CN103447046A - Stable and efficient wet oxidation catalyst and preparation method thereof - Google Patents

Stable and efficient wet oxidation catalyst and preparation method thereof Download PDF

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CN103447046A
CN103447046A CN2013102761021A CN201310276102A CN103447046A CN 103447046 A CN103447046 A CN 103447046A CN 2013102761021 A CN2013102761021 A CN 2013102761021A CN 201310276102 A CN201310276102 A CN 201310276102A CN 103447046 A CN103447046 A CN 103447046A
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CN103447046B (en
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张立红
李海洲
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Tianjin University
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Abstract

本发明公开了一种稳定高效的湿式氧化催化剂及其制备方法，属于水处理与材料制备技术领域。该催化剂制备是通过将含有铜、锌、铝、铁和镧的混合盐溶液与氢氧化钠溶液并流滴加到碳酸钠溶液中，然后经过晶化、过滤、洗涤、干燥和焙烧处理后得到复合氧化物催化剂，其前体具有层状类水滑石特征。该催化剂对工业废水和模拟污染物苯酚湿式催化氧化均表现出高效稳定的催化效果。该制备方法提高了铜基催化剂的活性和稳定性，拓宽了铜基催化剂的应用领域，并且合成的复合氧化物催化剂在湿式催化氧化处理高浓度有机废水领域具有重要的应用价值和前景。

Figure 201310276102

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 catalyst is prepared by adding the mixed salt solution containing copper, zinc, aluminum, iron and lanthanum and sodium hydroxide solution into the sodium carbonate solution, and then undergoes crystallization, filtration, washing, drying and roasting. A composite oxide catalyst whose precursor has layered hydrotalcite-like characteristics. The catalyst showed efficient and stable catalytic effect on wet catalytic oxidation of industrial wastewater and simulated pollutant phenol. The preparation method improves the activity and stability of the copper-based catalyst, broadens the application field of the copper-based catalyst, and the synthesized composite oxide catalyst has important application value and prospects in the field of wet catalytic oxidation treatment of high-concentration organic wastewater.

Figure 201310276102

Description

Wet oxidizing catalyst of a kind of stability and high efficiency and preparation method thereof
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)

