CN116813457B - Preparation method of anhydrous formaldehyde solution - Google Patents
Preparation method of anhydrous formaldehyde solution Download PDFInfo
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- CN116813457B CN116813457B CN202310433842.5A CN202310433842A CN116813457B CN 116813457 B CN116813457 B CN 116813457B CN 202310433842 A CN202310433842 A CN 202310433842A CN 116813457 B CN116813457 B CN 116813457B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000008098 formaldehyde solution Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 60
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920002545 silicone oil Polymers 0.000 claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- CAMXOLUXKJMDSB-UHFFFAOYSA-L copper;naphthalene-1-carboxylate Chemical compound [Cu+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 CAMXOLUXKJMDSB-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GGCJLWBMJYGIRE-UHFFFAOYSA-N ethanol;formaldehyde Chemical compound O=C.CCO GGCJLWBMJYGIRE-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 241000255969 Pieris brassicae Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/55—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of oligo- or polymeric oxo-compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of depolymerization of paraformaldehyde, in particular to a preparation method of anhydrous formaldehyde solution, and impurities are introduced when a large amount of alkali or acid is used for carrying out catalytic depolymerization on the paraformaldehyde. In the prior art, the direct heating depolymerization effect and the direct heating depolymerization effect in ethanol and methanol are not ideal, and the invention utilizes the dimethyl silicone oil microwave thermal depolymerization and uses copper naphthalate or copper stearate as a depolymerization catalyst. The microwave effect of the paraformaldehyde can reduce the depolymerization activation energy of the paraformaldehyde, and experimental results show that copper naphthalate or copper stearate and copper powder have catalytic effect on depolymerization of the paraformaldehyde under the action of microwaves, and the copper naphthalate and copper stearate can be well dispersed into the dimethyl silicone oil and catalyze the depolymerization of the paraformaldehyde.
Description
Technical Field
The invention belongs to the technical field of depolymerization of paraformaldehyde, and particularly relates to a preparation method of an anhydrous formaldehyde solution.
Background
The industrial products of paraformaldehyde in the market mainly have 92%, 95%, 96% and other content specifications, the content of which can be more than 98%, the products are solid, flexible in packaging, high in effective components, convenient for long-distance transportation, can be conveniently redissolved to prepare formaldehyde aqueous solution during use, can be depolymerized or reacted with organic solvents to generate anhydrous formaldehyde solution, is known as ideal pure formaldehyde source, is an excellent substitute for industrial formaldehyde, is mainly applied to pesticide and resin production, and also has certain application in the synthesis field of other chemicals, and further has the application of bactericides, fumigators and the like. Paraformaldehyde is easily soluble in hot water and slightly soluble in cold water, and can be dissolved in dilute acid and dilute alkali, and many depolymerization methods are studied, such as base-catalyzed depolymerization, acid-catalyzed depolymerization and the like, and some popular depolymerization methods. The acid catalyzed depolymerization is random chain scission, the main product is low molecular formaldehyde polymer, and the byproduct paraformaldehyde in the acid catalyzed digestion system can be used in the production process of trioxymethylene. Zhao Houquan, and the like, directly adding methanol into a harrow type dryer of paraformaldehyde for thermal depolymerization, depolymerizing for 60-80 min at 50-80 ℃, wherein the formaldehyde content of the produced anhydrous formaldehyde methanol solution reaches 45%, the moisture is lower than 1.9%, the labor and transportation cost are saved, but the disadvantage is that the depolymerization effect is common, the low-temperature stability is poor, polymerized formaldehyde solid can be produced under winter or refrigeration conditions, the use experience of downstream customers is poor, and the catalyst or the auxiliary agent is needed to be added and further heated for depolymerization during use. The method for synthesizing paraformaldehyde by microwave method is disclosed in the patent application. In 2017, china patent CN201710021891.2 Tian Yiqun and the like takes formaldehyde aqueous solution as raw materials, the whole process of dehydration, polymerization and depolymerization of aqueous formaldehyde is realized in 1 reaction kettle, organic amine is used as a catalyst to improve depolymerization quality and stability, depolymerization effect is good, the content of the produced anhydrous formaldehyde alcohol solution is stable, low-temperature stability is good, and the anhydrous formaldehyde alcohol solution can be conveyed to a glyphosate workshop through a pipeline for use. The Chinese patent CN201921899112.X utilizes a multistage series reactor to couple a dehydration tower, triethylamine is used as a catalyst to prepare anhydrous formaldehyde-alcohol solution, the depolymerization effect is good, the water content of the product can be as low as 0.04%, the low-temperature storage stability is good, the defects are large solvent amount, the effective formaldehyde content is low, the reaction efficiency is low, and the other defect is that the process route can not fundamentally eliminate the problems of packaging, dust and the like of paraformaldehyde. In order to solve the above problems, a preparation method and application of an anhydrous formaldehyde solution are needed to meet the existing market demands and performance requirements.
