CN105032473A - Method for preparing formaldehydedibutylacetal by adopting sulfuric acid modified process nano-grade HZSM-5 catalyst - Google Patents
Method for preparing formaldehydedibutylacetal by adopting sulfuric acid modified process nano-grade HZSM-5 catalyst Download PDFInfo
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- CN105032473A CN105032473A CN201510365206.9A CN201510365206A CN105032473A CN 105032473 A CN105032473 A CN 105032473A CN 201510365206 A CN201510365206 A CN 201510365206A CN 105032473 A CN105032473 A CN 105032473A
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Abstract
The invention discloses a method for preparing formaldehydedibutylacetal by adopting a sulfuric acid modified process nano-grade HZSM-5 catalyst, wherein the raw materials comprises formaldehyde and butyl alcohol, octyl alcohol or RO (CH2CH2O) nH, R=C1-C4 alkyl group, n=1,2, formaldehydedibutylacetal is synthesized under the effect of the sulfuric acid modified process nano-grade HZSM-5 catalyst, a kettle-type reaction is carried out, the reaction temperature is 65 to 260 DEG C, water generated during reaction is continuously collected and separated until the reaction is finished, and a catalyst is separated from residue, namely a crude product of the formaldehydedibutylacetal is obtained. The sulfuric acid modified process nano-grade HZSM-5 catalyst is recycled; the molar ratio of the formaldehyde to the alcohol is 1:2.5 to 6.0; the use amount of the sulfuric acid modified process nano-grade HZSM-5 catalyst accounts for 0.4 to 5.0 percent of the total mass of a reactant. According to the method, under the condition of improving the productivity, a proper solid acid catalyst with high activity, good electivity, easy recovery and long service life is developed, the environment pollution is reduced, and the catalyst is suitable for mass production in industry field.
Description
Technical field
The invention belongs to field of chemical technology, be specifically related to a kind of method adopting sulfuric acid modified process nanoscale HZSM-5 catalyst preparing dialkoxy methane.
Background technology
Dibutoxy methane has another name called butoxy-methane, formaldehyde contracts two butanols, 1,1'-[di-2-ethylhexylphosphine oxide (oxygen)] two butane, two-n-butoxy ethane.Be clear colorless liquid under normal temperature, be slightly soluble in water; Fusing point-58.1 DEG C; Boiling point is 180.5 DEG C; Flash-point is 62 DEG C; Vapour pressure (20 DEG C): <20hPa; At 20 DEG C, relative density is 0.835g/mL; At 25 DEG C, viscosity is 1.083mm
2/ s; Heat decomposition temperature is 300 DEG C.Be clear colorless liquid under propylal normal temperature, fusing point 25.4 DEG C; Boiling point is 143.7 DEG C; Relative density is 0.8 ± 0.1g/cm
3; Vapour pressure (25 DEG C): 6.6 ± 0.3mmHg.Butyl formal has another name called formaldehyde diglycol ethylene butyl ether.Be clear pale yellow look liquid under normal temperature, water insoluble.
Dialkoxy methane product has extensive use, is mainly used as industrial solvent and reaction reagent.As organic synthesis solvent, for alkylation, acyl group, organolithium reaction and Grignard reaction and oxidation reaction; As the auxiliary agent of polymer, as the end-capping reagent of copolymerized methanal, the yield of copolymerized methanal can be improved; As industrial solvent, be the fine solvent of casting arbor material, adhesive, coating, ink, effectively can also reduce the discharge of particle in diesel fuel combustion process, the Cetane number of diesel oil can be improved.As reaction reagent, as ethoxymethyl reagent, very useful to the ethoxymethylization of alcohol, phenol and amine; As the equivalent of formaldehyde, replace formalin, make reaction safer, not moisture and easily process; A kind of well carbonylation substrate, with carbon monoxide, ketenes effect obtained 2-ethyoxyl acetate and 3-ethoxy-c acid esters respectively.