1.一种稳定高效的湿式氧化催化剂，其特征在于，所述催化剂为CuZnAlFeLa复合氧化物催化剂，其中Cu和Zn为二价金属离子M2+，Al、Fe和La为三价金属离子M3+，其制备方法按照下述步骤进行：1. A stable and efficient wet oxidation catalyst, characterized in that the catalyst is a CuZnAlFeLa composite oxide catalyst, wherein Cu and Zn are divalent metal ions M 2+ , and Al, Fe and La are trivalent metal ions M 3 + , its preparation method is carried out according to the following steps: （1）步骤1，配置盐溶液，称取可溶性铜盐、锌盐、铝盐、铁盐和镧盐溶于水中，配制成总金属离子浓度为0.01～1.50mol/L的混合盐溶液，其中二价与三价金属离子摩尔比n[M2+]：n[M3+]=（2.0～4.0）：1，二价铜与锌离子摩尔比n[Cu2+]：n[Zn2+]=（0.3～3.0）：1；三价铝离子与其它三价离子总和的摩尔比n[Al3+]：n[Fe3++La3+]=（0.1～10.0）：1；三价镧与铁的摩尔比n[La3+]：n[Fe3+]=（0.05～2.0）：1(1) Step 1, prepare a salt solution, weigh soluble copper salt, zinc salt, aluminum salt, iron salt and lanthanum salt and dissolve in water to prepare a mixed salt solution with a total metal ion concentration of 0.01-1.50mol/L, wherein The molar ratio of divalent and trivalent metal ions n[M 2+ ]: n[M 3+ ]=(2.0～4.0): 1, the molar ratio of divalent copper and zinc ions n[Cu 2+ ]: n[Zn 2 + ]=(0.3～3.0): 1; the molar ratio of trivalent aluminum ion to the sum of other trivalent ions n[Al 3+ ]: n[Fe 3+ +La 3+ ]=(0.1～10.0): 1; Molar ratio of trivalent lanthanum to iron n[La 3+ ]: n[Fe 3+ ]=(0.05～2.0): 1 （2）步骤2，分别配制碱液和碳酸盐溶液，选择碱和碳酸盐分别溶于水中进行制备碱液和相应的碳酸盐溶液，其中所述两种溶液中碳酸根（CO3 2-）和氢氧根（OH-），与步骤1制备的混合盐溶液中阳离子配比要求如下：CO3 2-与三价金属离子（即Al、Fe和La金属离子的总和）摩尔比n[CO3 2-]/n[M3+]=（2.0～2.5）：1，OH-与总金属离子摩尔比n[OH-]/(2n[M2+]+3n[M3+])=（1.6～2.0）：1，其中所述总金属离子为混合盐溶液中金属离子的价态总电荷（Cu和Zn为二价金属离子M2+，Al、Fe和La为三价金属离子M3+），上述n[CO3 2-]和n[OH-]分别为碳酸盐和碱液中CO3 2-总摩尔数和OH-的总摩尔数(2) Step 2, prepare lye and carbonate solution respectively, choose alkali and carbonate to be dissolved in water respectively to prepare lye and corresponding carbonate solution, wherein the carbonate radical (CO 3 2- ) and hydroxide (OH - ), and the ratio of cations in the mixed salt solution prepared in step 1 is as follows: molar ratio of CO 3 2- to trivalent metal ions (ie the sum of Al, Fe and La metal ions) n[CO 3 2- ]/n[M 3+ ]=(2.0～2.5): 1, molar ratio of OH - to total metal ions n[OH - ]/(2n[M 2+ ]+3n[M 3+ ])=(1.6～2.0): 1, wherein the total metal ions are the total valence charges of metal ions in the mixed salt solution (Cu and Zn are divalent metal ions M 2+ , Al, Fe and La are trivalent metal ion M 3+ ), the above n[CO 3 2- ] and n[OH - ] are the total moles of CO 3 2- and OH - in carbonate and lye, respectively （3）步骤3，滴定，将步骤（1）中混合盐溶液和步骤（2）中碱液并流滴加到步骤（2）制备的碳酸盐溶液中，通过控制两种溶液的滴定速度以保持整个滴定体系的pH为10±0.2(3) Step 3, titration, add the mixed salt solution in step (1) and the lye in step (2) to the carbonate solution prepared in step (2), and control the titration speed of the two solutions To keep the pH of the whole titration system at 10±0.2 （4）步骤4，将步骤（3）得到的沉淀物于40～90℃条件下，搅拌晶化4～72h；然后将得到的浆料反复过滤水洗至中性，在40～150℃下烘干后，研磨成细粉，得到催化剂前体(4) Step 4, stir and crystallize the precipitate obtained in step (3) at 40-90°C for 4-72 hours; then repeatedly filter and wash the obtained slurry until neutral, and dry at 40-150°C After drying, it is ground into a fine powder to obtain the catalyst precursor （5）步骤5，焙烧：将步骤（4）得到的催化剂前体（粉体）置于马弗炉中，以1～10℃·min-1升温速率从室温20℃升温至400～800℃焙烧1～10h，然后随炉冷却至室温(5) Step 5, roasting: put the catalyst precursor (powder) obtained in step (4) in a muffle furnace, and raise the temperature from room temperature 20°C to 400-800°C at a heating rate of 1-10°C·min -1 Roast for 1 to 10 hours, then cool to room temperature with the furnace （6）步骤6，酸处理：将步骤（5）得到的氧化物粉体用0.10～1.00mol/L的稀酸滤洗，直到滤液中检测不到金属离子，再用清水滤洗4次，然后重复步骤（5）的条件将样品焙烧2h，得到催化剂。