CN102718740B - Trioxymethylene crystallization method - Google Patents
Trioxymethylene crystallization method Download PDFInfo
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- CN102718740B CN102718740B CN201210200530.1A CN201210200530A CN102718740B CN 102718740 B CN102718740 B CN 102718740B CN 201210200530 A CN201210200530 A CN 201210200530A CN 102718740 B CN102718740 B CN 102718740B
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Abstract
The invention relates to a trioxymethylene crystallization method and particularly provides a crystallization method for obtaining high-purity trioxymethylene. The method includes the steps: a) adding molten trioxymethylene and organic solvent at 30-35 DEG C into a container with a stirrer, well mixing, cooling by water bath at 30-35 DEG C, stirring for 2-8h, cooling by water bath at 18-25 DEG C, and stirring 1-4h to enable trioxymethylene to seed out; b) adding trioxymethylene suspension into a filter, standing, and subjecting the lower layer of the standing suspension to vacuum filtering; and c) adding solid obtained by filtering at the step b) into a drier to remove the residue solvent to obtain the trioxymethylene product. Trioxymethylene crystals obtained by the method are convenient for transport and storage, so that remote selling of the trioxymethylene is facilitated.
Description
Technical field
The present invention relates to a kind of crystallization method, particularly the crystallization method of trioxymethylene.
Background technology
Trioxymethylene is a kind of important industrial chemicals, of many uses, be mainly used in the first raw material monomer of engineering plastics copolymerized methanal, also can be used for preparing anhydrous formaldehyde and stablizer, smoke fumigant, sterilant, formed material, binding agent, sterilizing agent, antimicrobial drug etc.The depolymerization of trioxymethylene energy generates formaldehyde, so it almost completely can be in all formaldehyde reactions, particularly, when needs anhydrous formaldehyde is made reagent, its application is more valuable.
Current trioxymethylene is also fewer as commodity selling, trioxymethylene crystallization processes bibliographical information is less, the continuous process for freezing and crystallizing of trioxymethylene that Yunnan Yuntianhua Co., Ltd. adopts Poland to introduce, and its original tank crystallizer is transformed into double-pipe crystallizer (patent publication No. CN101074225).Reduce facility investment, reduced energy consumption, obtained certain correctional effect.But the cooling water in its double-pipe crystallizer is subzero 10 to subzero 13 ℃, need special refrigeration equipment certainly will increase the production cost of product.And be the middle portion in trioxymethylene production process, do not obtain highly purified trioxymethylene product (content of trioxymethylene is only 94.8%).
Method how low by energy consumption, that technical process is short, process cost is cheap realizes trioxymethylene crystallization, and obtains stable performance, and grain fineness number is more even, and purity is high, meets the market requirements such as anhydrous formaldehyde, is the Focal point and difficult point of trioxymethylene crystallization method.
Summary of the invention
Technical purpose
The object of this invention is to provide a kind of crystallization method that obtains highly purified trioxymethylene, the trioxymethylene xln obtaining by method of the present invention is convenient to transportation and storage, for trioxymethylene is remote, sells and offers convenience.
Technical scheme
To achieve these goals, the invention provides a kind of crystallization method of trioxymethylene, the method comprises the following steps:
A) organic solvent of molten state trioxymethylene and 30-35 ℃ is put into the container with agitator, after being uniformly mixed, use the water-bath of 30-35 ℃ to carry out cooling (once cooling), stir after 2-8h, cooling (secondary is cooling) carried out in the water-bath that re-uses 18-25 ℃, after stirring 1-4h, make trioxymethylene crystallization, wherein the temperature of molten state trioxymethylene is 70-90 ℃, described organic solvent is methyl alcohol, ethanol, toluene, benzene, ether, acetone, ethyl acetate or its arbitrary combination, the weight ratio of described trioxymethylene and organic solvent is 20:1-1:5, be preferably 5:1-1:3, described container is not particularly limited, and can be industrial conventional crystallizer,
B) trioxymethylene suspension is put into filtration unit, after standing, the lower floor of standing suspension is carried out to vacuum filtration, wherein filtration temperature is 20-30 ℃, vacuum tightness 0.03-0.095MPa, the supernatant liquor of standing suspension and filtrate can be recycled, as the organic solvent in a) as step; Described filtration unit is not particularly limited, and it can be conventional vacuum filter;
C) above-mentioned steps is filtered to gained solid and put into moisture eliminator to remove remaining solvent, thereby obtain trioxymethylene product, the purity 99.00-99.99wt% of gained trioxymethylene product wherein, the solvent of dried recovered can be recycled, as the organic solvent in a) as step.