The main synthetic method of dialkoxy methane has: carrene method, dimethyl sulfoxide method, chloramphenicol by-product method, acid catalyzed process etc.Carrene method is the method for synthesis dialkoxy methane comparatively early.This method adopts carrene and sodium alkoxide to synthesize dialkoxy methane under acid catalysis.Because reaction requires strict, not only need sodium alkoxide to make reagent, also require waterless operation, it is low to add yield, thus limits its development; Dimethyl sulfoxide method utilizes methyl-sulfoxide unstable to acid, and heat resolve generates formaldehyde, and formaldehyde and alcohol carry out addition reaction and obtains dialkoxy methane, but because the consumption of methyl-sulfoxide is many and output is not high, be thus unfavorable for large-scale production; Chloramphenicol by-product method utilizes in the production process of chloramphenicol, has and generate the methenamine solution of nitro-2-bromoacetophenone, add the alcoholic solution of hydrochloric acid in this solution, obtain byproduct dialkoxy methane.Many chloramphenicol producers utilize this method to obtain dialkoxy methane; Acid catalyzed process take strong acid as catalyst, and alcohol and formaldehyde prepare dialkoxy methane by condensation reaction, and this method is simple to operate, and reaction speed is fast, is the method that current researcher pays close attention to most.Other also just like: alkyl bromination magnesium and formaldehyde react at low temperatures prepares dialkoxy methane.Consider the factors such as the cost of raw material, operating condition and yield, it is preferable that acid catalyzed process.
The acid catalyzed process of current comparative maturity, synthesis technique substantially adopt interval, continuously and catalytic distillation three kinds of modes of operation carry out.Traditional aldolisation uses inorganic acid (as sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid etc.) and lewis acid (as ferric trichloride, alchlor etc.) catalyst, all there is good catalytic activity, but there is difficult separation and recycling, to the shortcoming such as equipment corrosion is serious.People develop solid acid catalyst for this reason, thus establish a kind of aldolisation rectifying new technology for suitability for industrialized production.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of easy and simple to handle, catalyst activity is high, equipment corrosion is little, can be recycled, the dialkoxy methane preparation method that production process is clean.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A kind of method adopting sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane: raw material is aldehyde, alcohol and water entrainer, dialkoxy methane is synthesized under sulfuric acid modified nanoscale HZSM-5 catalyst action, reaction temperature is 70 ~ 260 DEG C, the water that continuous collection, separating reaction produce, until reaction terminates, still liquid is isolated catalyst and is namely obtained dialkoxy methane crude product; Wherein, the molecular sieve catalyst recycling use of dialkoxy methane is synthesized; Formaldehyde and alcohol mol ratio are 1:2.5 ~ 6.0; Sulfuric acid modified nanoscale HZSM-5 catalyst amount is 0.5 ~ 5.0% of reactant gross mass.Alcohol comprises: alcohol is propyl alcohol, butanols, octanol or RO (CH
2cH
2o) nH, R=C
1-C
4alkyl, n=1,2.
Dialkoxy methane product comprises: propylal, dibutoxy methane, two octyl methane, formaldehyde condensed ethandiol ether, the third butoxy-methane etc.
Sulfuric acid modified nanoscale HZSM-5 catalyst is prepared by following methods: by nanoscale HZSM-5 at 550 DEG C of activation 3h, then flooding 5 ~ 15 times of mass concentrations is 1.0 ~ 6.0mol/L sulfuric acid solution; Stir under 100 ~ 500r/min, normal temperature backflow 3h, baking oven low temperature drying, 300 ~ 550 DEG C of roasting 1 ~ 5h; Cooling both obtained catalyst.
Preferred: the mol ratio of formaldehyde and alcohol is 1:2.5 ~ 1:6.0, and catalyst amount is 0.5 ~ 5.0% of reactant gross mass.More preferably: the mol ratio of formaldehyde and alcohol is 1:3 ~ 1:5.0, and catalyst amount is 1.0 ~ 4.0% of reactant gross mass.
Water entrainer is toluene, cyclohexane, consumption be aldehyde, alcohol quality sum 5 ~ 30%.
When the alcohol of raw material is butanols, in reaction raw materials, additionally do not add water entrainer.
Described is commercial Nano-sized HZSM-5 (from Nanjing Huang Ma Chemical Co., Ltd.), crystal grain 200 ~ 500nm.
What the present invention obtained is the thick product of refining dialkoxy methane.The thick product of dialkoxy methane is mainly containing acetal, alcohol, water entrainer, and this thick product, by refining, can remove alcohol wherein, water entrainer, the dialkoxy methane that obtained purity is greater than 98.0%.
The sulfuric acid modified nanoscale HZSM-5 catalyst of the invention, be the catalyst system of the commercial nanoscale HZSM-5 of sour modification, such catalyst preparation process is simple.
