CN105175389A - Method of synthesizing trioxymethylene by catalyzing formaldehyde through acid and salt - Google Patents
Method of synthesizing trioxymethylene by catalyzing formaldehyde through acid and salt Download PDFInfo
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Abstract
The invention provides a method of synthesizing trioxymethylene by catalyzing formaldehyde through acid and salt. According to the method, the acid and the salt are taken as catalysts, and a formaldehyde donor is catalyzed in an organic solvent to react so as to synthesize the trioxymethylene. Based on the weight of the organic solvent, the usage of the salt is 0.1 to 20 percent by weight, the usage of the formaldehyde donor is 5 to 80 percent by weight, and the usage of the acid is 0.001 to 5mol/kg. The method has the advantages that firstly, an experiment operation in the prior art that the formaldehyde donor is decomposed at a higher decomposition temperature which is higher than that in the method provided by the invention and then the trioxymethylene is prepared at a lower temperature after the temperature drops is reduced can be avoided, namely energy consumption caused by continuous temperature rise and temperature drop can be avoided; secondly, the conversion rate of converting the formaldehyde donor into the trioxymethylene can be improved, and the generation of a byproduct namely formic acid can be remarkably reduced; finally, the method is high in conversion rate, target products are easy to separate, and the separation energy consumption is lower.
Description
Technical field
The present invention relates to a kind of method utilizing acid and salt catalysis formaldehyde synthesizing triformol, belong to trioxymethylene synthesis technical field.
Background technology
Trioxymethylene is a kind of important industrial chemicals, has been widely used in products such as preparing anhydrous formaldehyde, sterilant, formed material, caking agent, sterilizing agent and antimicrobial drug.And now as the synthon of polyoxymethylene, the importance of trioxymethylene more and more comes into one's own.Polyoxymethylene product is owing to having excellent chemical-resistant stability, and higher physical strength and good plasticity-etc., in automobile industry, electrically, in electronics, agricultural, building materials and daily necessities etc. many aspects are widely used.Trioxymethylene is as the essential elements in polyoxymethylene synthesis, and the technology of synthesizing triformol just seems particularly important.
Formalin after current industrial main employing concentrates is raw material, take acid as catalyzer, trioxymethylene (low conversion rate of formaldehyde) is prepared by reactive distillation method, product is the azeotrope of water, formaldehyde and trioxymethylene, azeotrope need be prepared high-purity trioxymethylene further by extraction and rectificating method successively.As everyone knows, the vaporization heat of water is very high, and the energy consumption needed for rectification and purification process of concentrated formalin preparation feedback thing solution, reactive distillation processes, product is all very high; On the other hand, can generate a large amount of byproduct formic acid when utilizing formaldehyde solution to prepare trioxymethylene, reduce the transformation efficiency that formaldehyde conversion is trioxymethylene on the one hand, formic acid is very serious to the corrosion of follow-up equipment simultaneously, and process formic acid costly.
Therefore the novel method developing synthesizing triformol is particularly important.For this reason, patent US20140350216A1 and US20140316147A1 has invented the method utilizing acid catalysis to be dissolved in formaldehyde synthesizing triformol in organic solvent, be characterized in: paraformaldehyde is dissolved in organic solvent forms formaldehyde first at relatively high temperatures, then reduce temperature and add catalyzer making formaldehyde generation cyclization generate trioxymethylene (simultaneously generating more formic acid).Visible, the method does not relate to water, thus reduces the high energy consumption needed for vaporize water.But the method needs continuous heating, cooling, and obvious energy consumption is still higher, meanwhile, the method does not overcome a large amount of shortcoming generating byproduct formic acid.
The present invention is intended to overcome above-mentioned shortcoming, specifically, the following shortcoming of the method for patent US20140350216A1 and US20140316147A1 is overcome: the first overcomes need dissolve paraformaldehyde at relatively high temperatures when utilizing organic solvent to prepare trioxymethylene and generate formaldehyde, at a lower temperature formaldehyde cyclisation generated the shortcoming of trioxymethylene; It two is the generations significantly reducing formic acid; It three is improve the transformation efficiency that paraformaldehyde is converted into trioxymethylene further.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method utilizing acid and salt catalysis formaldehyde synthesizing triformol.
For reaching above-mentioned purpose, the invention provides and a kind ofly utilize acid and the method for salt catalysis formaldehyde synthesizing triformol, the method with sour and salt for catalyzer, catalysis formaldehyde donor Reactive Synthesis trioxymethylene in organic solvent;
With the weighing scale of organic solvent, the consumption of described salt is 0.1wt%-20wt%, and the consumption of formaldehyde donor is 5wt%-80wt%, and the consumption of acid is 0.001mol/kg-5mol/kg.
