CN107266412A - CO2Or carbonate or formates and water are method and the application that raw material prepares the cyclic ethers such as metaformaldehyde - Google Patents
CO2Or carbonate or formates and water are method and the application that raw material prepares the cyclic ethers such as metaformaldehyde Download PDFInfo
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Abstract
The present invention relates to one kind with CO2Or the method that carbonate or formates and water prepare metaformaldehyde and four polyformaldehyde and para-acetaldehyde and the cyclic ethers such as the methaldehyde and poly- glyoxal for raw material；And it is related to CO2Or carbonate or formates are used as a kind of application for the raw material for preparing metaformaldehyde this class cyclic ethers.Compared with traditional production technology, its unique feature is：Using CO2Or carbonate or formates and water are raw material, and the cyclic ethers type organic such as metaformaldehyde is prepared instead of the fossil feedstock such as formaldehyde or ethylene glycol or oxirane.Whole preparation process does not consume hydrogen or other any fossil resources, but with CO2For carbon source, cyclic ethers type organic is synthesized by hydrogen source of water.Therefore, the inventive method both significantly have dropped the cost for preparing the cyclic ethers product such as metaformaldehyde, a kind of endless renewable hydrocarbon organic matter (artificial oil) resource be have developed again, its essence is a kind of artificial photosynthesis of no light.
Description
First, technical field
The present invention relates to one kind with CO2Or carbonate or formates and water are that raw material prepares trimerization
The method of formaldehyde and four polyformaldehyde and para-acetaldehyde and the cyclic ethers such as the methaldehyde and poly- glyoxal；
And it is related to CO2Or carbonate or formates are used as a kind of metaformaldehyde this class cyclic ethers of preparing
The application of raw material.Compared with traditional production technology, its unique feature is：Adopt
Use CO2Or carbonate or formates and water are raw material, instead of formaldehyde or ethylene glycol or oxirane
The cyclic ethers type organic such as metaformaldehyde is prepared etc. fossil feedstock.Whole preparation process does not consume hydrogen
Gas or other any fossil resources, it is not necessary to input luminous energy and electric energy, but with CO2For carbon source,
Cyclic ethers type organic is synthesized by hydrogen source of water.Therefore, the inventive method both significantly declines
Prepare the cost of the cyclic ethers product such as metaformaldehyde, again have developed it is a kind of it is endless can be again
Raw hydrocarbon organic matter (artificial oil) resource, it is artificial photosynthetic its essence is a kind of no light
Effect.
2nd, background technology
The method of the present invention there are no any related document and the data even report of relevant information
The second law of thermodynamics on road, especially method and textbook of the invention seems to disagree,
The category of original innovation should be belonged to.So on the column of present context technology one, it is necessary to illustrate
The history of the present invention.
It is well known that oil is the core for weighing energy security.One national oil supply pair
The degree of outer dependence is higher, and its safety problem is more prominent.Chinese oil consumption in 2015
5.43 hundred million tons, external dependence degree head broken 60%.Moreover, China CO2Discharge capacity is estimated 2016
Year will exceed the U.S., rank the whole world first.At present, production of energy and consumptive link are caused
Environmental problem is seriously difficult to administer.The pollution of serious haze swept across China since 2013
Many vital areas, exactly most important of which disposal of pollutants source, the utilization of coal and oil.
Therefore the energy security of China is not only the diplomatic containing of international geopolitics fought with interests it is grand
Problem, even more realizes the active demand of domestic economy transition and sustainable development[1].It can not put
Doubt：If can be with CO2With water be the artificial synthesized oil of raw material, just look like forest pass through it is photosynthetic
Effect prepares that timber is the same, can must fundamentally solve oil exhausted and climate change
Problem, also can in time and expeditiously solve the problems, such as haze.But so far, people
Do not find a CO also2With the practicality that water is Material synthesis hydrocarbon (oil)
Method, method of the invention is exactly arisen at the historic moment for this, be a kind of practicality can be from root
The method that problem is solved in sheet.The present inventor is engaged in chemical pharmaceutical major technical work many decades,
CO is taken in January, 2012 in Christian era2Or sodium carbonate and it is hydrated into grinding for hydrocarbon
Study carefully, the CO of high yield and low cost was have successfully completed to 20152It is Material synthesis with water
The technology and industrialization process design of hydrocarbon organic matter (oil), have been provided with completely
Practicality.
But, perhaps it is this method with classical thermodynamics second law against people in the art
The extraordinary reliability for querying this method of member, therefore, enumerating following " facts 1 " in this specification
With the corresponding principles of chemistry of elaboration." fact is 1 " simple and easy to apply, chemical field it is common
University student can also carry out that " process of the fact 1 ", which simultaneously obtains sample, puts and in desktop or send authority
Department certification.Undoubtedly, as long as " fact 1 " is true and reliable, and this method is also inevitable true
It is real reliable.