(6) Step 6, acid treatment: filter and wash the oxide powder obtained in step (5) with 0.10-1.00mol/L dilute acid until no metal ions are detected in the filtrate, then filter and wash with water 4 times, Then repeat the conditions of step (5) to roast the sample for 2 hours to obtain the catalyst. 2.根据权利要求1所述的一种稳定高效的湿式氧化催化剂，其特征在于，在所述步骤1中，所述可溶性铜盐、锌盐、铝盐、铁盐和镧盐旨在提供相应的金属元素，选用硝酸盐、硫酸盐、磷酸盐、醋酸盐或者氯化物，二价铜与锌离子摩尔比n[Cu2+]：n[Zn2+]=（1～2）：1，三价铝离子与其它三价离子总和的摩尔比n[Al3+]：n[Fe3++La3+]=（1.5～2.5）：1；三价镧与铁的摩尔比n[La3+]：n[Fe3+]=优选（0.1～1）：1。2. A stable and efficient wet oxidation catalyst according to claim 1, characterized in that, in the step 1, the soluble copper salts, zinc salts, aluminum salts, iron salts and lanthanum salts are intended to provide corresponding The metal element, choose nitrate, sulfate, phosphate, acetate or chloride, divalent copper and zinc ion molar ratio n[Cu 2+ ]: n[Zn 2+ ]=(1～2):1 , the molar ratio of trivalent aluminum ions to the sum of other trivalent ions n[Al 3+ ]: n[Fe 3+ +La 3+ ]=(1.5～2.5): 1; the molar ratio of trivalent lanthanum to iron n[ La 3+ ]: n[Fe 3+ ]=preferred (0.1-1):1. 3.根据权利要求1所述的一种稳定高效的湿式氧化催化剂，其特征在于，所述步骤2中，提供氢氧根的碱选择氢氧化钠、氢氧化钾或者氨水；提供碳酸根的碳酸盐选择碳酸钠、碳酸钾或者碳酸铵；OH-与总金属离子摩尔比n[OH-]/(2n[M2+]+3n[M3+])=（1.6～1.8）：1，碱液中OH-的浓度选择0.01～3.00mol/L，碳酸盐溶液中CO3 2-的浓度选择0.01～3.00mol/L。3. A kind of stable and high-efficiency wet oxidation catalyst according to claim 1, it is characterized in that, in described step 2, the alkali that provides hydroxide is selected sodium hydroxide, potassium hydroxide or ammoniacal liquor; Select sodium carbonate, potassium carbonate or ammonium carbonate as acid salt; molar ratio of OH - to total metal ions n[OH - ]/(2n[M 2+ ]+3n[M 3+ ])=(1.6～1.8): 1, The concentration of OH- in the lye is selected from 0.01 to 3.00 mol/L, and the concentration of CO 3 2- in the carbonate solution is selected from 0.01 to 3.00 mol/L. 4.根据权利要求1所述的一种稳定高效的湿式氧化催化剂，其特征在于，在所述步骤3中，在滴加的同时进行搅拌200～500转/min，在滴加的同时得到沉淀物；在所述步骤4中，将步骤（3）得到的沉淀物于50～80℃条件下，搅拌晶化24～60h，搅拌速度100～300转/min；将得到的浆料反复过滤水洗至中性过程中，水溶液温度控制在20～60℃；烘干温度优选50～120℃，选择烘箱进行烘干，时间选择12～24h。4. A stable and efficient wet oxidation catalyst according to claim 1, characterized in that, in the step 3, stirring is performed at 200 to 500 rpm while adding dropwise, and precipitation is obtained while adding dropwise In the step 4, the precipitate obtained in the step (3) is stirred and crystallized for 24-60 hours under the condition of 50-80°C, and the stirring speed is 100-300 rpm; the obtained slurry is repeatedly filtered and washed with water During the neutralization process, the temperature of the aqueous solution is controlled at 20-60°C; the drying temperature is preferably 50-120°C, and an oven is selected for drying, and the time is selected for 12-24 hours. 5.根据权利要求1所述的一种稳定高效的湿式氧化催化剂，其特征在于，在所述步骤5中优选500～700℃焙烧2～6h；在所述步骤6中，所述稀酸选用盐酸、硫酸或硝酸。5. A stable and efficient wet oxidation catalyst according to claim 1, characterized in that, in the step 5, it is preferably calcined at 500-700°C for 2-6 hours; in the step 6, the dilute acid is selected from hydrochloric acid, sulfuric acid or nitric acid. 6.