According to the preferred embodiment of the present invention, with the weighing scale of organic solvent, the consumption of described salt is 0.1wt%-15wt%, and the consumption of formaldehyde donor is 5wt%-60wt%, and the consumption of acid is 0.001mol/kg-3mol/kg.
According to the preferred embodiment of the present invention, described temperature of reaction is 80-500 DEG C, is preferably 80-250 DEG C.
According to the preferred embodiment of the present invention, described reaction is carried out in confined conditions, and reaction pressure is 0.01MPa-30MPa.
According to the preferred embodiment of the present invention, the present invention, to the time not requirement of reaction, namely can think that reaction terminates after reaction system clarification.
According to the preferred embodiment of the present invention, described formaldehyde donor comprises the material that paraformaldehyde or polyoxymethylene etc. can provide high-concentration formaldehyde.
According to the preferred embodiment of the present invention, described formaldehyde donor comprises paraformaldehyde or polyoxymethylene.
According to the preferred embodiment of the present invention, the water content of described formaldehyde donor is less than 10wt%.
According to the preferred embodiment of the present invention, when described formaldehyde donor is solid matter, the effect of acid and salt first makes solid formaldehyde donor fracture decomposition reaction occur and generate formaldehyde (monomer) molecule, the effect of organic solvent is then dissolve these monomer formaldehyde molecules, form (formaldehyde molecule and solvent) solution system, the generation trioxymethylene and the formaldehyde in solution reacts under acid and salt katalysis.
According to the preferred embodiment of the present invention, the present invention's acid used can be any material that can provide hydrogen ion or proton, and preferred described acid comprises the acid that pKa is-15 to 11; Described acid comprises boric acid, acetic acid, tosic acid, methylsulphonic acid, phosphoric acid, camphorsulfonic acid, Phenylsulfonic acid, trifluoromethane sulfonic acid, perchloric acid etc. further
lewis acid or the ionic liquids such as acid and zinc chloride, magnesium chloride, boron trifluoride.
According to the preferred embodiment of the present invention, described acid comprises boric acid, acetic acid, tosic acid, methylsulphonic acid, phosphoric acid, camphorsulfonic acid, Phenylsulfonic acid, trifluoromethane sulfonic acid, perchloric acid, zinc chloride, magnesium chloride, boron trifluoride or ionic liquid.
According to the preferred embodiment of the present invention, the positively charged ion of described ionic liquid comprises the combination of one or more in alkyl imidazolium cation, pyridines positively charged ion, quaternary amines positively charged ion, quaternary phosphonium cationoid, quinoline positively charged ion, iloquinoline derivative positively charged ion, list-piperidines positively charged ion, two-piperidines positively charged ion, list-morpholine cationoid or two-morpholine cationoid;
The negatively charged ion of described ionic liquid comprises p-methyl benzenesulfonic acid root, trifluoromethane sulfonic acid root, methylsulphonic acid root, bisulfate ion, sulfate radical, formate, acetate moiety, trifluoroacetic acid root, phosphate radical, phosphoric acid one hydrogen root, dihydrogen phosphate, tetrafluoroborate, hexafluoro-phosphate radical, sulfonyloxy methyl imines, trifluoromethanesulp-onyl-onyl imide, trifluoromethyl imines, chlorion, bromide anion, methyl sulfate negatively charged ion, Ethyl Sulfate negatively charged ion, the combination of one or more in 4-chlorobenzenesulfonic acid root or p-chlorobenzenesulfonic acid root.
According to the preferred embodiment of the present invention, the positively charged ion of described ionic liquid comprises containing-SO
3the combination of one or more in the alkyl imidazolium cation of H or-COOH, pyridines positively charged ion, quaternary amines positively charged ion, quaternary phosphonium cationoid, quinoline positively charged ion, iloquinoline derivative positively charged ion, list-piperidines positively charged ion, two-piperidines positively charged ion, list-morpholine cationoid or two-morpholine cationoid.
According to the preferred embodiment of the present invention, the positively charged ion of described ionic liquid comprises containing-SO
3the alkyl imidazolium cation of H or-COOH, containing-SO
3the pyridines positively charged ion of H or-COOH, containing-SO
3the quaternary amines positively charged ion of H or-COOH, containing-SO
3the quaternary phosphonium cationoid of H or-COOH, containing-SO
3the quinoline positively charged ion of H or-COOH, containing-SO
3the iloquinoline derivative positively charged ion of H or-COOH, containing-SO
3list-piperidines the positively charged ion of H or-COOH, containing-SO
3h or-COOH two-piperidines positively charged ion, containing-SO
3list-morpholine the cationoid of H or-COOH or containing-SO
3h or-COOH two-morpholine cationoid in the combination of one or more.