" the fact 1 "：The common stirred reactor of selection, input mass concentration is 40-50%'s
100 grams of the KOH aqueous solution, put into again 99% 30 grams of potash solid reagent and common zinc powder
30 grams, start stirring, under conditions of open normal pressure, control 105 DEG C -140 DEG C of temperature,
Reaction 24-48 hours is continuously stirred, sample is taken, with radar stealthy materials or gas-chromatography or liquid phase color
The modern instrument such as spectrum or mass spectrum or nuclear magnetic resonance is analyzed and identified, and each analysis method is all
It can confirm：Potassium carbonate and water have been converted to the mixture (artificial oil) for hydrocarbon organic matter,
While the KOH of coproduction oxygen and equivalent；CO is absorbed with the KOH2Gas, generates equivalent
Potassium carbonate；In the presence of Zn/KOH, potassium carbonate and water are converted into hydrocarbon organic matter again；
Even natural vegetation grow environment temperature (- 10 DEG C -40 DEG C) under, potassium carbonate with
The reaction of this by-product oxygen can also occur for water, it is only necessary to when giving enough stirring reactions
Between (in 100 days), potassium carbonate is eventually converted into the conversion ratio accessible 100% of " artificial oil ".
Potassium carbonate and water are so irreversibly converted into hydrocarbon organic matter and oxygen and KOH, by this
KOH is used for the potash solid that absorbing carbon dioxide gas is converted into equivalent, and utilizing again should
Potash solid and water are that raw material prepares hydrocarbon organic matter coproduction oxygen and KOH simultaneously, are so followed
Ring is reciprocal, when constantly preparing hydrocarbon organic matter and oxygen forever, the raw material actually consumed
Only carbon dioxide and water, this exactly so-called " no light artificial photosynthesis " synthesis
The fact that " artificial oil "." fact 1 " repeatedly tests confirmation by tens of times,
Have become a hard fact.
Traditional《Carbon dioxide chemistry》Think：Due to " carbon dioxide thermodynamic stability
And kinetic inertness, to realize that effectively conversion with that must put into greatly again using carbon dioxide
The energy of amount, this is also effective conversion and utilizes the maximum obstacle of carbon dioxide.Solve the problems, such as
Key be utilize metal complex isoreactivity activation of catalyst carbon dioxide ".It is reported that
The catalyst of the activation carbon dioxide of open report has exceeded 5000, but neither one possesses
The practicality of problem can be solved in time, and the overwhelming majority can only rest on the paper of research
In, only a few is rested in demonstration plant.And the method for the present invention is fully proved：It is most normal
Advise most common catalyst --- Zn/KOH, exactly activate carbon dioxide most excellent most practical
Catalyst, this also exactly most important creativeness of the present invention.
The chemically angle analysis of pharmaceutical technology, CO2Molecular structure is both as the accumulation in dilute hydrocarbon is double
Key is again as the accumulation carbonyl of carbonyls.And the general knowledge of organic reaction informs us：Typically
Cumulated double bond has active reactivity worth, especially as CO2This small molecule accumulation carbonylation
Compound, does not contain any other element in addition to C and O such as hydrogen, therefore is directed to CO in theory2
Not only influence the spatial obstacle very little of its reactivity, and CO2Can not occur general carbonyl
The side reaction of the types such as aldol condensation, Kang Nizhaluo that compound often has, CO2Intrinsic selection
Property should be higher.Exactly under this guiding theory, and complementary design and successfully realize
Following " facts 2 ".
" the fact 2 "：The common container of selection, input mass concentration is 85% KOH and pure
Water is respectively 50 grams, and 99% 20 grams of potash solid is put into again, is well mixed；It is placed in
In the vacuum tank for completely cutting off air, at ambient temperature, 40 days are stood, sample 1 is taken；Continue
150 days are stood, sample 2 is taken；Continue to stand 360 days, sample 3 is taken, with radar stealthy materials or gas
Phase chromatogram or liquid chromatogram or the identification of mass spectrum or nuclear magnetic resonance spectroscopy, can all be proved
The compound containing C-H bond is generated, the total recovery of hydrocarbon organic matter is 10% for sample 1
More than；It is more than 75% for sample 2；It is more than 99%, coproduction equivalent for sample 3
KOH, the oxygen of by-product can be collected from vacuum tank.