Disclosure of Invention
The invention aims to provide a preparation method and application of an anhydrous formaldehyde solution.
A method for depolymerizing paraformaldehyde, comprising the steps of:
firstly, adding paraformaldehyde particles at the bottom of a microwave reaction kettle with a stirring device, then adding silicone oil, wherein the liquid level of the silicone oil exceeds that of the paraformaldehyde particles and a depolymerization catalyst accounting for 0.03% -0.05% of the mass of the paraformaldehyde particles, the depolymerization catalyst is copper naphthalate or copper stearate, then adding an alcohol solvent at the liquid level of the silicone oil and layering on the liquid level of the silicone oil, and placing a stirring paddle of the stirring device below the liquid level of the silicone oil;
and secondly, stirring is started, microwave heating, condensing and refluxing are carried out for 43-51 min, standing and layering are carried out, and then the alcohol solvent solution is recovered by liquid separation, so that the depolymerized formaldehyde solution is obtained.
Further, the mass ratio of the silicone oil to the paraformaldehyde is 1:0.4-0.5.
Further, the mass ratio of the alcohol solvent to the silicone oil is 4:3.86-4.8.
Further, the alcohol solvent is selected from one of methanol and ethanol.
The formaldehyde-ethanol solution can be used for soaking and sterilizing in an operating room, is efficient, quick and low in price, has clear liquid medicine, and is convenient for taking and fishing the surgical tool articles from the liquid medicine. The formaldehyde-methanol solution can be used as raw material to synthesize high-performance resin raw material products such as hexamethylol melamine, methylal, alpha-cyanoacrylate and the like. In addition, formaldehyde-ethanol solutions are also widely used as fixatives.
Further, the silicone oil is 201 methyl silicone oil.
201 Methyl silicone oil is a novel organic silicon synthetic material and is colorless and transparent oily liquid in appearance. The chemical composition of the composition is linear polysiloxane. Because of the stability of the silicon-oxygen bond and the hydrophobicity and structural characteristics of methyl, the methyl silicone oil has strong heat resistance, high flash point, difficult volatilization, small viscosity temperature coefficient, large compression resistance, small surface capacity, stable chemical property, good electrical insulation performance, water resistance, moisture resistance and no toxic or harmful effect on organisms.
And it is notable that methyl silicone oil is insoluble in formaldehyde and ethanol; formaldehyde is mixed with methanol and ethanol in any ratio.
Further, the stirring device in the first step is one of magnetic rotor stirring and mechanical anchor stirring.
Further, the surface temperature of the silicone oil in the second step is 83-95 ℃.
Further, the stirring speed of the second step is 300-600 rpm.
Further, the purity of the paraformaldehyde particles is 92% -96%, and the moisture content is 1.6% -2.2%.
Further, the microwave power is 3000-3200W, and the frequency is 2450MHz.
