CN105032483B - Synthesize catalyst of N methyl alcamine compounds and preparation method thereof, application - Google Patents
Synthesize catalyst of N methyl alcamine compounds and preparation method thereof, application Download PDFInfo
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Abstract
The invention discloses a kind of catalyst of synthesis N methyl alcamine compounds, it is characterised in that the catalyst is made through the mesopore molecular sieves of source metal solution modification MCM 41, and the ratio between amount of material of metallic element and element silicon is 1 in catalyst：0.025 ~ 1, the metallic element is titanium, iron or zirconium.The specific surface area of catalyst of the present invention is big, service life length and with abundant acid active sites, to amine（Fatty amine and aromatic amine）N methyl hydramine is synthesized with epoxide liquid phase method has extraordinary catalytic performance, and the high conversion rate of amine, the selectivity to N methyl hydramine is good.It is carrier with mesoporous MCM 41 the invention also discloses a kind of preparation method of the catalyst of synthesis N methyl alcamine compounds, be modified source solution using the source metal containing metallic element is modified to mesoporous MCM 41.The preparation method of the present invention, step is simple, and course of reaction is stably and controllable, workable.
Description
Technical field
The present invention relates to a kind of catalyst, a kind of catalyst more particularly, to synthesis N- methyl alcamine compounds and its
Preparation method, application.
Background technology
N- methyl alcamine compounds are important fine chemical products in one, are widely used in chemical fertilizer factory, synthesis ammonia
Factory, oil plant, the desulfurization and decarburization agent of pharmaceutical factory, produce medicine intermediate, paint solvent, manufacture non-ionic detergent, emulsification
Agent and activator etc..It is used to prepare polyurethane foam, and coating, paint, ink apply also for the conjunction of water soluble paint resin
Into, polyurethane coating water process, gas treatment ion exchange resin paper making additive and leather, textile auxiliary, particularly in oil field
In terms of gas and coal gas, the desulfurizing and purifying of natural gas, N-methyl alcamine compound has irreplaceable status, and this is in the energy
It is significant in terms of exploitation, environmental protection.
The traditional production technology of N- methyl alcamine compounds is that the solution reaction of halohydrin and fatty amine or aromatic amine is given birth to
Into N- methyl ethanol amine compounds, but reaction yield is relatively low, reaction time length, urgent need to resolve the problems such as side reaction is more.From
These problems directly affect purification, cost of equipment and the energy consumption cost of reaction product from the point of view of technological angle, reaction heating and most
Rectifying product afterwards will need to consume substantial amounts of heat energy.Epoxyethane method synthesis N- methyl alcamine compounds are by epoxy second
The method that the solution reaction of alkane or epoxide and fatty amine or aromatic amine generates N- methyl ethanol amine compounds, this method
With the features such as reaction raw materials are with low cost, reaction is simple, byproduct of reaction is less, therefore, epoxyethane method synthesizes N- methyl
Ethanolamines product has good economic advantages and environment-friendly advantage.
For example, European patent EP-A-70978 discloses temperature at 150 DEG C or so, sodium borohydride is used as catalyst ring
Oxidative ethane method synthesizes N- methyl amine alcohols, and its alkalescence can effectively reduce the generation of the quarternary ammonium salt compound in N- methyl hydramine, energy
The color characteristics and quality of product are improved well, but product separation is complicated, catalyst recycling rate of waterused is low.
Japan Patent JP-A-01/160 947 is disclosed under water catalytic action, while Ru/C catalyst is added, can be effective
Reduction epoxide quaternary ammonium compound generation and the generation of autohemagglutination.The product excitation obtained after distillation is very
Height, but water is easy to epoxide as nucleopilic reagent occurs side reaction and catalyst costly, prepares cost high.
The catalyst of the prior arts such as above-mentioned sodium borohydride, Ru/C catalyst, which exists, prepares cost height, and side reaction is more, weight
Multiple utilization rate is low, causes the defects such as product separation, purification complexity.Therefore, find and N- methyl is catalyzed and synthesized under condition of no solvent
The catalyst of alcohol amine compound has great importance.
The content of the invention
The present invention be in order to which the catalyst preparation cost for solving the synthesis N- methyl alcamine compounds of prior art is high, it is secondary
Reaction is more, and recycling rate of waterused is low, and the problem of causing product separation, purification complexity, service life was long there is provided a kind of cost is low,
Catalytic performance is good, the high conversion rate of amine, to the catalyst of N- methyl hydramine selectively good synthesis N- methyl alcamine compounds.