" fact 2 " is proved：Only rely on KOH strength, under conditions of normal temperature and pressure,
Carbonate and water just can be irreversibly converted into compound (" the artificial stone containing C-H bond
Oil ").Only rely on KOH strength, additionally it is possible to which potassium carbonate and water are converted into rock sugar, see
Following " facts 3 ".
" the fact 3 "：40% 150 grams of the KOH aqueous solution is added March 2014 Christian era
In beaker, it is statically placed in air 25-35 days, then takes wherein colourless transparent liquid to be placed in 20ml
Glass sample bottle in, screw the bottle cap of sample bottle, be stored in sample cabinet, to Christian era 2016
It is March in year, it is seen that one layer of lump shaped crystalline is arranged at the bottom of sample bottle, takes out the crystallization, final true
Surely it is polycrystalline rock sugar.
Above-mentioned " fact 1 " or " fact 2 " or " fact 3 " is each chemical personage
Can body face field experiment and obtain the thing of conclusion, should also be the common of petrochemical plant
Workman's body faces scene and sees process smelling with regard to the thing that can understand, therefore is the thing of undeniable iron
It is real, it is with CO2It is that raw material prepares hydrocarbon organic matter or " artificial oil " technology is even with water
The successful exploitation of " artificial synthesized grain " technology has established solid foundation with realization, especially
It is to provide one in time conscientiously to safeguard national security and synchronously solving haze pollution problem
Feasible technology path, is the solid reliable background technology of the present invention.
In addition, the present inventor had once summed up the iron rule of an organic reaction：It is every to contain=C=O
The compound of (carbonyl) group, including carbonate and chemical fertilizer, it is dissolved in the molten of super base
In liquid, including the KOH aqueous solution that mass concentration is more than 40%, necessarily can not be steady in a long-term
In the presence of chemical conversion reaction must occur for=C=O groups, be converted into-O-C-C-O- groups
Or-O-C-O- groups or CH2Group or=C=C=groups.It is converted primarily into as which kind of group, by
The process conditions specifically reacted and the domination of base strength.During general lower temperature, often occur
C-C coupling reaction, primary product is the chemical combination such as ethylene glycol and hydroxyacetic acid and glycollic aldehyde
Thing.And the temperature that the present invention is selected is higher, more than 138 DEG C, it is more difficult to occur carbon-to-carbon coupling
Reaction, primary product is polyformaldehyde and the ring-type ethers compound such as metacetaldehyde and poly- glyoxal.
By searching for document on the net, it is a unknown reaction to find this, can be described as " carbonyl C-O
It is coupled annulation ", it is a kind of inverse composition reaction method to belong in nature.Experiment is proved：Choosing
It is reverse that as raw material this is carried out with carbonate or formates or carboxylate than group compounds of aldehydes and ketones
Synthetic reaction it is better.Its reaction mechanism is：The compound of the group containing C=O, dense
In KOH solution, under the temperature conditionss more than 140 DEG C, by being converted into very unstable hydroxyl
Base Cabbeen intermediate, immediately occurs bimolecular C-O coupling annulation, generation hexatomic ring and
The ring-type ethers compound such as octatomic ring.Potassium carbonate generates dihydroxy methylene Cabbeen, potassium formate
Generate monohydroxy methylene Cabbeen.For example with potassium formate synthesizing triformol and four polyformaldehyde,
With the potassium acetate synthesis methaldehyde, with formaldehyde or acetaldehyde synthesizing triformol or para-acetaldehyde,
Poly- glyoxal etc. is synthesized with glyoxal, these successful chemical cases are also the present invention's
One of background technology.
3rd, the content of the invention
It is an object of the invention to provide one kind with CO2It is raw material or carbonate with water and water is former
Material or formates and water prepare metaformaldehyde and four polyformaldehyde and para-acetaldehyde and four for raw material and gathered
There is provided CO for the method for acetaldehyde and the cyclic ethers such as poly- glyoxal and glycolaldehyde dimer and oxirane2
Or carbonate or formates as one kind prepare metaformaldehyde and four polyformaldehyde and para-acetaldehyde and
The raw material or reagent of the methaldehyde and poly- glyoxal and glycolaldehyde dimer and oxirane should
With.
One kind prepares metaformaldehyde and four polyformaldehyde and para-acetaldehyde and the methaldehyde and poly- second two
The method of the cyclic ethers such as aldehyde and glycolaldehyde dimer and oxirane, it is characterized in that from Zn/KOH
For catalyst, CO is chosen2Or the raw material or reagent that carbonate or formates are synthetic reaction；Its
Middle KOH represents metal hydroxides, including sodium hydroxide and potassium hydroxide and lithium hydroxide and
Calcium hydroxide etc., Zn represents metal and non-metal simple-substance or their alloy, including zinc list
Matter and iron simple substance and titanium simple substance and carbon simple substance and sulphur simple substance and alumel and iron-carbon alloy etc.