The invention has the beneficial effects that:
Firstly, the invention adopts the dimethyl silicone oil which is insoluble in water and in ethanol and methanol as a depolymerization medium of paraformaldehyde, the dimethyl silicone oil has good heat resistance, uniform heat transfer and no formaldehyde dissolution, and the density is larger than that of ethanol and methanol and smaller than that of paraformaldehyde, when paraformaldehyde particles are added at the bottom of a microwave reaction kettle with a stirring device, due to the gravity and the stirring effect of the stirring device, the paraformaldehyde is arranged above the kettle bottom and below the liquid level of the dimethyl silicone oil, the solvent layer of ethanol or methanol is arranged above the liquid level of the silicone oil, after the paraformaldehyde is depolymerized, formaldehyde is not dissolved in the dimethyl silicone oil, and escapes to be dissolved by the methanol or ethanol above the liquid level of the dimethyl silicone oil, after the reaction is stopped, the solution is stood for layering, and the alcohol solvent and the dimethyl silicone oil are separated to obtain the depolymerized paraformaldehyde solution. In addition, because proper amount of water existing in the paraformaldehyde plays a role of a chain transfer agent, microwave heating and a copper naphthalate or copper stearate catalyst play a role of catalyzing depolymerization, unstable hemiacetal terminal hydroxyl groups are continuously generated at two ends of molecules, and are continuously broken at two ends of a molecular chain, so that the depolymerization is accelerated, and the depolymerization is close to complete depolymerization.
Compared with the prior art, the invention has the following advantages:
The large amount of alkali or acid is used for catalyzing depolymerization of paraformaldehyde and simultaneously introducing impurities. In the prior art, the direct heating depolymerization effect and the direct heating depolymerization effect in ethanol and methanol are not ideal, and the invention utilizes the dimethyl silicone oil microwave thermal depolymerization and uses copper naphthalate or copper stearate as a depolymerization catalyst. The microwave effect of the paraformaldehyde can reduce the depolymerization activation energy of the paraformaldehyde, and experimental results show that copper naphthalate or copper stearate and copper powder have catalytic effect on depolymerization of the paraformaldehyde under the action of microwaves, and copper powder has poor catalytic effect due to the copper powder.
In practice, it was found that the copper powder, which is a component impurity, has a certain catalytic effect on the depolymerization of paraformaldehyde, but the copper powder is not easily and uniformly dispersed into the methyl silicone oil due to being a solid, and has less chance of being used as a base for paraformaldehyde. Copper naphthalate and copper stearate are selected to be better dispersed into the dimethyl silicone oil and catalyze depolymerization of paraformaldehyde.
Description of the embodiments
The invention is illustrated, but not limited, by the following specific examples.
Examples
First step, preparing raw materials and equipment: white solid particles of paraformaldehyde with the purity of 97 percent and the polymerization degree of 41.7, the Eastern Mountain organic silicon 201-350 simethicone, copper shanxi Zhongda naphthoate and a methanol superior product for the coking industry of melt are produced by Anhui Ruibu New material Co-Ltd, and a reaction kettle MKD-H4C1 is synthesized by microwaves; KATEWINSLET straight cylindrical c16×100 magnetic rotors; the stirring device is in a double stirring mode of mechanical stirring and magnetic stirring;
Secondly, adding paraformaldehyde particles and copper naphthalate accounting for 0.05% of the mass of the paraformaldehyde particles into the bottom of a microwave reaction kettle with a stirring device, wherein the water content of the paraformaldehyde particles is 1.6%, then adding silicone oil, wherein the mass ratio of the silicone oil to the paraformaldehyde is 1:0.5, the liquid level of the silicone oil exceeds that of the paraformaldehyde particles, adding methanol into the liquid level of the silicone oil, layering on the liquid level of the silicone oil, wherein the mass ratio of the methanol to the silicone oil is 4:3.86, and placing a stirring paddle of the stirring device below the liquid level of the silicone oil;
And thirdly, stirring at the stirring speed of 300rpm, wherein the surface temperature of the silicone oil is 83 ℃, and after microwave heating, condensing and refluxing for 43min, the wave power is 3200W, the frequency is 2450MHz, standing and layering, and separating to recover the alcohol solvent solution, thus obtaining the depolymerized formaldehyde solution.