Present invention also offers a kind of method for preparing catalyst of synthesis N- methyl alcamine compounds, step is simple, instead
Answer process stabilization controllable, it is workable.
To achieve these goals, the present invention uses following technical scheme：
A kind of catalyst of synthesis N- methyl alcamine compounds, the catalyst is situated between through source metal solution modification MCM-41
Porous molecular sieve is made, and the ratio between amount of material of metallic element and element silicon is 1 in catalyst：0.025 ~ 1, the metallic element is
Titanium, iron or zirconium.The catalyst of the present invention is used for amine（Fatty amine or aromatic amine）N- first is synthesized by liquid phase method with epoxide
Base alcamine compound, introducing metal heteroatom, surface has abundant B sour and L acid activities position simultaneously, and still has MCM-
41 hexagonal hole road structure and higher specific surface area, to amine（Fatty amine and aromatic amine）N- is synthesized with epoxide liquid phase method
Methyl hydramine has extraordinary catalytic performance, and the high conversion rate of amine, the selectivity of N- methyl hydramine is good, and reaction condition is relative
Gently, it is easy to industry's enlarging production.
A kind of method for preparing catalyst of synthesis N- methyl alcamine compounds, comprises the following steps：
（1）Using cetyl trimethylammonium bromide as template, using cetyl trimethylammonium bromide as template, by ten
Six alkyl trimethyl ammonium bromides are dissolved in the alkaline solution that pH is 9 ~ 10, add tetraethyl orthosilicate, stir 5 ~ 10 h, molten with sulfuric acid
After liquid regulation pH to 8 ~ 13, obtain white precipitate solution, wherein the material of cetyl trimethylammonium bromide and tetraethyl orthosilicate
The ratio between amount is 0.2 ~ 0.4：1.
（2）The ratio between amount of material by metallic element and element silicon is 1：0.025 ~ 1, by the source metal containing metallic element
Modified solution in being added dropwise in white precipitate solution dropwise in 15min, and it is 20 ~ 50 DEG C to control temperature, and it is molten that 1 ~ 10h of stirring obtains gel
Liquid, wherein the source metal modified solution is [(CH3(CH2)2O]4Ti solution, ZrOCl2·8H2O solution or Fe (NO3)3·9H2O
Solution.
（3）Gel solution is transferred in stainless steel hydrothermal reaction kettle, in 80 ~ 120 DEG C of 24 ~ 48h of crystallization, deionized water is used
Washing, filtering, dry laggard row order ladder roasting at a temperature of 60 ~ 100 DEG C by filtrate and produce for synthesizing N- methyl alcamines
The catalyst of compound.
Preferably, the alkaline solution is NaOH solution or KOH solution.
Preferably, step（2）In, adjust pH to 9 ~ 10, with sulfuric acid solution
Preferably, the concentration of the sulfuric acid solution is 0.1 ~ 1.0 mol/L.
Preferably, step（2）In, the source metal modifier concentration is 1.0 ~ 2.0 mol/L.
Preferably, step（3）In, what ladder was calcined concretely comprises the following steps：It is warming up to 3 ~ 15 DEG C/min programming rate
After 300 ~ 700 DEG C, 3 ~ 8h of constant temperature calcining.3 ~ 15 DEG C of heating rate of control is to avoid catalyst from being burst because heating up too fast；And with
The rise catalyst activity increase of sintering temperature, sintering temperature is too high, can cause catalyst activity reduction, therefore the present invention
Middle control sintering temperature is at 300 ~ 700 DEG C, in the active highest of the temperature range, catalyst activity highest；In addition, roasting time pair
Catalyst activity influence is very big, and roasting time is long, and the activated centre of catalyst surface is destroyed, and roasting time is too short, no
Catalytic center can be made to activate completely, therefore the present invention controls roasting time to be 3 ~ 8h.
Preferably, programming rate is 5 ~ 8 DEG C/min, 5 ~ 6h of roasting time.
A kind of catalyst of synthesis N- methyl alcamine compounds answering when catalyzing and synthesizing N- methyl alcamine compounds
With.
Therefore, the present invention has the advantages that：
（1）The specific surface area of catalyst of the present invention is big, service life length and with abundant acid active sites, to amine（Fat
Fat amine and aromatic amine）N- methyl hydramine is synthesized with epoxide liquid phase method has extraordinary catalytic performance, the conversion ratio of amine
Height, the selectivity to N- methyl hydramine is good；
（2）The preparation method of the present invention, step is simple, and course of reaction is stably and controllable, workable.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
（1）Using cetyl trimethylammonium bromide as template, it is 9 that cetyl trimethylammonium bromide is dissolved in into pH
In NaOH solution, tetraethyl orthosilicate is added, 5h is stirred, is adjusted with concentration for 0.1 mol/L sulfuric acid solution after pH to 8, obtains white
The ratio between amount of material of color precipitation solution, wherein cetyl trimethylammonium bromide and tetraethyl orthosilicate is 0.2：1.
