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CN101507917B - Solid base catalyst for synthesis of alkanolamide compounds and preparation method thereof - Google Patents

Solid base catalyst for synthesis of alkanolamide compounds and preparation method thereof Download PDF

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CN101507917B
CN101507917B CN2009100813345A CN200910081334A CN101507917B CN 101507917 B CN101507917 B CN 101507917B CN 2009100813345 A CN2009100813345 A CN 2009100813345A CN 200910081334 A CN200910081334 A CN 200910081334A CN 101507917 B CN101507917 B CN 101507917B
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magnesium
preparation
aluminum
hours
solid base
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CN101507917A (en
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张法智
李海艳
卢伟
徐赛龙
雷晓东
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to PCT/CN2009/072508 priority patent/WO2010111849A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding

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  • Materials Engineering (AREA)
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Abstract

The invention relates to a solid base catalyst for synthesizing alkanolamide compounds and a preparation method thereof, and belongs to the technical field of solid base catalyst. Magnalium hydrotalcite is taken as a precursor of the catalyst and used to prepare the solid base catalyst through calcination and rehydration, and the formulation of the magnalium hydrotalcite solid base catalyst is Mg1-xAlx(OH)2<x+>(OH-)x.mH2O. The alkanolamide compounds are reaction products, have good surface activity, are one of the most important varieties of non-ionic surface active agents, are important active monomers of a modern synthetic detergent, and are widely applied to detergents, foam stabilizers, thickeners, softening agents, anti-rust agents, antistatic agents, and the like.