The product is as follows: the formaldehyde content of the produced formaldehyde-methanol solution reaches 46.5%, the appearance is transparent liquid, no suspended matters exist, no large white turbidity exists at low temperature, the moisture is 0.9%, the iron content is less than 0.001%, the formic acid is less than 0.02%, and the formaldehyde yield is 99.5%.
Examples
First step, preparing raw materials and equipment: white solid particles of paraformaldehyde with the purity of 95 percent and the polymerization degree of 32.1, wanhua organosilicon SF60-100 dimethyl silicone oil, copper elegance maide stearate, a high-grade industrial ethanol product with the purity of 99.5 percent of the grain biochemistry in the clam port are produced by Anhui Ruibu new material Co-Ltd, and a reaction kettle MKD-H4C1 is synthesized by microwaves; KATE WINSLET straight cylindrical c16×100 magnetic rotors; the stirring device is in a magnetic stirring mode;
Secondly, adding paraformaldehyde particles and copper stearate accounting for 0.03 percent of the mass of the paraformaldehyde particles at the bottom of a microwave reaction kettle with a stirring device, wherein the water content is 2.2 percent, then adding silicone oil, wherein the mass ratio of the silicone oil to the paraformaldehyde is 1:0.4, the liquid level of the silicone oil exceeds the paraformaldehyde particles, adding an alcohol solvent at the liquid level of the silicone oil, layering on the liquid level of the silicone oil, wherein the mass ratio of the ethanol to the silicone oil is 4:4.8, and placing a stirring paddle of the stirring device below the liquid level of the silicone oil;
And thirdly, stirring is started, the stirring speed is 600rpm, the surface temperature of the silicone oil is 95 ℃, after the silicone oil is subjected to microwave heating, condensing and refluxing for 51min, the wave power is 3000W, the frequency is 2450MHz, and after standing and layering, the ethanol solution is recovered by separating liquid, so that the depolymerized formaldehyde solution is obtained.
The product is as follows: the formaldehyde content of the produced formaldehyde-ethanol solution reaches 45.8%, the appearance is transparent liquid, no suspended matters exist, no large white turbidity exists at low temperature, the water content is 1.0%, the iron content is less than 0.001%, the formic acid is less than 0.02%, and the formaldehyde yield is 99.4%.
Examples
First step, preparing raw materials and equipment: white solid particles of paraformaldehyde with the purity of 95 percent and the polymerization degree of 32.1 are produced by Anhui Ruibai new material limited company, wanhua organosilicon SF 60-100 dimethyl silicone oil, 350 meshes of copper powder of the constant of the Ruhuding, 99.5 percent of industrial ethanol superior products of grain biochemistry in the clam ports are produced, and a reaction kettle MKD-H4C1 is synthesized by microwaves; KATE WINSLET straight cylinder-shaped C16×100 magnetic rotor, and the stirring device is in a mechanical stirring mode;
Secondly, adding paraformaldehyde particles and 350-mesh copper powder accounting for 0.2% of the mass of the paraformaldehyde particles into the bottom of a microwave reaction kettle with a stirring device, wherein the mass ratio of the paraformaldehyde particles to the silicon oil is 1:0.4, adding ethanol into the liquid level of the silicon oil to exceed the paraformaldehyde particles, layering on the liquid level of the silicon oil, wherein the mass ratio of the ethanol to the silicon oil is 4:4.8, and placing a stirring paddle of the stirring device below the liquid level of the silicon oil;
And thirdly, stirring at the stirring speed of 500rpm, wherein the surface temperature of the silicone oil is 90 ℃, microwave heating, condensing and refluxing for 45min, the wave power is 3000W, the frequency is 2450MHz, standing and layering are carried out, unreacted copper powder is precipitated at the bottom of the reaction kettle, and the ethanol solution is recovered after separating liquid, so that the depolymerized formaldehyde ethanol solution is obtained, and the formaldehyde yield is 97.9%.