Deng.
With CO2Or carbonate or formates are Material synthesis metaformaldehyde and four polyformaldehyde and three
Metacetaldehyde and the methaldehyde and the cyclic ethers such as poly- glyoxal and glycolaldehyde dimer and oxirane
Method, includes several steps of following sequence：
Selection common electric stirring reactor or filler tower reactor, and install one instead
The circulating pump of material is answered, while installing the filtering of a duct type in the exit of the circulating pump
Device；The high concentration KOH aqueous solution and common zinc powder or activity of amount of calculation are put into the reactor
Titanium valve or technique of activated ferrous powder with or activated carbon powder or their alloyed powder, or by these zero-valent metals with
Nonmetallic and its their alloy is used as the filler in filler tower reactor；Start stirring and
Circulating pump, under conditions of open normal pressure, controls 138 DEG C -170 DEG C of temperature, controlledly
Put into the CO of amount of calculation2Or carbonate or formates, continuously stir or pump circulation 4-10 hours
Left and right；Then filter while hot, by filtrated stock in crystallizing at room temperature 1-4 hours, then normal temperature mistake
Leaching goes out crystal, is to contain three in the mixture of metaformaldehyde and four polyformaldehyde, filtrated stock
Metacetaldehyde and poly- glyoxal hydrate, can directly be applied mechanically, can also be by separation Posterior circle set
With；The methaldehyde and other cyclic ether compounds for being insoluble in water are taken out from pipelined filter；
The gases such as the oxirane and ketenes that are discharged with solvent absorption from the gas vent of reactor；
The KOH of coproduction is deposited in filtrated stock, and the oxygen of by-product is directly discharged into air.
KOH in above-mentioned steps represents sodium hydroxide or potassium hydroxide or lithium hydroxide or hydrogen-oxygen
Change the metal hydroxides such as calcium.
4th, specific embodiment
Embodiment 1
The common electric stirring reactor with condenser of selection, installs a reaction mass and follows
Ring pump, and the pipelined filter that is installed in series in the exit of the circulating pump, material from
The lower curtate outlet of reactor flows through circulating pump and filter, passes through the upper entrance stream of reactor
Enter reactor；Put into the CO that mass concentration is 99%2Or potassium carbonate or 100 grams of potassium formate or 300
Gram, while putting into 1000 grams of the KOH hydrothermal solutions that mass concentration is 40-70%, put into again
Common zinc powder or technique of activated ferrous powder with or active titanium valve or activated carbon powder or al-ni alloy powder or active iron
300 grams of carbon alloy powder, starts stirring and circulating pump, under conditions of open normal pressure, control
Temperature is 138 DEG C -170 DEG C, maintains the reflux for state, and the time continuously stirred with pump circulation is
4-10 hours, stop stirring and circulating pump, while hot (90 DEG C -110 DEG C) filterings；Will filtering mother
Liquid is down to room temperature, stands still for crystals 1-4 hours, and filtering is taken out crystal and dried, and obtains dry product 47
Gram, it is the mixing crystal of metaformaldehyde and four polyformaldehyde, wherein the content of metaformaldehyde is 90%
More than；There are acetaldehyde and formaldehyde and glyoxal and oxirane from condensator outlet in course of reaction
Overflow, absorbed respectively with water and acetone equal solvent with the mixed gas of ketenes；From circulating pump
Taken out in the pipelined filter of outlet the methaldehyde and anhydrous poly- glyoxal and four polyformaldehyde and
Other cyclic ether compounds solids for being insoluble in water, totally 13 grams；The para-acetaldehyde and KOH of coproduction
It is deposited in filtrated stock, can directly applies mechanically, or passes through ion-exchange membrane electrodialysis method
Used after the para-acetaldehyde separation and recovery in filtrated stock, then by the pure KOH aqueous solution of recovery
In the synthetic reaction of next batch；The oxygen of coproduction is directly discharged into air.
