphate, 11.50g zinc sulfate, 6.66 aluminum sulfate, 4.00g ferric sulfate and 0.20g lanthanum nitrate are dissolved in 100ml water, are mixed with mixing salt solution.Respectively 4.80g NaOH and 3.07g ammonium carbonate are dissolved in 100ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and sodium hydroxide solution slowly are added drop-wise in the sal volatile of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 40 ℃ of water bath condition, stir crystallization 24h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 40 ℃, then be placed in Muffle furnace, with 5 ℃ of min
-1heating rate is warming up to 600 ℃ of roasting 4h from room temperature, by the dilute sulfuric acid diafiltration of 0.5mol/l for product of roasting, until can't detect metal ion in filtrate, then uses the clear water diafiltration 4 times, and then in Muffle furnace with 5 ℃ of min
-1heating rate is warming up to 600 ℃ of roasting 2h from room temperature and obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 86%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 6419.32mg/l, NH
3-N is down to 3651.71mg/l, and pH is 7.51, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.1mg/l.
Embodiment 8
2.56g copper chloride, 2.04g zinc chloride, 1.07 aluminium chloride, 0.32g iron chloride and 0.20g lanthanum nitrate are dissolved in 100ml water, are mixed with mixing salt solution.Respectively 3.20g NaOH and 1.59g ammonium carbonate are dissolved in 100ml water, are mixed with aqueous slkali and carbonate solution.Mixing salt solution and sodium hydroxide solution slowly are added drop-wise in the sal volatile of vigorous stirring simultaneously, control the rate of addition of salt and alkali, keeping pH is 10 ± 0.2, and salting liquid to be mixed runs out of, and stops dripping, by sediment under 60 ℃ of water bath condition, stir crystallization 24h, the slurries filtration obtained is washed to neutrality, and by filter cake dried overnight in the baking oven of 60 ℃, then be placed in Muffle furnace, with 10 ℃ of min
-1heating rate is warming up to 650 ℃ of roasting 4h from room temperature, by the watery hydrochloric acid diafiltration of 0.2mol/l for product of roasting, until can't detect metal ion in filtrate, then uses the clear water diafiltration 4 times, and then in Muffle furnace with 10 ℃ of min
-1heating rate is warming up to 650 ℃ of roasting 2h from room temperature and obtains O composite metallic oxide catalyst.
Catalyst is respectively used to phenol solution and the processing of saccharin sodium production comprehensive wastewater, and condition is with embodiment 1, and after reaction 1h, the conversion ratio of phenol is 95%, in reacted solution, metal ion do not detected.After saccharin sodium is produced the comprehensive wastewater processing, COD
crbe down to 4230.21mg/l, NH
3-N is down to 2769.22mg/l, and pH is 7.98, and color is colourless, and in reactant liquor, the copper ion concentration of stripping is less than 0.2mg/l.
Above-described embodiment basic expressions identical with embodiment 1 and or consistent character, catalyst structure is front identical with reaction, and the stability of its structure is described.
Above the present invention has been done to exemplary description; should be noted that; in the situation that do not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. the wet oxidizing catalyst of a stability and high efficiency, is characterized in that, described catalyst is the CuZnAlFeLa composite oxide catalysts, and wherein Cu and Zn are bivalent metal ion M
2+, Al, Fe and La are trivalent metal ion M
3+, its preparation method carries out according to following step:
(1) step 1, the configuration salting liquid, take soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt soluble in water, is mixed with the mixing salt solution that total concentration of metal ions is 0.01～1.50mol/L, wherein divalence and trivalent metal ion mol ratio n[M
2+]: n[M
3+]=(2.0～4.0): 1, cupric and zinc ion mol ratio n[Cu
2+]: n[Zn
2+]=(0.3～3.0): 1; The mol ratio n[Al of trivalent aluminium ion and other trivalent ion summation
3+]: n[Fe
3++ La
3+]=(0.1～10.0): 1; The mol ratio n[La of trivalent lanthanum and iron
3+]: n[Fe
3+]=(0.05～2.0): 1
(2) step 2, prepare respectively alkali lye and carbonate solution, selects alkali and carbonate alkali lye and corresponding carbonate solution, the carbonate (CO in wherein said two kinds of solution of being prepared soluble in water respectively
3 2-) and hydroxyl (OH
-), as follows with cation ratio requirement in the mixing salt solution of step 1 preparation: CO
3 2-with trivalent metal ion (being the summation of Al, Fe and La metal ion) mol ratio n[CO
3 2-]/n[M
3+]=(2.0～2.5): 1, OH
-with total metal ion mol ratio n[OH
-]/(2n[M
2+]+3n[M
3+])=(1.6～2.0): 1, (Cu and Zn are bivalent metal ion M to the valence state total electrical charge that wherein said total metal ion is metal ion in mixing salt solution
2+, Al, Fe and La are trivalent metal ion M
3+), said n [CO
3 2-] and n[OH
-] be respectively CO in carbonate and alkali lye
3 2-total mole number and OH
-total mole number
(3) step 3, titration, be added to alkali lye drip in mixing salt solution in step (1) and step (2) in carbonate solution prepared by step (2), and take by the rate of titration of controlling two kinds of solution the pH that keeps whole titration system is 10 ± 0.2
(4) step 4, the sediment that step (3) is obtained, under 40～90 ℃ of conditions, stirs crystallization 4～72h; Then by the slurry that obtains repeatedly filtered water be washed till neutrality, after drying, grind to form fine powder under 40～150 ℃, obtain catalyst precarsor
(5) step 5, roasting: the catalyst precarsor (powder) that step (4) is obtained is placed in Muffle furnace, with 1～10 ℃ of min
-1heating rate is warming up to 400～800 ℃ of roasting 1～10h from 20 ℃ of room temperatures, then cools to room temperature with the furnace
(6) step 6, acid treatment: the diluted acid diafiltration of 0.10～1.00mol/L for the oxide powder that step (5) is obtained, until can't detect metal ion in filtrate, then use the clear water diafiltration 4 times, then the condition of repeating step (5), by sample roasting 2h, obtains catalyst.