Description

Solid base catalyst for synthesizing alkanolamide type compound and preparation method
Technical field
The invention belongs to the solid base catalyst technical field, particularly relate to a kind of synthetic alkanolamide compounds solid base catalyst of catalysis and preparation method of being used for.
Background technology
Biodiesel claims fatty acid methyl ester again, is a kind of novel biomass fuel, is the fossil fuel substitute of high-quality, and the performance that it is superior to the friendly and the recyclability thereof of environment, has obtained paying attention to.But, its expensive industrialization process that hinders biomass fuel.Chemical products by the production high added value increase the hot issue that profit is present research.With the natural acid is the grease derivative that raw material is made, and then synthetic alkanolamide compounds.Not only can turn waste into wealth, and the products obtained therefrom excellent performance, biological degradability is good, pollution is little, safety in utilization is good.
Alkanolamide is a kind of new non-ionic surfactants, faint yellow solid, nontoxic nonirritant.Have amido link in its molecule, do not dissociate in the aqueous solution, its hydrophilic group mainly is to be made of some hydroxyls.These characteristics have determined non-ionic surface active agent in some aspects than ionic surfactant superior performance just.Because be not ionic condition in solution, so good stability, be not subject to strong electrolyte and have influence, be not subject to the influence of soda acid yet, good with other type activating agent intermiscibility, can easier mix use,, in water and in the organic solvent, different solvabilities be arranged all along with the variation of structure, there be not cloud point with the difference of other surfactant with it, performances such as good thickening, steady bubble, foam enhancing, decontamination, calcium soap dispersion, emulsification are arranged, be widely used in washing agent, foam stabiliser, thickener, softening agent, antirust agent, antistatic additive etc.
Adopt fatty acid methyl ester and MEA to carry out amidation process in the traditional handicraft and produce the alkanolamide compounds.Reaction catalyst commonly used mainly is a liquid alkali catalyst, such as potash, sodium carbonate, potassium hydroxide, NaOH, sodium methoxide, caustic alcohol etc.Wherein catalyst selectivitys such as potash, sodium carbonate, potassium hydroxide, NaOH are relatively poor, are difficult for reclaiming, and severe corrosion equipment causes very big pollution to environment; Though and catalyst such as sodium methoxide, caustic alcohol make the product purity height, accessory substance is few, and its cost is higher and stable bad.Sodium chemistry character is very active, and transportation is preserved inconvenient; Sodium methoxide is to oxygen sensitive, and is inflammable, is dissolved in methyl alcohol, ethanol, meets water and resolves into methyl alcohol and NaOH, decomposes in the air more than 126.6 ℃.As everyone knows, compare with liquid alkali catalyst, solid base catalyst have not etching apparatus, environmental pollution little, be easy to advantages such as recovery.
Houghite is a class layered inorganic functional material, have the adjustable of laminate chemical composition, structural advantages such as interlayer ion kind and adjustable number, be widely used as catalyst, release agent, ion-exchange and adsorbent etc., can be used as the adsorbent of hydrophobic compound with the LDHs of Al and Li and straight-chain acid formation.[J.Phys.Chem., 1989,93:376-382]; Utilize selectivity and the different insertion ability of isomers of LDHs to come separating isomerism body [J.Am.Chem.Soc., 1984,106:5772-5779]; From waste water, adsorb trichlorophenol, 2,4,6,-T, trinitrophenol or the like [Appl.Clay Sci., 1995,10:131-145].The solid base catalyst that particularly with the hydrotalcite is the presoma preparation has demonstrated catalytic performance preferably in multiple catalytic reaction, people such as Zoltan with Mg/Al than being 3 MgAl-LDHs base catalyst [J.Mol.Catal.A:Chemical as intramolecular cyclization reaction and intermolecular cyclization reaction, 2000,161:149-155].People such as Rousselot are used for the Knoevenagel condensation reaction with Mg-Ga-Al-LDHs as base catalyst, have very high reactivity [Int.J.Inorg.Mater., 1999,1:165-174].People such as Reichle study different aldehyde ketone condensation reactions on MgAl (O) composite oxides, point out that this class base catalyst has the high life than the heterogeneous catalyst that other is used for the aldehyde ketone condensation reaction, high stability, high selectivity and stronger advantages such as reproducibility [J.Catal., 1980,63:295-306].And being applied to synthetic alkanolamide compounds as solid base catalyst, houghite also do not have pertinent literature or application report at present.