According to the preferred embodiment of the present invention, the present invention's salt used can be any salt formed by positively charged ion and negatively charged ion, preferred described salt comprises basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the organic acid salt of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the halogenide of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the vitriol of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the hydrosulfate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the carbonate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the supercarbonate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the nitrate of cuprous or aluminium,
More preferably described basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, organic acid salt that is cuprous or aluminium comprise basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, the camsilate of cuprous or aluminium, acetate, tosilate, metilsulfate or benzene sulfonate.
According to the preferred embodiment of the present invention, above-mentioned basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, halogenide that is cuprous or aluminium comprise basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, the fluorochemical of cuprous or aluminium, muriate, bromide and iodide.
According to the preferred embodiment of the present invention, the present invention's salt used comprises sodium-chlor, sodium camphorsulfonate, zinc chloride, magnesium chloride, cuprous chloride, cupric chloride, magnesiumcarbonate, magnesium sulfate, aluminum chloride, novalgin or saltpetre.
According to the preferred embodiment of the present invention, acid of the present invention can be to carry protogenic Lewis acid, as zinc chloride, magnesium chloride etc., simultaneously these Lewis acids such as zinc chloride, magnesium chloride are also salt, and therefore technical scheme of the present invention comprises Lewis acids such as being used alone above-mentioned zinc chloride, magnesium chloride or combinationally uses any two kinds of depolymerization of catalysis formaldehyde donor and the technical schemes of synthesizing triformol in organic solvent in above-mentioned Lewis acid; Also comprise and use the Lewis acid such as above-mentioned zinc chloride, magnesium chloride and non-Lewis acid (as the acid) depolymerization of catalysis formaldehyde donor and the technical scheme of synthesizing triformol in organic solvent; Also comprise and use the Lewis acid such as above-mentioned zinc chloride, magnesium chloride and non-lewis acidic salt (as the salt) depolymerization of catalysis formaldehyde donor and the technical scheme of synthesizing triformol in organic solvent;
When being used alone the Lewis acids such as above-mentioned zinc chloride, magnesium chloride or combinationally use any two kinds in above-mentioned Lewis acid, the Lewis acid now added both can play the effect that sour effect also can play salt, and its add-on both can have been carried out adding according to the consumption of acid and also can have been added according to the consumption of salt;
When using the Lewis acids such as above-mentioned zinc chloride, magnesium chloride and non-Lewis acid (as acid), now Lewis acid also can play the effect of acid and salt simultaneously, but its add-on is added according to the consumption of salt;
When using the Lewis acids such as above-mentioned zinc chloride, magnesium chloride and non-lewis acidic salt (as salt), now Lewis acid also can play the effect of acid and salt simultaneously, but its add-on is added according to the consumption of acid.
According to the preferred embodiment of the present invention, described organic solvent comprises the organic solvent of boiling point more than 120 DEG C.
According to the preferred embodiment of the present invention, described organic solvent should be selected under the existence of acid and salt can the organic solvent of dissolved solids formaldehyde donor, and the solubility property of its PARA FORMALDEHYDE PRILLS(91,95) donor is more high more pays the utmost attention to; In addition, boiling point should be selected higher, and chemical stability is good, and the organic solvent that get along well formaldehyde or catalyst acid and salt react, the temperature needed for solid formaldehyde donor decomposes is higher, and therefore the boiling point of organic solvent should more than 120 DEG C.
According to the preferred embodiment of the present invention, described organic solvent comprises the material described in formula (1):
In formula (1), R
1and R
2be separately hydrogen, halogen, aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
According to the preferred embodiment of the present invention, described organic solvent comprises formula (2) or the material described in formula (3):
In formula (2), n is the integer of 1-15;
In formula (3), R
3and R
4be separately aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
According to the preferred embodiment of the present invention, described organic solvent comprises formula (4) or the material described in formula (5):
In formula (4), n is the integer of 1-15;
In formula (5), R
5and R
6be separately aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
According to the preferred embodiment of the present invention, those skilled in the art can need to select suitable method to be separated target product trioxymethylene according to site work, in the preferred embodiment of the invention, after reaction terminates, the trioxymethylene that obtains can by distill or the method such as extraction is separated.
The method of acid and salt catalysis formaldehyde synthesizing triformol that utilizes of the present invention adopts acid and salt to be catalyst system, this catalyst system can the decomposition reaction of first catalysis formaldehyde donor (during solid), make formaldehyde donor at a lower temperature decomposition reaction occur, obtain the formaldehyde prepared needed for trioxymethylene and be dissolved in organic solvent; Then the formaldehyde generation cyclization that acid and salt catalyst system can continue in Organic Solvents at the same temperature generates trioxymethylene.Wherein salt add the target that can realize following three aspects:
1, the catalytic performance of sour PARA FORMALDEHYDE PRILLS(91,95) donor decomposition reaction is strengthened;
2, the generation concentration of trioxymethylene is increased;
3, the generation concentration of formic acid is reduced.