The product is as follows: the formaldehyde content of the produced formaldehyde-ethanol solution reaches 45.1%, the appearance is transparent liquid, no suspended matters exist, no large white turbidity exists at low temperature, the water content is lower than 1.0%, the iron content is less than 0.001%, and the formic acid content is less than 0.02%.
Note that: the detection is carried out with reference to GB/T9009-2011 industrial formaldehyde solution.
Claims (5)
1. A method for depolymerizing paraformaldehyde, comprising the steps of:
Firstly, adding paraformaldehyde particles and a depolymerization catalyst accounting for 0.03-0.05% of the mass of the paraformaldehyde particles and accounting for 0.03-0.05% of the mass of the paraformaldehyde particles into the bottom of a microwave reaction kettle with a stirring device, adding silicon oil, wherein the liquid level of the silicon oil exceeds the paraformaldehyde particles, adding an alcohol solvent into the liquid level of the silicon oil, layering on the liquid level of the silicon oil, placing a stirring paddle of the stirring device below the liquid level of the silicon oil, wherein the depolymerization catalyst is copper naphthalate or copper stearate, the mass ratio of the silicon oil to the paraformaldehyde is 1:0.4-0.5, the mass ratio of the alcohol solvent to the silicon oil is 4:3.86-4.8, the silicon oil is 201 methyl silicone oil, the alcohol solvent is one of methanol and ethanol, the microwave power is 3000-3200W, and the frequency is 2450MHz;
And secondly, stirring is started, microwave heating is carried out for 3-5 min at intervals, after microwave heating, condensing and refluxing for 43-51 min, standing and layering are carried out, and then the alcohol solvent solution is recovered by liquid separation, so that the depolymerized formaldehyde solution is obtained.
2. The method for depolymerizing paraformaldehyde according to claim 1, wherein said stirring means in the first step is one of magnetic rotor stirring and mechanical anchor stirring.
3. The depolymerization method of paraformaldehyde according to claim 1, wherein the surface temperature of the silicone oil in the second step is 83-95 ℃.
4. The depolymerization method of paraformaldehyde according to claim 1, wherein the stirring speed in the second step is 300-600 rpm.
5. The method for depolymerizing paraformaldehyde according to claim 1, wherein the purity of paraformaldehyde particles is 92% -96%.
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| GB953389A (en) * | 1961-03-09 | 1964-03-25 | Leuna Werke Veb | Process for the production of anhydrous formaldehyde |
| CN1029623C (en) * | 1989-06-15 | 1995-08-30 | 纳幕尔杜邦公司 | Stabilized polyacetal compositions |
| CN101723815A (en) * | 2009-10-16 | 2010-06-09 | 南京大学 | Technology for resource recovery of formaldehyde in pesticide waste water by utilizing catalytic rectification |
| CN103641970B (en) * | 2013-12-04 | 2015-07-29 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of high-solid-content melamino-formaldehydresine resine |
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| CN113666803B (en) * | 2021-08-30 | 2023-09-01 | 四川众邦新材料股份有限公司 | Method for synthesizing propargyl alcohol |
| CN114853590A (en) * | 2022-04-24 | 2022-08-05 | 漳州市龙文翰苑化工有限公司 | Novel polyformaldehyde depolymerization method |
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| CN116589646A (en) * | 2023-04-21 | 2023-08-15 | 安徽瑞柏新材料有限公司 | Production process method of paraformaldehyde |
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