Summary of the invention
The object of the present invention is to provide a kind of solid base catalyst for synthesizing alkanolamide type compound and preparation method, have active height, applied widely, prepare characteristics such as simple, with low cost.
The preparation method of solid base catalyst provided by the invention at first utilizes common houghite preparation methods such as nucleation/crystallization isolation method and urea method to prepare particle diameter to be nanoscale or micron-sized magnesia-alumina hydrotalcite precursor, then with the roasting and rehydrated of precursor process, obtain this solid base catalyst, be used for the synthetic alkanolamide compounds of catalysis.
The synthetic alkanolamide compounds solid base catalyst of catalysis that is used for provided by the invention, its chemical general formula is:
[Mg 1-xAl x(OH) 2] x+(OH -) x·mH 2O
Wherein, the span of x is (0.2＜x＜0.33); M is the quantity (0.1＜m＜10) of the crystallization water.
The concrete preparation process of magnesia-alumina hydrotalcite solid base catalyst provided by the invention is as follows:
At first utilize common houghite preparation methods, prepare magnesia-alumina hydrotalcite precursor as nucleation/crystallization isolation method and urea method, with the roasting and rehydrated of precursor process, obtain this solid base catalyst, carrying out the XRD sign then, and be used for the synthetic alkanolamide compounds of catalysis, utilize the productive rate and the selectivity of liquid-phase chromatographic analysis reaction.
1. prepare magnesia-alumina hydrotalcite precursor, its chemical general formula is:
[Mg 1-xAl x(OH) 2] x+(CO 3 2-) x/2·nH 2O
Wherein, the span of x is (0.2＜x＜0.33); N is the quantity (0.1＜n＜10) of the crystallization water.
The mixing salt solution of A preparation divalence solubility magnesium salts and trivalent aluminum soluble salt, wherein bivalent metal ion concentration is 0.12-12mol/L, divalence, trivalent metal ion mol ratio are 2-4 times;
Described divalence magnesium soluble-salt is a kind of of nitrate, sulfate, acetate or chlorate, is preferably magnesium nitrate; Described trivalent aluminium soluble-salt is a kind of in nitrate, sulfate, acetate or the chlorate, is preferably aluminum nitrate;
The mixed-alkali solution of B preparation alkali and soluble inorganic salt, wherein the concentration of alkali is 0.096-9.6mol/L, the mol ratio of alkali and inorganic potassium (or sodium) salt is 2.4-3.2 times;
Described alkali is NaOH, and potassium hydroxide a kind of is preferably NaOH; Described inorganic salts are sodium carbonate, and a kind of in the potash is preferably sodium carbonate;
The urea liquid of C preparation 0.1-5mol/L;
When D nucleation crystallization isolation method prepares catalyst, it is characterized in that: with the mixing salt solution of steps A preparation and the mixed-alkali solution of step B preparation, be added in the colloid mill at 5-70 ℃ and drip, back-mixing number minute, move in the there-necked flask then, reacted 4-100 hour down at 10 ℃-100 ℃, get magnesia-alumina hydrotalcite precursor slurry;
When the E urea method prepares catalyst, it is characterized in that:, after evenly mixing, move in the band teflon-lined stainless steel cauldron the mixing salt solution of steps A preparation and the urea liquid of step C preparation, 10 ℃-110 ℃ reactions 4-100 hour, get magnesia-alumina hydrotalcite precursor slurry;
The slurries of F nucleation crystallization isolation method or the resulting magnesia-alumina hydrotalcite of urea method precursor for several times to pH to 7-8, behind dry 24h under 10-120 ℃, promptly get magnesia-alumina hydrotalcite precursor through centrifuge washing.
2. the preparation of Al-Mg composite metal oxide
The magnesia-alumina hydrotalcite precursor of nucleation crystallization isolation method or urea method preparation is put into the atmosphere kiln roasting of nitrogen protection; heating rate is 1-50 ℃/min; rise to 100-1000 ℃ by room temperature; roasting time is 1-50 hour; after roasting is finished; naturally be cooled to room temperature, product of roasting is an Al-Mg composite metal oxide.
3. the preparation of magnesia-alumina hydrotalcite solid base catalyst