In the preparation method of above-mentioned dialkoxy methane, under normal pressure, controlling reaction temperature is 70 ~ 260 DEG C, the water that constantly collection, separating reaction produce, until reaction terminates, catalyst separation Posterior circle uses.The suitable mol ratio of formaldehyde and alcohol is 1:2.5 ~ 1:6.0; The optimum mol ratio of formaldehyde and alcohol is 1:3 ~ 1:5.Appropriate catalysts consumption is 0.5 ~ 5.0% of reactant gross mass, and optimum catalyst amount is 1.0 ~ 4.0% of reactant gross mass.
In the preparation method of above-mentioned dialkoxy oxygen base, it is 75.0 ~ 95.0% alcoholic solutions that raw alcohol can be the mass fraction reclaimed after commercial technical grade higher alcohols, gylcol ether or dialkoxy methane crude product are purified; Raw material formaldehyde can be the formaldehyde that paraformaldehyde, the technical grade formalin of mass concentration 37% or their composite mass concentrations are greater than 37%.
Beneficial effect: compared with prior art, advantage of the present invention has: adopt sulfuric acid modified nanoscale HZSM-5 catalyst compound probability level dialkoxy methane, this sulfuric acid modified nanoscale HZSM-5 method for preparing catalyst is simple, raw material is easy to get, high, selective good, the good stability of catalyst activity, catalyst preparing economy, be easily separated with product, little to equipment corrosion, waste catalyst recovery, process easy; Catalyze and synthesize dialkoxy methane activity high, catalyst can be recycled.
Detailed description of the invention
The invention is further illustrated by the following examples.
The raw material that the present invention uses is technical grade, sulfuric acid modified nanoscale HZSM-5 catalyst self-control.Product dialkoxy methane purity and alcohol content adopt chromatographic.
Embodiment 1
Sulfuric acid modified nanoscale HZSM-5 catalyst: taking commercial nanoscale HZSM-5 is 50g, the sulfuric acid solution impregnated zeolite of 550 DEG C of roasting 3h, 250g5mol/L; Under 200r/min, normal temperature and pressure, stir 3h.Baking oven low temperature drying, 550 DEG C of roasting 3h; Cool and obtain sulfuric acid modified nanoscale HZSM-5 catalyst.Pore Characterization is carried out, specific area 270.4m to the catalyst of preparation
2/ g, aperture 26.4nm.
Embodiment 2
Sulfuric acid modified nanoscale HZSM-5 catalyst: take 50g nanoscale HZSM-5, the sulfuric acid solution impregnated zeolite of 550 DEG C of roasting 3h, 300g3mol/L; Under 200r/min, normal temperature and pressure, stir 3h.Baking oven low temperature drying, 500 DEG C of roasting 5h; Cool and obtain sulfuric acid modified nanoscale HZSM-5 catalyst.Pore Characterization is carried out, specific area 262.9m to the catalyst of preparation
2/ g, aperture 26.7nm.
Embodiment 3
In the 500mL four-hole boiling flask that thermometer, water knockout drum and condenser are housed, add mass fraction is respectively 37.0% formalin 40.4g, butanols 110.85g, sulfuric acid modified nanoscale HZSM-5 catalyst 0.75g prepared by embodiment 2, with the heating jacket of band magnetic agitation, stir and heat up, start the water collecting separating reaction generation, until reaction terminates.Collect the thick product 109.8g of dibutoxy methane, gas chromatographic analysis dibutoxy methane purity 63.1%, butanol content 35.9%.This thick product is by the refining dibutoxy methane that can obtain purity and be greater than 99.0%.
Embodiment 4
In the 500mL four-hole boiling flask that thermometer, water knockout drum and condenser are housed, add mass fraction is respectively 37.0% formalin 40.4g, reclaim the butanols 92.3g that purity is 96%, sulfuric acid modified nanoscale HZSM-5 catalyst 2.66g prepared by embodiment 1, with the heating jacket of band magnetic agitation, stir and heat up, start the water collecting separating reaction generation, until reaction terminates.Collect the thick product 90.9g of dibutoxy methane, gas chromatographic analysis dibutoxy methane purity 75.7%, butanol content 22.6%.This thick product is by the refining dibutoxy methane that can obtain purity and be greater than 99.0%.