As can be seen here, method of the present invention makes the decomposition of formaldehyde donor and the generation of trioxymethylene carry out at the same temperature, avoid in prior art and make formaldehyde donor decompose (and decomposition temperature is higher than decomposition temperature of method of the present invention) first at relatively high temperatures, then lower the temperature and prepare the experimental implementation of trioxymethylene at a lower temperature, that is, the energy consumption caused by continuous heating, cooling can be avoided.
And the present invention decomposes with the formaldehyde donor such as paraformaldehyde, polyoxymethylene the formaldehyde generated and prepares trioxymethylene for raw material, avoid owing to adopting formalin for high energy consumption problem when trioxymethylene prepared by raw material caused by the high vaporization heat of water.
Meanwhile, while raising formaldehyde donor is converted into the transformation efficiency of trioxymethylene, the generation of byproduct formic acid is significantly reduced.
Finally, the method transformation efficiency of acid and salt catalysis formaldehyde synthesizing triformol that utilizes of the present invention is high, and target product is separated simple, and separating energy consumption is also lower.
Embodiment
The Advantageous Effects of implementation process of the present invention and generation will be explained by specific embodiment below, be intended to help reader to understand essence of the present invention and feature better, but not as can the restriction of practical range to this case.
In the following embodiments, reaction is all carried out in airtight reactor, and reactor is wanted can resistance to certain pressure (30MPa), and heating and temperature controlling device generally is oil bath temperature control, reacted mixture analysis is gas chromatographic analysis, adopts marker method to carry out quantitatively.
In all embodiments of the present invention and comparative example, use the acid number (take formic acid as standard) of volumetry to mixed solution to measure, namely the variable quantity of acid number can embody the changing value of the amount of formic acid before and after reaction.
Acid content (acid number) in mixed solution is calculated according to following formula (1):
Formic acid content (ppm)=V × N × 46 × 1000/Ws formula (1)
In formula (1): V represents the volume of titration dehydrogenation sodium oxide used, mL; N represents the volumetric molar concentration of sodium hydroxide solution, molL
– 1;
Ws represents sample quality, g;
46 is the molecular weight of formic acid.
Embodiment 1
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g paraformaldehyde, the sulfolane solution of the 20wt% trifluoromethane sulfonic acid of 0.478g, 0.054g magnesium chloride, sampling after 1 hour is reacted at 110 DEG C, utilize gas chromatographic analysis, analytical results shows: in mixed solution, the content of trioxymethylene: 5.95wt%, formaldehyde content: 2.86wt%, the transformation efficiency of paraformaldehyde: 66.3%.Acid number changes: 1356ppm.
Embodiment 2
Present embodiments provide the depolymerization experiment of paraformaldehyde in the organic solvent being added with acid, it comprises following concrete steps:
In the closed reactor of 25mL, add 24.60g tetramethylene sulfone, the paraformaldehyde (accounting for the 9.92wt% of solvent) of 2.44g, 1.88g camphorsulfonic acid, place after one hour at 110 DEG C, solution becomes clarification, illustrates that paraformaldehyde depolymerization is complete simultaneously;
Similarly, at 145 DEG C, in the airtight reactor of 25mL, add 20.57g tetramethylene sulfone, the paraformaldehyde (accounting for the 14.97wt% of solvent) of 2.44g and 1.48g magnesium chloride, placed after one hour simultaneously, find that solution becomes clarification, illustrate that paraformaldehyde depolymerization is complete.
Embodiment 3
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 22.32g tetramethylene sulfone simultaneously, 3.35g paraformaldehyde, 1.01 zinc chloride and 0.45g sodium camphorsulfonate, react sampling after 1 hour, utilize gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 6.86wt%, formaldehyde content: 1.63wt%, the transformation efficiency of paraformaldehyde: 55.53%.Acid number changes: 2213ppm.
Embodiment 4
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g paraformaldehyde, 0.38g perchloric acid and 0.49g magnesium chloride, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 5.64wt%, formaldehyde content: 1.86wt%, the transformation efficiency of paraformaldehyde: 64.51%.Acid number changes: 2023ppm.
Embodiment 5
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 22.95g tetramethylene sulfone simultaneously, 2.27g paraformaldehyde, 0.87g phosphoric acid and 0.46g zinc chloride, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 5.68wt%, formaldehyde content: 1.54%, the transformation efficiency of paraformaldehyde: 68.53%.Acid number changes: 1132ppm.