With step 2 gained Al-Mg composite metal oxide, put into CO 2Carry out rehydrated when the hydration of gram Al-Mg composite metal oxide (every need remove the volume of CO2 water be 20-200ml) in the water; adopt nitrogen protection; the rehydrated time is 1-50 hour; reaction finishes; product is carried out quick pumping rate; in 10-80 ℃ of following vacuum drying chamber dry 5-48 hour, the material that obtains was the magnesia-alumina hydrotalcite solid base catalyst.
But the amidation process of solid base catalyst catalysis ester class of the present invention and monoethanolamine, its chemical equation is:
RCOOR 1+H 2NC 2H 4OH→RCONHC 2H 4OH+HOR 1，
Wherein, R is the alkane with different carbon atom numbers with R1, and the carbon atom number of R is 12～18, R 1The carbon atom number be 1～10.
The invention has the advantages that, product is the alkanolamide compounds, has the surface of good activity, being one of most important kind in the non-ionic surface active agent, is activated monomer important in the modern synthetic detergent, is widely used in washing agent, foam stabiliser, thickener, softening agent, antirust agent and antistatic additive etc.
Description of drawings
Fig. 1 is that the magnalium of nucleation/crystallization isolation method preparation is than being 2/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 2 is that the magnalium of nucleation/crystallization isolation method preparation is than being 3/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 3 is that the magnalium of nucleation/crystallization isolation method preparation is than being 4/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 4 for the magnalium of urea method preparation than being 2/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof.
The specific embodiment
Embodiment 1
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, concentration sodium hydroxide is 1.9 mol, and the concentration of sodium carbonate is 0.8 mol.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask 95 ℃ of following backflow crystallization 5 hours, use the deionized water centrifuge washing between the pH value scope 7-8 in the gained slurries, at 100 ℃ of dry 24h, grind then, place atmosphere furnace again in 500 ℃ of roastings 15 hours, put into carbon dioxide water hydration 8 hours again, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst, and its chemical composition is [Mg 2Al (OH) 6] (OH -) 2H 2O.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase efficient liquid phase chromatographic analysis, the conversion ratio 92.2% of methyl stearate are carried out in sampling, the selectivity of stearyl monoethanolamine is 77.7%, and productive rate is 71.6%.
Embodiment 2
In 100ml polytetrafluoroethylcontainer container or glass container, with Mg (NO 3) 2.6H 2O and Al (NO 3) 3.9H 2O is dissolved in the 75ml deionized water by 2: 1 mol ratios, is mixed with the solution that total concentration is 0.3M.Ratio in urea/NO3-=4.0 adds urea and makes it dissolving, and airtight container was in 90 ℃ of following isothermal reactions 3 days, after treating the solution cooling, filter and wash the white precipitate of gained, dry 24h under 100 ℃ promptly gets magnalium carbonate hydrotalcite, grind, place atmosphere furnace in 500 ℃ of roastings 15 hours again, put into carbon dioxide water hydration 8 hours again, 40 ℃ of following vacuum drying are 24 hours then, promptly make the magnesia-alumina hydrotalcite solid base catalyst, its chemical composition is [Mg 2Al (OH) 6] (OH -) 2H 2O.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 89.4% of methyl stearate, the selectivity of stearyl monoethanolamine are 98.2%, and productive rate is 87.8%.
Embodiment 3
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 1.2mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 2.56mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.8mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 96.3% of methyl stearate, the selectivity of stearyl monoethanolamine are 95.4%, and productive rate is 91.9%.
Embodiment 4
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.2mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 1.6mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.4mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g.MEA 3.36g, catalyst 0.915g puts into the 100ml there-necked flask, and reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 95.0% of methyl stearate, the selectivity of stearyl monoethanolamine is 66.2%, productive rate is 62.9%.
Embodiment 5
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 1.9mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.8mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 87.1% of methyl stearate, the selectivity of stearyl monoethanolamine are 67.1%, and productive rate is 58.4%.