（2）The ratio between amount of material by metallic element and element silicon is 1：0.025, the source metal containing metallic element is changed
Property solution in being added dropwise to dropwise in 15min in white precipitate solution, control temperature be 20 DEG C, stirring 1h obtain gel solution, wherein
The source metal modified solution is concentration 1.0mol/L [(CH3(CH2)2O]4Ti solution.
（3）Gel solution is transferred in stainless steel hydrothermal reaction kettle, in 80 DEG C of crystallization 24h, is washed with deionized, mistake
Filter, after filtrate is dried at a temperature of 60 DEG C, is warming up to after 300 DEG C, constant temperature calcining 3h is produced with 3 DEG C/min programming rate
Catalyst for synthesizing N- methyl alcamine compounds.
Embodiment 2
The present embodiment and the difference of embodiment 1 are：Step（1）In, with the sulfuric acid solution that concentration is 0.1 mol/L
Adjust pH to 9；Step（3）In, 300 DEG C are warming up to 5 DEG C/min programming rate, other are identical, therefore do not repeat herein.
Embodiment 3
（1）Using cetyl trimethylammonium bromide as template, it is 9.5 that cetyl trimethylammonium bromide is dissolved in into pH
In NaOH solution, tetraethyl orthosilicate is added, 8h is stirred, is adjusted after pH to 8.5, obtained for 0.5 mol/L sulfuric acid solution with concentration
The ratio between amount of material of white precipitate solution, wherein cetyl trimethylammonium bromide and tetraethyl orthosilicate is 0.3：1.
（2）The ratio between amount of material by metallic element and element silicon is 1：0.03, the source metal containing metallic element is changed
Property solution in being added dropwise to dropwise in 15min in white precipitate solution, control temperature be 25 DEG C, stirring 5h obtain gel solution, wherein
The source metal modified solution is concentration 1.5mol/L ZrOCl2·8H2O solution.
（3）Gel solution is transferred in stainless steel hydrothermal reaction kettle, in 100 DEG C of crystallization 28h, be washed with deionized,
Filtering, after filtrate is dried at a temperature of 80 DEG C, is warming up to after 500 DEG C, constant temperature calcining 6h is with 4 DEG C/min programming rate
The catalyst for synthesizing N- methyl alcamine compounds must be used for.
Embodiment 4
The present embodiment and the difference of embodiment 3 are：Step（1）In, with the sulfuric acid solution that concentration is 0.5 mol/L
Adjust pH to 9.5；Step（3）In, 500 DEG C are warming up to 6 DEG C/min programming rate, other are identical, therefore do not go to live in the household of one's in-laws on getting married herein
State.
Embodiment 5
（1）Using cetyl trimethylammonium bromide as template, it is 10 that cetyl trimethylammonium bromide is dissolved in into pH
In KOH solution, tetraethyl orthosilicate is added, 10 h are stirred, is adjusted after pH to 13, obtained for 1.0 mol/L sulfuric acid solution with concentration
The ratio between amount of material of white precipitate solution, wherein cetyl trimethylammonium bromide and tetraethyl orthosilicate is 0.4：1.
（2）The ratio between amount of material by metallic element and element silicon is 1：1, the source metal containing metallic element is modified molten
Liquid in being added dropwise in white precipitate solution dropwise in 15min, and it is 50 DEG C to control temperature, and stirring 10h obtains gel solution, wherein described
Source metal modified solution is the mol/L of concentration 2.0 Fe (NO3)3·9H2O solution.
（3）Gel solution is transferred in stainless steel hydrothermal reaction kettle, in 120 DEG C of crystallization 48h, be washed with deionized,
Filtering, after filtrate is dried at a temperature of 100 DEG C, is warming up to after 700 DEG C, constant temperature calcining 8h with 15 DEG C/min programming rate
Produce the catalyst for synthesizing N- methyl alcamine compounds.
Embodiment 6
The present embodiment and the difference of embodiment 5 are：Step（1）In, with the sulfuric acid solution that concentration is 1.0 mol/L
Adjust pH to 10；Step（3）In, 700 DEG C are warming up to 8 DEG C/min programming rate, other are identical, therefore do not go to live in the household of one's in-laws on getting married herein
State.