Embodiment 5
In the 500mL four-hole boiling flask that thermometer, water knockout drum and condenser are housed, add mass fraction is respectively 37.0% formalin 40.5g, butanols 92.2g, embodiment 3 reclaims catalyst 0.66g, with the heating jacket of band magnetic agitation, stir and heat up, start the water collecting separating reaction generation, until reaction terminates.Collect the thick product 87.5g of dibutoxy methane, gas chromatographic analysis dibutoxy methane purity 82.2%, butanol content 10.3%.This thick product is by the refining dibutoxy methane that can obtain purity and be greater than 99.0%.
Embodiment 6
In the 500mL four-hole boiling flask that thermometer, water knockout drum and condenser are housed, add mass fraction is respectively 37.0% formalin 40.6g, butyl 121.6g, cyclohexane 24.3g, sulfuric acid modified nanoscale HZSM-5 catalyst 6.5g prepared by embodiment 2, with the heating jacket of band magnetic agitation, stir and heat up, start the water collecting separating reaction generation, until reaction terminates.Collect the thick product 133.2g of butyl formal, gas chromatographic analysis butyl formal purity 66.0%, butyl content 15.9%, cyclohexane content 16.3%.This thick product is by the refining butyl formal that can obtain purity and be greater than 98.0%.
Embodiment 7
In the 500mL four-hole boiling flask that thermometer, water knockout drum and condenser are housed, add mass fraction is respectively 37.0% formalin 40.9g, butyl 202.8g, toluene 36.6g, sulfuric acid modified nanoscale HZSM-5 catalyst 9.6g prepared by embodiment 2, with the heating jacket of band magnetic agitation, stir and heat up, start the water collecting separating reaction generation, until reaction terminates.Collect the thick product 222.7g of butyl formal, gas chromatographic analysis butyl formal purity 61.3%, butyl content 23.6%, toluene level 13.9%.This thick product is by the refining butyl formal that can obtain purity and be greater than 98.0%.
Claims (7)
1. one kind adopts the method for sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, it is characterized in that: raw material is aldehyde, alcohol and water entrainer, react under sulfuric acid modified nanoscale HZSM-5 catalyst action, reaction temperature is 65 ~ 260 DEG C, the water that continuous collection, separating reaction produce, until reaction terminates, still liquid is isolated catalyst and is namely obtained dialkoxy methane crude product; Wherein, sulfuric acid modified process nanoscale HZSM-5 catalyst circulation uses; Formaldehyde and alcohol mol ratio are 1:2.5 ~ 6.0; Sulfuric acid modified process nanoscale HZSM-5 catalyst amount is 0.5 ~ 5.0% of reactant gross mass, and alcohol is propyl alcohol, butanols, octanol or RO (CH
2cH
2o) nH, R=C
1-C
4alkyl, n=1,2.
2. the method for employing according to claim 1 sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, it is characterized in that: sulfuric acid modified nanoscale HZSM-5 catalyst is prepared by following methods: by commercial nanoscale HZSM-5 at 550 DEG C of activation 3h, then flooding 5 ~ 15 times of mass concentrations is 1 ~ 6mol/L sulfuric acid solution; Stir under 100 ~ 500r/min, normal temperature backflow 2 ~ 5h, baking oven low temperature drying, 300 ~ 550 DEG C of roasting 1 ~ 5h; Cooling both obtained catalyst.
3. the method for employing according to claim 1 sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, is characterized in that: the mol ratio of formaldehyde and alcohol is 1:2.5 ~ 5.0, and catalyst amount is 0.5 ~ 4.5% of reactant gross mass.
4. the method for the sulfuric acid modified nanoscale HZSM-5 of the employing according to claim 1 or 3 catalyst preparing dialkoxy methane, is characterized in that: the mol ratio of formaldehyde and alcohol is 1:2.5 ~ 4.5, and catalyst amount is 0.5 ~ 4.0% of reactant gross mass.
5. the method for employing according to claim 1 sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, is characterized in that: formalin is mass concentration is 37.0 ~ 70%.
6. the method for employing according to claim 1 sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, is characterized in that: water entrainer is toluene, cyclohexane, consumption be aldehyde, alcohol quality sum 5 ~ 30%.
7. the method for employing according to claim 1 sulfuric acid modified nanoscale HZSM-5 catalyst preparing dialkoxy methane, is characterized in that: when the alcohol of raw material is butanols, additionally do not add water entrainer in reaction raw materials.
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| CN110785476A (en) * | 2017-07-19 | 2020-02-11 | 沙特基础工业全球技术有限公司 | Cetane number enhanced fuel additive, method of making and use thereof |
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