2. the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 1, it is characterized in that, in described step 1, described soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt aim to provide corresponding metallic element, select nitrate, sulfate, phosphate, acetate or chloride, cupric and zinc ion mol ratio n[Cu
2+]: n[Zn
2+]=(1～2): 1, the mol ratio n[Al of trivalent aluminium ion and other trivalent ion summation
3+]: n[Fe
3++ La
3+]=(1.5～2.5): 1; The mol ratio n[La of trivalent lanthanum and iron
3+]: n[Fe
3+]=preferably (0.1～1): 1.
3. the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 1, is characterized in that, in described step 2, provides alkali hydroxy to select NaOH, potassium hydroxide or ammoniacal liquor; Provide the carbonate of carbonate to select sodium carbonate, potash or ammonium carbonate; OH
-with total metal ion mol ratio n[OH
-]/(2n[M
2+]+3n[M
3+])=(1.6～1.8): 1, OH in alkali lye
-concentration select 0.01～3.00mol/L, CO in carbonate solution
3 2-concentration select 0.01～3.00mol/L.
4. the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 1, is characterized in that, in described step 3, when dripping, stirred 200～500 turn/min, when dripping, is precipitated thing; In described step 4, the sediment that step (3) is obtained, under 50～80 ℃ of conditions, stirs crystallization 24～60h, turn/min of mixing speed 100～300; By the slurry that obtains repeatedly filtered water be washed till in neutral process, aqueous temperature is controlled at 20～60 ℃; Preferably 50～120 ℃ of bake out temperatures, select baking oven to be dried, selection of time 12～24h.
5. the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 1, is characterized in that, preferred 500～700 ℃ of roasting 2～6h in described step 5; In described step 6, described diluted acid is selected hydrochloric acid, sulfuric acid or nitric acid.
6. the preparation method of the wet oxidizing catalyst of a stability and high efficiency, is characterized in that, according to following step, carries out:
(1) step 1, the configuration salting liquid, take soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt soluble in water, is mixed with the mixing salt solution that total concentration of metal ions is 0.01～1.50mol/L, wherein divalence and trivalent metal ion mol ratio n[M
2+]: n[M
3+]=(2.0～4.0): 1, cupric and zinc ion mol ratio n[Cu
2+]: n[Zn
2+]=(0.3～3.0): 1; The mol ratio n[Al of trivalent aluminium ion and other trivalent ion summation
3+]: n[Fe
3++ La
3+]=(0.1～10.0): 1; The mol ratio n[La of trivalent lanthanum and iron
3+]: n[Fe
3+]=(0.05～2.0): 1
(2) step 2, prepare respectively alkali lye and carbonate solution, selects alkali and carbonate alkali lye and corresponding carbonate solution, the carbonate (CO in wherein said two kinds of solution of being prepared soluble in water respectively
3 2-) and hydroxyl (OH
-), as follows with cation ratio requirement in the mixing salt solution of step 1 preparation: CO
3 2-with trivalent metal ion (being the summation of Al, Fe and La metal ion) mol ratio n[CO
3 2-]/n[M
3+]=(2.0～2.5): 1, OH
-with total metal ion mol ratio n[OH
-]/(2n[M
2+]+3n[M
3+])=(1.6～2.0): 1, (Cu and Zn are bivalent metal ion M to the valence state total electrical charge that wherein said total metal ion is metal ion in mixing salt solution
2+, Al, Fe and La are trivalent metal ion M
3+), said n [CO
3 2-] and n[OH
-] be respectively CO in carbonate and alkali lye
3 2-total mole number and OH
-total mole number
(3) step 3, titration, be added to alkali lye drip in mixing salt solution in step (1) and step (2) in carbonate solution prepared by step (2), and take by the rate of titration of controlling two kinds of solution the pH that keeps whole titration system is 10 ± 0.2
(4) step 4, the sediment that step (3) is obtained, under 40～90 ℃ of conditions, stirs crystallization 4～72h; Then by the slurry that obtains repeatedly filtered water be washed till neutrality, after drying, grind to form fine powder under 40～150 ℃, obtain catalyst precarsor
(5) step 5, roasting: the catalyst precarsor (powder) that step (4) is obtained is placed in Muffle furnace, with 1～10 ℃ of min
-1heating rate is warming up to 400～800 ℃ of roasting 1～10h from 20 ℃ of room temperatures, then cools to room temperature with the furnace
(6) step 6, acid treatment: the diluted acid diafiltration of 0.10～1.00mol/L for the oxide powder that step (5) is obtained, until can't detect metal ion in filtrate, then use the clear water diafiltration 4 times, then the condition of repeating step (5), by sample roasting 2h, obtains catalyst.