Embodiment 6
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 20.57g tetramethylene sulfone simultaneously, 3.08g paraformaldehyde, 99%) and 0.42g sodium camphorsulfonate 0.60gN-octylpyrrolidone metilsulfate (the prompt Chemical Co., Ltd. of upper marine origin, purity:, sampling after 1 hour is reacted at 150 DEG C, utilize gas chromatographic analysis, analytical results shows: in mixed solution, the content of trioxymethylene: 8.77wt%, formaldehyde content: 2.14%, the transformation efficiency of paraformaldehyde: 70.24%.Acid number changes: 842ppm.
Embodiment 7
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises following step:
In the reactor that 25mL is airtight, add 21.53g tetramethylene sulfone simultaneously, 3.22g paraformaldehyde, 0.64g camphorsulfonic acid and 0.43g sodium camphorsulfonate, react sampling after 1 hour, utilize gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 8.68wt%, formaldehyde content: 2.34%, the transformation efficiency of paraformaldehyde: 69.60%.Acid number changes: 1768ppm.
Sample after 2 hours, utilize gas chromatographic analysis, analytical results shows: in mixed solution, and the content of trioxymethylene is: 8.47wt%, and formaldehyde content is: 2.62wt%, the transformation efficiency of paraformaldehyde: 67.91%.Acid number changes: 1436ppm.
Embodiment 8
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 19.05g1-chloronaphthalene simultaneously, 1.88g paraformaldehyde, 99%) and 0.38g saltpetre 0.54g pyrrolidone hydrosulfate (the prompt Chemical Co., Ltd. of upper marine origin, purity:, sampling after 1 hour is reacted at 110 DEG C, utilize gas chromatographic analysis, analytical results shows: in mixed solution, the content of trioxymethylene: 4.34wt%, formaldehyde content: 2.41wt%, the transformation efficiency of paraformaldehyde: 49.56%.Acid number changes: 965ppm.
Embodiment 9
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 21.00g dimethyl sulfoxide (DMSO) simultaneously, 2.08g paraformaldehyde, 1.61 camphorsulfonic acids and 1.05g magnesiumcarbonate, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 4.76wt%, formaldehyde content: 2.53wt%, the transformation efficiency of paraformaldehyde: 56.50%.Acid number changes: 989ppm.
Embodiment 10
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises following experimental procedure:
In the reactor that 25mL is airtight, add 22.06g diethyl sulfone simultaneously, 2.18g paraformaldehyde, 1.61 camphorsulfonic acids and 0.44g copper sulfate, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 4.36wt%, formaldehyde content: 2.47wt%, the transformation efficiency of paraformaldehyde: 51.7%.Acid number changes: 1863ppm.
Embodiment 11
Present embodiments provide a kind of acid and the salt depolymerization of catalysis polyoxymethylene and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g polyoxymethylene, 0.05161g trifluoromethane sulfonic acid and 0.49g sodium-chlor, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 5.87wt%, formaldehyde content: 1.76wt%, the transformation efficiency of paraformaldehyde: 66.35%.Acid number changes: 1963ppm.
Embodiment 12
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g paraformaldehyde, 0.05161g perchloric acid and 0.49g cuprous chloride, react sampling after 1 hour, utilize gas chromatographic analysis at 90 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 5.70wt%, formaldehyde content: 1.82wt%, the transformation efficiency of paraformaldehyde: 64.43%.Acid number changes: 3023ppm.
Embodiment 13
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 20.57g tetramethylene sulfone simultaneously, 3.08g paraformaldehyde, 1.57g camphorsulfonic acid and 1.03g Repone K, react sampling after 1 hour, utilize gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 8.43wt%, formaldehyde content: 2.06wt%, the transformation efficiency of paraformaldehyde: 71.84%.Acid number changes: 1056ppm.
Embodiment 14
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 20.57g tetramethylene sulfone simultaneously, 6.17g paraformaldehyde, 0.31g trifluoromethane sulfonic acid and 1.03g neutralized verdigris, react sampling after 1 hour, utilize gas chromatographic analysis at 180 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 10.21wt%, formaldehyde content: 2.89wt%, the transformation efficiency of paraformaldehyde: 46.46%.Acid number changes: 2056ppm.
Embodiment 15
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 18.87g tetramethylene sulfone simultaneously, 7.55g paraformaldehyde, 0.31g trifluoromethane sulfonic acid and 1.51g aluminum chloride, react sampling after 1 hour, utilize gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 11.21wt%, formaldehyde content: 2.46wt%, the transformation efficiency of paraformaldehyde: 41.21%.Acid number changes: 1865ppm.
Embodiment 16
Present embodiments provide a kind of acid and the salt depolymerization of catalysis paraformaldehyde and the method for synthesizing triformol in organic solvent, the method comprises the following steps:
In the reactor that 25mL is airtight, add 20.57g tetramethylene sulfone simultaneously, 1.03g paraformaldehyde, 2.54g boric acid and 0.04g paratoluenesulfonic acid sodium salt, react sampling after 1 hour, utilize gas chromatographic analysis at 220 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 2.05wt%, formaldehyde content: 0.89wt%, the transformation efficiency of paraformaldehyde: 51.05%.Acid number changes: 862ppm.