The present invention catalyst synthesize N- methyl alcamine compounds when concrete application method be：By catalyst pressure
Piece, excessively grinding, 20 ~ 60 mesh sieves, press amine and epoxide using peristaltic meatering pump the amount ratio 1 ~ 5.0 of material：1（It is preferred that
3.5：1）Autoclave is pumped into, catalyst amount is 0.2 ~ 1.2 g（It is preferred that 0.8 ~ 1.0 g）, in 60 ~ 190 DEG C of reaction temperature
（It is preferred that 100 ~ 145 DEG C）, the MPa of reaction pressure 1 ~ 3.5（It is preferred that 1.5 ~ 2.2 MPa）Under conditions of reacted.
After used catalyst is washed with methanol, it is put into air dry oven and dries, then activated removing solvent point
After son, it just can re-start and use.
The catalyst of the present invention has meso-hole structure through XRD detections, and specific surface area is detected as through nitrogen adsorption desorption
253.65 ~869.03 m2/ g, for amine（Fatty amine and aromatic amine）N- methyl hydramine is synthesized with epoxide liquid phase method
During class compound, the conversion ratio of epoxide up to more than 96%, N- methyl hydramine selectivity up to more than 86%, it follows that
The catalyst of the present invention is to amine（Fatty amine and aromatic amine）N- methyl alcamine compound tool is synthesized with epoxide liquid phase method
There is extraordinary catalytic performance, the high conversion rate of amine, the selectivity of N- methyl hydramine is good, and reaction condition is relatively mild, be adapted to
For industry's enlarging production.
Embodiment described above is a kind of preferably scheme of the present invention, not makees any formal to the present invention
Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (6)
1. a kind of catalyst of synthesis N- methyl alcamine compounds, it is characterised in that the catalyst changes through source metal solution
Property MCM-41 mesopore molecular sieves be made, the ratio between amount of material of metallic element and element silicon is 1 in catalyst：0.025 ~ 1, it is described
Metallic element is titanium, iron or zirconium, and the catalyst of described synthesis N- methyl alcamine compounds is made by the following method：
（1）Using cetyl trimethylammonium bromide as template, cetyl trimethylammonium bromide is dissolved in the alkali that pH is 9 ~ 10
Property solution in, add tetraethyl orthosilicate, stir 5 ~ 10 h, with sulfuric acid solution adjust pH to 8 ~ 13 after, obtain white precipitate solution, its
The ratio between amount of material of middle cetyl trimethylammonium bromide and tetraethyl orthosilicate is 0.2 ~ 0.4：1；
（2）The ratio between amount of material by metallic element and element silicon is 1：0.025 ~ 1, by the concentration containing metallic element be 1.0 ~
2.0 mol/L source metal modified solution in being added dropwise in white precipitate solution dropwise in 15min, and it is 20 ~ 50 DEG C to control temperature,
1 ~ 10h of stirring obtains gel solution, wherein the source metal modified solution is [(CH3(CH2)2O]4Ti solution, ZrOCl2·8H2O is molten
Liquid or Fe (NO3)3·9H2O solution；
（3）Gel solution is transferred in stainless steel hydrothermal reaction kettle, in 80 ~ 120 DEG C of 24 ~ 48h of crystallization, is washed with deionized water
Wash, filter, filtrate is dried into laggard row order ladder roasting at a temperature of 60 ~ 100 DEG C produces for synthesizing N- methyl alcamines
The catalyst of compound, what ladder was calcined concretely comprises the following steps：It is warming up to 3 ~ 15 DEG C/min programming rate after 300 ~ 700 DEG C, it is permanent
3 ~ 8h of temperature roasting.
2. a kind of catalyst of synthesis N- methyl alcamine compounds according to claim 1, it is characterised in that the alkali
Property solution be NaOH solution or KOH solution.
3. a kind of catalyst of synthesis N- methyl alcamine compounds according to claim 1, it is characterised in that step
（2）In, adjust pH to 9 ~ 10 with sulfuric acid solution.
4. a kind of catalyst of synthesis N- methyl alcamine compounds according to claim 1 or 3, it is characterised in that institute
The concentration for stating sulfuric acid solution is 0.1 ~ 1.0 mol/L.
5. a kind of catalyst of synthesis N- methyl alcamine compounds according to claim 1, it is characterised in that step
（3）In, programming rate is 5 ~ 8 DEG C/min, 5 ~ 6h of roasting time.
6. a kind of catalyst of synthesis N- methyl alcamine compounds as claimed in claim 1 is catalyzing and synthesizing N- methyl hydramine
Application during class compound.
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