Claims (1)

1.一种烷醇酰胺合成用固体碱催化剂的制备方法，其特征在于：包括以下步骤：1. a kind of preparation method of alkanolamide solid base catalyst for synthesis, is characterized in that: comprise the following steps: (1)制备镁铝类水滑石前体；(1) preparing magnesium aluminum hydrotalcite precursor; (2)镁铝复合金属氧化物的制备(2) Preparation of magnesium-aluminum composite metal oxide 将成核晶化隔离法或尿素法制备的镁铝类水滑石前体放入氮气保护的气氛炉中焙烧，升温速率为1-50℃/min，由室温升至100-1000℃，焙烧时间为1-50小时，焙烧完成后，自然降温至室温，焙烧产物即镁铝复合金属氧化物；Put the magnesium-aluminum hydrotalcite precursor prepared by the nucleation crystallization isolation method or the urea method into an atmosphere furnace protected by nitrogen and roast at a heating rate of 1-50°C/min, from room temperature to 100-1000°C, and the roasting time 1-50 hours. After the roasting is completed, the temperature is naturally lowered to room temperature, and the roasted product is magnesium-aluminum composite metal oxide; (3)镁铝类水滑石固体碱催化剂的制备(3) Preparation of magnesium-aluminum hydrotalcite solid base catalyst 将步骤(2)所得镁铝复合金属氧化物，放入去CO2水中进行再水合，采用氮气保护，再水合时间为1-50个小时，反应完毕，对产物进行快速抽滤，于10-80℃下真空干燥箱中干燥5-48小时，得到的物质即镁铝类水滑石固体碱催化剂；再水合时，每克镁铝复合金属氧化物需去CO2水的体积为20-200ml；Put the magnesium-aluminum composite metal oxide obtained in step (2) into deCO2 water for rehydration, use nitrogen protection, and the rehydration time is 1-50 hours. After the reaction is completed, the product is subjected to rapid suction filtration. Dry in a vacuum drying oven at 80°C for 5-48 hours, and the obtained material is a solid alkali catalyst of magnesium-aluminum hydrotalcite; when rehydrating, the volume of CO 2 water required per gram of magnesium-aluminum composite metal oxide is 20-200ml; 所述的制备镁铝类水滑石前体的制备步骤为：The preparation steps of the described preparation magnesium aluminum hydrotalcite precursor are: A配制二价可溶性镁盐和三价可溶性铝盐的混合盐溶液，其中二价金属离子浓度为0.12-12mol/L，二价，三价金属离子摩尔比为2-4；A prepares the mixed salt solution of divalent soluble magnesium salt and trivalent soluble aluminum salt, wherein the concentration of divalent metal ions is 0.12-12mol/L, and the molar ratio of divalent and trivalent metal ions is 2-4; 所述的二价镁可溶性盐为硝酸盐、硫酸盐、醋酸盐或氯化盐的一种；The soluble salt of divalent magnesium is a kind of nitrate, sulfate, acetate or chloride; 所述的三价铝可溶性盐为硝酸盐、硫酸盐、醋酸盐或氯化盐中的一种；The soluble salt of trivalent aluminum is one of nitrate, sulfate, acetate or chloride; B配制碱和可溶性无机盐的混合碱性溶液，其中碱的浓度为0.096-9.6mol/L，碱与无机盐的摩尔比为2.4-3.2；B prepares the mixed alkaline solution of alkali and soluble inorganic salt, wherein the concentration of alkali is 0.096-9.6mol/L, and the mol ratio of alkali and inorganic salt is 2.4-3.2; 所述的碱为氢氧化钠，氢氧化钾的一种；所述的无机盐为碳酸钠，碳酸钾中的一种；Described alkali is sodium hydroxide, a kind of potassium hydroxide; Described inorganic salt is sodium carbonate, a kind of in potassium carbonate; C配制0.1-5mol/L的尿素溶液；C prepares the urea solution of 0.1-5mol/L; D成核晶化隔离法制备催化剂时，将步骤A配制的混合盐溶液与步骤B配制的混合碱性溶液，在5-70℃并流滴加到胶体磨中，返混数分钟，然后移入三口瓶中，在10℃-100℃下反应4-100小时，得镁铝类水滑石前体的浆液；D. When preparing the catalyst by nucleation, crystallization and isolation, the mixed salt solution prepared in step A and the mixed alkaline solution prepared in step B are added dropwise to the colloid mill at 5-70°C, back mixed for several minutes, and then transferred into In a three-neck flask, react at 10°C-100°C for 4-100 hours to obtain a slurry of magnesium-aluminum hydrotalcite precursor; 尿素法制备催化剂时，将步骤A配制的混合盐溶液与步骤C配制的尿素溶液，均匀混合后，移入带聚四氟乙烯内衬的不锈钢反应釜中，在10℃-110℃反应4-100小时，得镁铝类水滑石前体的浆液；When the catalyst is prepared by the urea method, mix the mixed salt solution prepared in step A and the urea solution prepared in step C evenly, and then move it into a stainless steel reaction kettle with a polytetrafluoroethylene liner, and react at 10°C-110°C for 4-100 hours, to obtain the slurry of magnesium aluminum hydrotalcite precursor; E成核晶化隔离法或尿素法所得到的镁铝类水滑石前体的浆液，经离心洗涤数次至pH至7-8，在10-120℃下干燥24h后，得镁铝类水滑石前体；E. The slurry of the magnesium-aluminum hydrotalcite precursor obtained by the nucleation crystallization isolation method or the urea method is centrifuged and washed several times until the pH reaches 7-8, and after drying at 10-120°C for 24 hours, the magnesium-aluminum hydrotalcite precursor is obtained. Talc precursor; 所述的镁铝类水滑石前体的化学通式为：[Mg1-xAlx(OH)2]x+(CO3 2-)x/2·nH2O，其中，x的取值范围为0.2＜x＜0.33；n为结晶水的数量，0.1＜n＜10。The general chemical formula of the magnesium-aluminum hydrotalcite precursor is: [Mg 1-x Al x (OH) 2 ] x+ (CO 3 2- ) x/2 nH 2 O, wherein the value range of x 0.2<x<0.33; n is the amount of crystal water, 0.1<n<10.
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CN116081671B (en) * 2023-01-17 2024-09-17 广东华特气体股份有限公司 A porous double metal hydroxide and its preparation method and application
CN116726868B (en) * 2023-07-28 2025-07-25 新特能源股份有限公司 Hydrotalcite adsorbent, preparation method thereof and application of hydrotalcite adsorbent in chlorosilane impurity removal
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CN117563586A (en) * 2023-11-24 2024-02-20 山东长泽新材料科技有限公司 A solid-state catalyst and method for efficiently synthesizing methacrolein

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467177A (en) * 2002-06-24 2004-01-14 北京化工大学 Method for assembling anion type supramolecular intercalation structure material
CN101284679A (en) * 2008-05-05 2008-10-15 哈尔滨工程大学 Preparation method of anionic pillared hydrotalcite

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2729137A1 (en) * 1995-01-06 1996-07-12 Atochem Elf Sa SELECTIVE ALDOLIZATION OF ACETONE IN DIACETONEALCOOL BY A SOLID BASIC CATALYST
CN1288078A (en) * 1999-09-14 2001-03-21 北京化工大学 Method for synthesis of well-dispersed and super fine anion laminated material
CN100496726C (en) * 2005-11-03 2009-06-10 北京化工大学 Hydrotalcite like structural catalyst with mica as matrix and preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467177A (en) * 2002-06-24 2004-01-14 北京化工大学 Method for assembling anion type supramolecular intercalation structure material
CN101284679A (en) * 2008-05-05 2008-10-15 哈尔滨工程大学 Preparation method of anionic pillared hydrotalcite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李蕾.类水滑石材料新制备方法及结构与性能的理论研究.北京化工大学博士学位论文.2005,第51页第4.4.1节第1-11行. *

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