Embodiment 17
Present embodiments provide a kind of zinc chloride depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, this embodiment mainly embodies zinc chloride both can as acid, can use in the solution of the present invention as salt again, the method comprises the following steps:
In the reactor that 25mL is airtight, add 22.32g tetramethylene sulfone simultaneously, 3.35g paraformaldehyde, 1.01 zinc chloride, react sampling after 1 hour, utilize gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 6.32wt%, formaldehyde content: 1.53wt%, the transformation efficiency of paraformaldehyde: 50.33%.Acid number changes: 2717ppm.
Comparative example 1
This comparative example provides a kind of method that acid catalyzes and synthesizes trioxymethylene in organic solvent, and the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone, after being warming up to 145 DEG C, add 2.44g paraformaldehyde, stir after paraformaldehyde is dissolved; After being cooled to 120 DEG C, at this temperature, add the sulfolane solution 0.478g of 20wt% trifluoromethane sulfonic acid, 60 DEG C of samplings are cooled to after reaction 1min, utilize gas chromatographic analysis, analytical results shows: in mixed solution, the content of trioxymethylene: 3.76wt%, formaldehyde content: 2.99wt%, the transformation efficiency of paraformaldehyde: 42.40%.Acid number changes: 2826ppm.
Comparative example 2
This comparative example provides a kind of acid depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, and the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g paraformaldehyde, the sulfolane solution of the 20wt% trifluoromethane sulfonic acid of 0.478g, reacts sampling after 1 hour, utilizes gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 4.32wt%, formaldehyde content: 2.89wt%, the transformation efficiency of paraformaldehyde: 48.72%.Acid number changes: 1788ppm.
Comparative example 3
This comparative example provides paraformaldehyde depolymerization experiment in organic solvent, and it mainly contrasts with embodiment 2, and to embody the Advantageous Effects of the inventive method, the method comprises the following steps:
In the airtight reactor of 25mL, first add 24.60g tetramethylene sulfone, the paraformaldehyde (accounting for the 9.92wt% of solvent) of 2.44g, place one hour at 110 DEG C, then find that solution becomes muddy, illustrate that paraformaldehyde does not have depolymerization complete;
In the airtight reactor of 25mL, first add 24.60g tetramethylene sulfone, the paraformaldehyde (accounting for the 9.92wt% of solvent) of 2.44g, place one hour at 120 DEG C, then find that solution becomes muddy, illustrate that paraformaldehyde does not have depolymerization complete;
Similarly, at 145 DEG C, in the airtight reactor of 25mL, first add 20.57g tetramethylene sulfone, the paraformaldehyde (accounting for the 14.97wt% of solvent) of 3.08g, placed after one hour, find solution be also muddy, illustrate paraformaldehyde same be do not have depolymerization complete.
Comparative example 4
This comparative example provides a kind of acid depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, and the method comprises the following steps:
In the reactor that 25mL is airtight, add 24.60g tetramethylene sulfone simultaneously, 2.44g paraformaldehyde, 0.38g perchloric acid, reacts sampling after 1 hour, utilizes gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 4.89wt%, formaldehyde content: 2.06wt%, the transformation efficiency of paraformaldehyde: 54.95%.Acid number changes: 4645ppm.
Comparative example 5
This comparative example provides a kind of acid depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, and the method comprises the following steps:
In the reactor that 25mL is airtight, add 22.95g tetramethylene sulfone simultaneously, 2.27g paraformaldehyde, 0.87g phosphoric acid, reacts sampling after 1 hour, utilizes gas chromatographic analysis at 110 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 5.23wt%, formaldehyde content: 2.16%, the transformation efficiency of paraformaldehyde: 60.11%.Acid number changes: 1643ppm.
Comparative example 6
This comparative example provides a kind of acid depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, and the method comprises following experimental procedure:
In the reactor that 25mL is airtight, add 20.57g tetramethylene sulfone simultaneously, 3.08g paraformaldehyde, 0.60gN-octylpyrrolidone metilsulfate, reacts sampling after 1 hour, utilizes gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 8.52wt%, formaldehyde content: 2.06%, the transformation efficiency of paraformaldehyde: 67.08%.Acid number changes: 1025ppm.