一种稳定高效的湿式氧化催化剂的制备方法，其特征在于，按照下述步骤进行：6. A preparation method of a stable and efficient wet oxidation catalyst, characterized in that, it is carried out according to the following steps: （1）步骤1，配置盐溶液，称取可溶性铜盐、锌盐、铝盐、铁盐和镧盐溶于水中，配制成总金属离子浓度为0.01～1.50mol/L的混合盐溶液，其中二价与三价金属离子摩尔比n[M2+]：n[M3+]=（2.0～4.0）：1，二价铜与锌离子摩尔比n[Cu2+]：n[Zn2+]=（0.3～3.0）：1；三价铝离子与其它三价离子总和的摩尔比n[Al3+]：n[Fe3++La3+]=（0.1～10.0）：1；三价镧与铁的摩尔比n[La3+]：n[Fe3+]=（0.05～2.0）：1(1) Step 1, prepare a salt solution, weigh soluble copper salt, zinc salt, aluminum salt, iron salt and lanthanum salt and dissolve in water to prepare a mixed salt solution with a total metal ion concentration of 0.01-1.50mol/L, wherein The molar ratio of divalent and trivalent metal ions n[M 2+ ]: n[M 3+ ]=(2.0～4.0): 1, the molar ratio of divalent copper and zinc ions n[Cu 2+ ]: n[Zn 2 + ]=(0.3～3.0): 1; the molar ratio of trivalent aluminum ion to the sum of other trivalent ions n[Al 3+ ]: n[Fe 3+ +La 3+ ]=(0.1～10.0): 1; Molar ratio of trivalent lanthanum to iron n[La 3+ ]: n[Fe 3+ ]=(0.05～2.0): 1 （2）步骤2，分别配制碱液和碳酸盐溶液，选择碱和碳酸盐分别溶于水中进行制备碱液和相应的碳酸盐溶液，其中所述两种溶液中碳酸根（CO3 2-）和氢氧根（OH-），与步骤1制备的混合盐溶液中阳离子配比要求如下：CO3 2-与三价金属离子（即Al、Fe和La金属离子的总和）摩尔比n[CO3 2-]/n[M3+]=（2.0～2.5）：1，OH-与总金属离子摩尔比n[OH-]/(2n[M2+]+3n[M3+])=（1.6～2.0）：1，其中所述总金属离子为混合盐溶液中金属离子的价态总电荷（Cu和Zn为二价金属离子M2+，Al、Fe和La为三价金属离子M3+），上述n[CO3 2-]和n[OH-]分别为碳酸盐和碱液中CO3 2-总摩尔数和OH-的总摩尔数(2) Step 2, prepare lye and carbonate solution respectively, choose alkali and carbonate to be dissolved in water respectively to prepare lye and corresponding carbonate solution, wherein the carbonate radical (CO 3 2- ) and hydroxide (OH - ), and the ratio of cations in the mixed salt solution prepared in step 1 is as follows: molar ratio of CO 3 2- to trivalent metal ions (ie the sum of Al, Fe and La metal ions) n[CO 3 2- ]/n[M 3+ ]=(2.0～2.5): 1, molar ratio of OH - to total metal ions n[OH - ]/(2n[M 2+ ]+3n[M 3+ ])=(1.6～2.0): 1, wherein the total metal ions are the total valence charges of metal ions in the mixed salt solution (Cu and Zn are divalent metal ions M 2+ , Al, Fe and La are trivalent metal ion M 3+ ), the above n[CO 3 2- ] and n[OH - ] are the total moles of CO 3 2- and OH - in carbonate and lye, respectively （3）步骤3，滴定，将步骤（1）中混合盐溶液和步骤（2）中碱液并流滴加到步骤（2）制备的碳酸盐溶液中，通过控制两种溶液的滴定速度以保持整个滴定体系的pH为10±0.2(3) Step 3, titration, add the mixed salt solution in step (1) and the lye in step (2) to the carbonate solution prepared in step (2), and control the titration speed of the two solutions To keep the pH of the whole titration system at 10±0.2 （4）步骤4，将步骤（3）得到的沉淀物于40～90℃条件下，搅拌晶化4～72h；然后将得到的浆料反复过滤水洗至中性，在40～150℃下烘干后，研磨成细粉，得到催化剂前体(4) Step 4, stir and crystallize the precipitate obtained in step (3) at 40-90°C for 4-72 hours; then repeatedly filter and wash the obtained slurry until neutral, and dry at 40-150°C After drying, it is ground into a fine powder to obtain the catalyst precursor （5）步骤5，焙烧：将步骤（4）得到的催化剂前体（粉体）置于马弗炉中，以1～10℃·min-1升温速率从室温20℃升温至400～800℃焙烧1～10h，然后随炉冷却至室温(5) Step 5, roasting: put the catalyst precursor (powder) obtained in step (4) in a muffle furnace, and raise the temperature from room temperature 20°C to 400-800°C at a heating rate of 1-10°C·min -1 Roast for 1 to 10 hours, then cool to room temperature with the furnace （6）步骤6，酸处理：将步骤（5）得到的氧化物粉体用0.10～1.00mol/L的稀酸滤洗，直到滤液中检测不到金属离子，再用清水滤洗4次，然后重复步骤（5）的条件将样品焙烧2h，得到催化剂。(6) Step 6, acid treatment: filter and wash the oxide powder obtained in step (5) with 0.10-1.00mol/L dilute acid until no metal ions are detected in the filtrate, then filter and wash with water 4 times, Then repeat the conditions of step (5) to roast the sample for 2 hours to obtain the catalyst. 7.根据权利要求6所述的一种稳定高效的湿式氧化催化剂的制备方法，其特征在于，在所述步骤1中，所述可溶性铜盐、锌盐、铝盐、铁盐和镧盐旨在提供相应的金属元素，选用硝酸盐、硫酸盐、磷酸盐、醋酸盐或者氯化物，二价铜与锌离子摩尔比n[Cu2+]：n[Zn2+]=（1～2）：1，三价铝离子与其它三价离子总和的摩尔比n[Al3+]：n[Fe3++La3+]=（1.5～2.5）：1；三价镧与铁的摩尔比n[La3+]：n[Fe3+]=优选（0.1～1）：1。