Beneficial effect
The present invention has following advantage:
1) above-mentioned technique institute use equipment is conventional equipment, does not want special processing, reduce facility investment, and technical process is simple, and overall investment is less;
2) industrial refrigerating apparatus, the heating installation of not needing, can adopt and produce the needed industrial circulating water of trioxymethylene and a water, and energy consumption is low, and working cost is low;
3) constant product quality, crystallization uniformity coefficient is high, and purity is high, does not have insolubles to generate;
4) organic solvent can reuse, not loss;
5) environmentally friendly, three-waste free discharge.
Accompanying drawing explanation
Fig. 1 is the schema of trioxymethylene crystallization method of the present invention.
Embodiment
Molten state trioxymethylene in following embodiment is the molten state trioxymethylene that Hebei province's coal chemical industry engineering Technical Research Center trioxymethylene production line is produced, and the purity of trioxymethylene is 99.96%.Purity determination in following embodiment adopts Agilent company gas-chromatography 7890 quantitative, and methylal, formaldehyde adopt gas-chromatography quantitative equally, and the quantivative approach of formic acid, formaldehyde all adopts chemical titration.
Embodiment 1
In 1L round-bottomed flask, add 80 ℃ of molten state trioxymethylene 400g, add the fresh methanol of 30 ℃ (, the methyl alcohol of non-recovery) 160g, be uniformly mixed and be placed in 30 ℃ of water crystallisation by cooling, stir 3h, then water temperature is cooled to 20 ℃, at 20 ℃, mix 1h, stop stirring, supernatant liquid is poured out, and vacuum filtration at 25 ℃ of lower floors, after filtration, in Rotary Evaporators, controlling vacuum tightness is-0.06MPa, dry 3h at 30 ℃, discharging, the product of weighing and obtaining, this product crystal is tiny, uniform particles.Quality is 239g, yield 59.75%.Trioxymethylene purity is 99.8wt%, formic acid content 30ppm, formaldehyde content 60ppm, methylal content 30ppm, methanol content 200ppm.
The low reason of trioxymethylene crystal yield obtaining has in this embodiment been to use fresh methyl alcohol, and the trioxymethylene of part is dissolved in the methanol solution that has formed saturated trioxymethylene in methyl alcohol.
Embodiment 2
Method is with embodiment 1 trioxymethylene consumption 243g, methanol solution (methyl alcohol of recovery) consumption 360g.Obtain solid 241.9g, yield 99.5%.Polyoxymethylene purity is 99.75wt%, formic acid content 40ppm, and formaldehyde content 55ppm, methylal content does not detect, methanol content 220ppm.
Because used the methyl alcohol of recycling, that is, the saturated solution of methyl alcohol, so the product yield obtaining is very high in this embodiment.
Embodiment 3
Method is with embodiment 2, trioxymethylene consumption 239.7g, and be 5h time of drying, obtains crystal 238.1g, yield 99.33%.Trioxymethylene purity is 99.75wt%, formic acid content 38ppm, formaldehyde content 63ppm, methylal content 20ppm, methanol content 120ppm.
Embodiment 4
Method is with embodiment 1, and employing ethanol is solvent, and the solid that obtains trioxymethylene is 230g, and yield is 57.5%.Trioxymethylene purity is 99.6%, formic acid content 30ppm, and formaldehyde content 60ppm, methylal content 30ppm, ethanol content 1000ppm, the content of methyl alcohol is 40ppm.