7. the preparation method of the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 6, it is characterized in that, in described step 1, described soluble copper salt, zinc salt, aluminium salt, molysite and lanthanum salt aim to provide corresponding metallic element, select nitrate, sulfate, phosphate, acetate or chloride, cupric and zinc ion mol ratio n[Cu
2+]: n[Zn
2+]=(1～2): 1, the mol ratio n[Al of trivalent aluminium ion and other trivalent ion summation
3+]: n[Fe
3++ La
3+]=(1.5～2.5): 1; The mol ratio n[La of trivalent lanthanum and iron
3+]: n[Fe
3+]=preferably (0.1～1): 1.
8. the preparation method of the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 6, is characterized in that, in described step 2, provides alkali hydroxy to select NaOH, potassium hydroxide or ammoniacal liquor; Provide the carbonate of carbonate to select sodium carbonate, potash or ammonium carbonate; OH
-with total metal ion mol ratio n[OH
-]/(2n[M
2+]+3n[M
3+])=(1.6～1.8): 1, OH in alkali lye
-concentration select 0.01～3.00mol/L, CO in carbonate solution
3 2-concentration select 0.01～3.00mol/L.
9. the preparation method of the wet oxidizing catalyst of a kind of stability and high efficiency according to claim 6, is characterized in that, in described step 3, when dripping, stirred 200～500 turn/min, when dripping, is precipitated thing; In described step 4, the sediment that step (3) is obtained, under 50～80 ℃ of conditions, stirs crystallization 24～60h, turn/min of mixing speed 100～300; By the slurry that obtains repeatedly filtered water be washed till in neutral process, aqueous temperature is controlled at 20～60 ℃; Preferably 50～120 ℃ of bake out temperatures, select baking oven to be dried, selection of time 12～24h; Preferred 500～700 ℃ of roasting 2～6h in described step 5; In described step 6, described diluted acid is selected hydrochloric acid, sulfuric acid or nitric acid.
10. the application of wet oxidizing catalyst as described as one of claim 1-5 in wet oxidation catalytic treatment phenolic waste water or saccharin sodium production comprehensive wastewater, described saccharin sodium is produced in comprehensive wastewater, the chemical oxygen demand COD of measuring with potassium dichromate method
cr=17339.32mg/l, ammonia-nitrogen content NH
3-N=6439.22mg/l, pH=8.17, black.
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Cited By (8)
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| CN104689821A (en) * | 2015-03-20 | 2015-06-10 | 天津工业大学 | Preparation method of wet catalytic oxidation catalyst |
| CN106362751A (en) * | 2016-08-29 | 2017-02-01 | 江苏海普功能材料有限公司 | Heterogeneous catalyst, and preparation method and application method thereof |
| CN109289857A (en) * | 2018-09-17 | 2019-02-01 | 同济大学 | Rare earth doped layered composite metal hydroxides and its preparation and application |
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| CN111056612A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Treatment method and application of sulfur-containing wastewater |
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| CN104689821A (en) * | 2015-03-20 | 2015-06-10 | 天津工业大学 | Preparation method of wet catalytic oxidation catalyst |
| CN104689821B (en) * | 2015-03-20 | 2017-06-16 | 天津工业大学 | A kind of preparation method of catalytic wet oxidation catalyst |
| CN106362751A (en) * | 2016-08-29 | 2017-02-01 | 江苏海普功能材料有限公司 | Heterogeneous catalyst, and preparation method and application method thereof |
| CN109289857A (en) * | 2018-09-17 | 2019-02-01 | 同济大学 | Rare earth doped layered composite metal hydroxides and its preparation and application |
| CN111056612A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Treatment method and application of sulfur-containing wastewater |
| CN111056612B (en) * | 2018-10-16 | 2021-12-17 | 中国石油化工股份有限公司 | Treatment method and application of sulfur-containing wastewater |
| CN111072124A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Method for treating industrial acrylic acid wastewater by wet oxidation |
| CN111318283A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Wastewater treatment catalyst and preparation method thereof |
| CN110171839A (en) * | 2019-05-14 | 2019-08-27 | 南京科津新材料研究院有限公司 | A kind of smooth demagnetization material and its preparation method and application |
| CN111659402A (en) * | 2020-05-21 | 2020-09-15 | 中国科学院广州能源研究所 | CO (carbon monoxide)2Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof |
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