7. the preparation method of a kind of stable and efficient wet oxidation catalyst according to claim 6, is characterized in that, in described step 1, described soluble copper salt, zinc salt, aluminum salt, iron salt and lanthanum salt are meant When providing the corresponding metal elements, choose nitrate, sulfate, phosphate, acetate or chloride, the molar ratio of divalent copper to zinc ions n[Cu 2+ ]: n[Zn 2+ ]=(1～2 ): 1, the molar ratio of trivalent aluminum ions to the sum of other trivalent ions n[Al 3+ ]: n[Fe 3+ +La 3+ ]=(1.5～2.5): 1; the molar ratio of trivalent lanthanum to iron Ratio n[La 3+ ]:n[Fe 3+ ]=preferred (0.1-1):1. 8.根据权利要求6所述的一种稳定高效的湿式氧化催化剂的制备方法，其特征在于，所述步骤2中，提供氢氧根的碱选择氢氧化钠、氢氧化钾或者氨水；提供碳酸根的碳酸盐选择碳酸钠、碳酸钾或者碳酸铵；OH-与总金属离子摩尔比n[OH-]/(2n[M2+]+3n[M3+])=（1.6～1.8）：1，碱液中OH-的浓度选择0.01～3.00mol/L，碳酸盐溶液中CO3 2-的浓度选择0.01～3.00mol/L。8. the preparation method of a kind of stable and efficient wet oxidation catalyst according to claim 6, is characterized in that, in described step 2, the alkali that provides hydroxide is selected sodium hydroxide, potassium hydroxide or ammoniacal liquor; Provides carbonic acid The carbonate of the root is sodium carbonate, potassium carbonate or ammonium carbonate; the molar ratio of OH - to total metal ions n[OH - ]/(2n[M 2+ ]+3n[M 3+ ])=(1.6～1.8) : 1. The concentration of OH - in the lye is selected from 0.01 to 3.00 mol/L, and the concentration of CO 3 2- in the carbonate solution is selected from 0.01 to 3.00 mol/L. 9.根据权利要求6所述的一种稳定高效的湿式氧化催化剂的制备方法，其特征在于，在所述步骤3中，在滴加的同时进行搅拌200～500转/min，在滴加的同时得到沉淀物；在所述步骤4中，将步骤（3）得到的沉淀物于50～80℃条件下，搅拌晶化24～60h，搅拌速度100～300转/min；将得到的浆料反复过滤水洗至中性过程中，水溶液温度控制在20～60℃；烘干温度优选50～120℃，选择烘箱进行烘干，时间选择12～24h；在所述步骤5中优选500～700℃焙烧2～6h；在所述步骤6中，所述稀酸选用盐酸、硫酸或硝酸。9. The preparation method of a stable and efficient wet oxidation catalyst according to claim 6, characterized in that, in said step 3, stirring is carried out at 200 to 500 revolutions/min while dropping, and the At the same time, the precipitate is obtained; in the step 4, the precipitate obtained in the step (3) is stirred and crystallized at 50-80°C for 24-60h, and the stirring speed is 100-300 rpm; the obtained slurry In the process of repeated filtration and washing to neutrality, the temperature of the aqueous solution is controlled at 20-60°C; the drying temperature is preferably 50-120°C, and the oven is selected for drying, and the time is selected for 12-24h; in the step 5, it is preferably 500-700°C Roasting for 2-6 hours; in the step 6, the dilute acid is selected from hydrochloric acid, sulfuric acid or nitric acid. 10.如权利要求1－5之一所述的湿式氧化催化剂在湿式氧化催化处理苯酚废水或者糖精钠生产综合废水中的应用，所述糖精钠生产综合废水中，以重铬酸钾法测定的化学需氧量CODCr=17339.32mg/l，氨氮含量NH3-N=6439.22mg/l，pH=8.17，黑色。10. The application of the wet oxidation catalyst as claimed in any one of claims 1 to 5 in the wet oxidation catalytic treatment of phenol wastewater or the comprehensive wastewater produced by sodium saccharin, wherein in the comprehensive wastewater produced by sodium saccharin, the potassium dichromate method is used to determine the Chemical oxygen demand COD Cr =17339.32mg/l, ammonia nitrogen content NH 3 -N=6439.22mg/l, pH=8.17, black.
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CN104689821A (en) * 2015-03-20 2015-06-10 天津工业大学 A kind of preparation method of catalytic wet 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 element doped layered composite metal hydroxide 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 A kind of 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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