Comparative example 7
This comparative example provides a kind of acid depolymerization of catalysis paraformaldehyde and method of synthesizing triformol in organic solvent, and the method comprises following experimental procedure:
In the reactor that 25mL is airtight, add 21.53g tetramethylene sulfone simultaneously, 3.22g paraformaldehyde, 0.64g camphorsulfonic acid, reacts sampling after 1 hour, utilizes gas chromatographic analysis at 150 DEG C, analytical results shows: in mixed solution, the content of trioxymethylene: 8.56wt%, formaldehyde content: 2.06%, the transformation efficiency of paraformaldehyde: 67.49%.Acid number changes: 2647ppm;
Sample after 2 hours, utilize gas chromatographic analysis, analytical results shows: in mixed solution, and the content of trioxymethylene is: 7.86wt%, and formaldehyde content is: 2.42wt%, the transformation efficiency of paraformaldehyde: 61.97%.Acid number changes: 2573ppm.
Wherein, comparative example 1,2 is the comparative example of embodiment 1, and comparative example 3 is the comparative example of embodiment 2, and comparative example 4 is the comparative example of embodiment 4, and comparative example 5 is the comparative example of embodiment 5, and comparative example 6 is the comparative example of embodiment 6, and comparative example 7 is the comparative example of embodiment 7.
From comparative example 1 and comparative example 1,2: comparative example 1 is experimental technique disclosed in patent US20140350216A1 and patent US20140316147A1, comparative example 2 is for adopting method of the present invention, but do not add salt, embodiment 1 is the system of acid of the present invention and salt.Can be found by contrast, method of the present invention is simple to operate, and effect is better than method disclosed in patent US20140350216A1 and patent US20140316147A1, and the effect after salt adding of the present invention simultaneously also has lifting.
From comparative example 2 and comparative example 3: deposit in case in acid or salt, the formaldehyde donor solubleness of solid phase is obviously greater than not acid adding, thus salt or acid add the depolymerization or dissolving that can promote formaldehyde donor.
From embodiment 4,5,6 and comparative example 4,5,6: the increasing amount utilizing the method for acid and salt catalysis formaldehyde synthesizing triformol can reduce formic acid of the present invention, namely method of the present invention can suppress the generation of formic acid, method of the present invention can improve the transformation efficiency of paraformaldehyde simultaneously, improves the productive rate of trioxymethylene.
From embodiment 7 and comparative example 7: the decomposition adding the trioxymethylene that can also suppress generation of salt, as: in comparative example 7, sample time extended to 2 hours by 1 hour, and the content of trioxymethylene is down to 7.86wt% by 8.56wt%, have dropped 0.70 percentage point; And in embodiment 7, due to adding of sodium camphorsulfonate, sample time extended to 2 hours by 1 hour, and the content of trioxymethylene is down to 8.47wt% by 8.68wt%, only have dropped 0.21 percentage point, what salt was described adds the decomposition that can suppress product trioxymethylene.
Claims (10)
1. utilize acid and the method for salt catalysis formaldehyde synthesizing triformol, wherein, the method with sour and salt for catalyzer, catalysis formaldehyde donor Reactive Synthesis trioxymethylene in organic solvent;
With the weighing scale of organic solvent, the consumption of described salt is 0.1wt%-20wt%, and the consumption of formaldehyde donor is 5wt%-80wt%, and the consumption of acid is 0.001mol/kg-5mol/kg;
The consumption of preferred described salt is 0.1wt%-15wt%, and the consumption of formaldehyde donor is 5wt%-60wt%, and the consumption of acid is 0.001mol/kg-3mol/kg;
Also preferred described temperature of reaction is 80-500 DEG C, is more preferably 80-250 DEG C.
2. method according to claim 1, wherein, described reaction is carried out in confined conditions, and reaction pressure is 0.01MPa-30MPa.
3. method according to claim 1, wherein, described method comprises: by described organic solvent, formaldehyde donor, acid and salt mixing, confined reaction, obtains trioxymethylene.
4. method according to any one of claim 1-3, wherein, described formaldehyde donor comprises paraformaldehyde or polyoxymethylene;
Preferably, the water content of described formaldehyde donor is less than 10wt%.