Embodiment 5
Method is with embodiment 2, and adopting the ethanol reclaiming is solvent, and the solid that obtains trioxymethylene is 241.3g, and yield is 99.3%.Trioxymethylene purity is 99.7wt%, formic acid content 30ppm, and formaldehyde content 40ppm, methylal content 12ppm, ethanol content 366ppm, the content of methyl alcohol is 22ppm.
Embodiment 6
Method is with embodiment 1, and employing benzene is solvent, and the add-on of trioxymethylene is 300g, and the add-on of benzene is 300g, and the solid that obtains trioxymethylene is 130g, and yield is 43.3%.Trioxymethylene purity is 99.9wt%, formic acid content 30ppm, and formaldehyde content 60ppm, methylal content 30ppm, the content of benzene is 160ppm, the content of methyl alcohol is 20ppm.
Embodiment 7
Method is with embodiment 2, and adopting the benzene reclaiming is solvent, and the add-on of trioxymethylene is 130g, and the add-on of benzene is 470g, and the solid that obtains trioxymethylene is 129.6g, and yield is 99.69%.Trioxymethylene purity is 99.91wt%, formic acid content 30ppm, and formaldehyde content 50ppm, methylal content 10ppm, the content of toluene is 220ppm, the content of methyl alcohol is 10ppm.
Claims (7)
1. a crystallization method for trioxymethylene, the method comprises the following steps:
A) organic solvent of molten state trioxymethylene and 30-35 ℃ is put into the container with agitator, after being uniformly mixed, use the water-bath of 30-35 ℃ to carry out cooling, stir after 2-8h, re-use the water-bath of 18-25 ℃ and carry out coolingly, make trioxymethylene crystallization after stirring 1-4h;
B) trioxymethylene suspension is put into filtration unit, standing after, the lower floor of standing suspension is carried out to vacuum filtration;
C) by above-mentioned steps b) filter gained solid and put into moisture eliminator to remove remaining solvent, thus obtain trioxymethylene product.
2. crystallization method according to claim 1, wherein, the temperature of described molten state trioxymethylene is 70-90 ℃.
3. crystallization method according to claim 1, wherein, described organic solvent is methyl alcohol, ethanol, toluene, benzene, ether, acetone, ethyl acetate or its arbitrary combination.
4. crystallization method according to claim 1, wherein, the weight ratio of described trioxymethylene and organic solvent is 20:1-1:5.
5. crystallization method according to claim 4, wherein, the weight ratio of described trioxymethylene and organic solvent is 5:1-1:3.
6. the filtration temperature crystallization method according to claim 1, wherein, step b) is 20-30 ℃, and vacuum tightness 0.03-0.095MPa.
7. crystallization method according to claim 1, wherein, the organic solvent in step in a) is step b) in supernatant liquor and the filtrate of standing suspension, or be step c) in the solvent of dried recovered.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978438A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing tripoly aldehyde by ionic liquid catalysis of aldehyde |
| CN101074225A (en) * | 2007-04-02 | 2007-11-21 | 云南云天化股份有限公司 | Process for freezing and crystallizing triformol continuouslly by sleeved crystallizer |
| CN102020630A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for synthesizing trioxymethylene by catalyzing formaldehyde cyclization reaction through bifunctional ionic liquid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978438A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing tripoly aldehyde by ionic liquid catalysis of aldehyde |
| CN101074225A (en) * | 2007-04-02 | 2007-11-21 | 云南云天化股份有限公司 | Process for freezing and crystallizing triformol continuouslly by sleeved crystallizer |
| CN102020630A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for synthesizing trioxymethylene by catalyzing formaldehyde cyclization reaction through bifunctional ionic liquid |
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Address after: 100070 301, 3 floor, 21 building, 188 District, South Fourth Ring Road, Fengtai District, Beijing. Patentee after: BEIJING RISUN TECHNOLOGY CO., LTD. Address before: 100070 building 21, zone 188, South Fourth Ring Road, Fengtai District, Beijing. Patentee before: Beijing Xuyang Chemical Technology Research Institute Co., Ltd. |