5. method according to any one of claim 1-3, wherein, described acid comprises the acid that pKa is-15 to 11;
Preferred described acid comprises boric acid, acetic acid, tosic acid, methylsulphonic acid, phosphoric acid, camphorsulfonic acid, Phenylsulfonic acid, trifluoromethane sulfonic acid, perchloric acid, zinc chloride, magnesium chloride, boron trifluoride or ionic liquid;
More preferably the positively charged ion of described ionic liquid comprises the combination of one or more in alkyl imidazolium cation, pyridines positively charged ion, quaternary amines positively charged ion, quaternary phosphonium cationoid, quinoline positively charged ion, iloquinoline derivative positively charged ion, list-piperidines positively charged ion, two-piperidines positively charged ion, list-morpholine cationoid or two-morpholine cationoid;
The negatively charged ion of described ionic liquid comprises p-methyl benzenesulfonic acid root, trifluoromethane sulfonic acid root, methylsulphonic acid root, bisulfate ion, sulfate radical, formate, acetate moiety, trifluoroacetic acid root, phosphate radical, phosphoric acid one hydrogen root, dihydrogen phosphate, tetrafluoroborate, hexafluoro-phosphate radical, sulfonyloxy methyl imines, trifluoromethanesulp-onyl-onyl imide, trifluoromethyl imines, chlorion, bromide anion, methyl sulfate negatively charged ion, Ethyl Sulfate negatively charged ion, the combination of one or more in 4-chlorobenzenesulfonic acid root or p-chlorobenzenesulfonic acid root,
The positively charged ion of further preferred described ionic liquid comprises containing-SO
3the alkyl imidazolium cation of H or-COOH, containing-SO
3the pyridines positively charged ion of H or-COOH, containing-SO
3the quaternary amines positively charged ion of H or-COOH, containing-SO
3the quaternary phosphonium cationoid of H or-COOH, containing-SO
3the quinoline positively charged ion of H or-COOH, containing-SO
3the iloquinoline derivative positively charged ion of H or-COOH, containing-SO
3list-piperidines the positively charged ion of H or-COOH, containing-SO
3h or-COOH two-piperidines positively charged ion, containing-SO
3list-morpholine the cationoid of H or-COOH or containing-SO
3h or-COOH two-morpholine cationoid in the combination of one or more.
6. method according to any one of claim 1-3, wherein, described salt comprises basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the organic acid salt of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the halogenide of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the vitriol of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the hydrosulfate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the carbonate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the supercarbonate of cuprous or aluminium, basic metal, alkaline-earth metal, iron, ferrous, zinc, copper, the nitrate of cuprous or aluminium,
Preferred described basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, organic acid salt that is cuprous or aluminium comprise basic metal, alkaline-earth metal, iron, ferrous iron, zinc, copper, the camsilate of cuprous or aluminium, acetate, tosilate, metilsulfate or benzene sulfonate;
Also preferred described salt comprises sodium-chlor, sodium camphorsulfonate, zinc chloride, magnesium chloride, cuprous chloride, cupric chloride, magnesiumcarbonate, magnesium sulfate, aluminum chloride, novalgin or saltpetre.
7. the method according to any one of claim 1-3, wherein, described organic solvent comprises the organic solvent of boiling point more than 120 DEG C;
Being preferably can the organic solvent of dissolved solids formaldehyde donor under acid and salt existence.
8. method according to claim 7, wherein, described organic solvent comprises the material described in formula 1:
In formula 1, R
1and R
2be separately hydrogen, halogen, aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
9. method according to claim 7, wherein, described organic solvent comprises formula 2 or the material described in formula 3:
In formula 2, n is the integer of 1-15; In formula 3, R
3and R
4be separately aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
10. method according to claim 7, wherein, described organic solvent comprises formula 4 or the material described in formula 5:
In formula 4, n is the integer of 1-15; In formula 5, R
5and R
6be separately aryl, C
1-C
16alkyl or C
3-C
16cycloalkyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397325A (en) * | 2016-08-31 | 2017-02-15 | 林州市科能材料科技有限公司 | Imidazole-type ionic liquid and application thereof to degradation of polyformaldehyde |
| CN106518837A (en) * | 2016-10-14 | 2017-03-22 | 中国石油大学(北京) | Method for synthesizing trioxymethylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633769A (en) * | 2012-04-01 | 2012-08-15 | 邢台旭阳煤化工有限公司 | Method and device for producing trioxymethylene |
| CN103373980A (en) * | 2012-04-16 | 2013-10-30 | 中国海洋石油总公司 | Method for synthesizing trioxymethylene |
| CN104024240A (en) * | 2011-11-24 | 2014-09-03 | 提克纳有限公司 | Process For Producing A Cyclic Acetal In A Heterogeneous Reaction System |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104024240A (en) * | 2011-11-24 | 2014-09-03 | 提克纳有限公司 | Process For Producing A Cyclic Acetal In A Heterogeneous Reaction System |
| CN102633769A (en) * | 2012-04-01 | 2012-08-15 | 邢台旭阳煤化工有限公司 | Method and device for producing trioxymethylene |
| CN103373980A (en) * | 2012-04-16 | 2013-10-30 | 中国海洋石油总公司 | Method for synthesizing trioxymethylene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397325A (en) * | 2016-08-31 | 2017-02-15 | 林州市科能材料科技有限公司 | Imidazole-type ionic liquid and application thereof to degradation of polyformaldehyde |
| CN106518837A (en) * | 2016-10-14 | 2017-03-22 | 中国石油大学(北京) | Method for synthesizing trioxymethylene |
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