Embodiment 2
The common electric stirring reactor with condenser pipe of selection, puts into mass concentration
60%-70% KOH 100 grams of saturated aqueous solutions of overheat, while putting into common zinc powder or active titanium
30 grams of the zero-valent metal such as powder or technique of activated ferrous powder with or activated carbon powder and non-metal simple-substance powder, startup is stirred
Mix, under conditions of open normal pressure, be warming up to reflux temperature, and maintain the reflux for state, have
CO is added dropwise in control ground2Or 10 grams or 30 grams of carbonate or formates, control feeds 1 each time
Gram or 3 grams or so, add flowed back 20 minutes after material each time, then will by the control of valve
Phegma is introduced into another low temperature (- 5 DEG C) crystallizer, and is kept to reactor supplement water
Reactor inner horizontal is constant, thus control ground charging 10 times, 10 grams of CO2Or 30 grams
Carbonate or 30 grams of formates are added；Then stop supplement water, stop stirring, by low temperature knot
The crystal filtering precipitated in brilliant device, obtains 4.2 grams or so of metaformaldehyde crystal, content is 95%,
The filtrated stock is the aqueous solution containing para-acetaldehyde and metaformaldehyde, and lower process can be sent to separate
Reclaiming turns into para-acetaldehyde product and metaformaldehyde product；Simultaneously by the feed liquid mistake in reactor
Filter, filtrated stock directly applies mechanically, and uses acetone solution filter cake, isolate the metal of addition with it is non-
Metal powder, then acetone soln is distilled, crystallize, filter, and obtains the methaldehyde and anhydrous
1.1 grams of trimerization glyoxal (bicyclic glycolide) solid mixture.
Embodiment 3
The common filler tower reactor of selection, supporting installation condenser and reaction mass circulation
Pump, circulating-pump outlet installs a pipelined filter, using zinc or zeroth order titanium or Zero-valent Iron
Or activated carbon or alumel or iron-carbon alloy are material, preparing turns into screen waviness packings,
It is used as the packing layer of the filler tower reactor；1000 grams of the KOH hot solutions of input 70% or so,
Open the circulation pump, under conditions of normal mouth normal pressure, controls 140 DEG C -170 DEG C of temperature, from this
The charging aperture of reactor is homogeneously added into CO2150 grams of gas, or it is homogeneously added into potassium carbonate
300 grams or 300 grams of sodium formate, it is reflux state, pump circulation to keep the temperature in reactor
After 3-5 hours, by the material in reactor with being pumped into low temperature crystallization device more than 100 DEG C
In, 70 DEG C or so stand 1 hour filtering, drying, obtain 13 grams of four polyformaldehyde solid or
8.6 grams, content is 98%, and the filtrated stock then is stood into 3-5 hours below 20 DEG C,
Again by crystal filtering, the drying of precipitation, 65 grams or 44 grams of metaformaldehyde solid, content are obtained
For 98%, the secondary filter mother liquor is the KOH containing para-acetaldehyde and poly- glyoxal hydrate
The aqueous solution, can be applied mechanically with direct circulation and be reprocessed after 15 times, if that add is pure CO2Gas
Body, can be to reprocess after recycled 200 times；The secondary filter mother liquor can also be sent into
Lower process separation and recovery turns into para-acetaldehyde product and poly- glyoxal hydrate product；While from
Methaldehyde product is collected in pipelined filter and anhydrous poly- glyoxal product amounts to 17 grams
Or more than 11 grams；The ethylene oxide gas and ketene gas of by-product pass through absorption distillation process
As aqueous solution of ethylene oxide product and ketene dimer product, the oxygen of by-product is directly discharged into greatly
Gas.
KOH in above-described embodiment 1 or embodiment 2 or embodiment 3 represents sodium hydroxide or hydrogen
The metal hydroxides such as potassium oxide or calcium hydroxide or lithium hydroxide.
Embodiment 4
The common electric stirring reactor of selection, input mass concentration is water-soluble for 50% KOH
100 grams of liquid, put into again common zinc powder or active titanium valve or technique of activated ferrous powder with or al-ni alloy powder or
Active iron-carbon alloy powder or activated carbon powder or 30 grams of sulphur simple substance powder, while putting into 10 grams of CO2
Or the carbonate or the formates of 30 gram 99% of input of 30 gram 99% of input, start stirring,
Under conditions of open normal pressure, it is less than 40 DEG C to control temperature, and stirring reaction 48 hours is quiet
Put, filter, filtrated stock is the aqueous alkali of poly- glyoxal hydrate, poly- glyoxal water
The content of compound is 5% or so, and separation KOH is carried out with common ion-exchange membrane electrodialyser
With poly- glyoxal, poly- 32 grams of glyoxal water solution is obtained, its mass concentration is 20% or so.
Embodiment 5
One common electric stirring reactor with condenser pipe of selection, puts into 90 gram masses
Concentration is 99% KOH solids and 10 grams of water, and technique of activated ferrous powder with or activated carbon powder 30 are put into again
Gram；Start stirring, be slowly warming up to backflow, under conditions of normal mouth normal pressure and reflux temperature,
Gradually add 9 gram 99% of CO2, gradually add 99% 30 grams of sodium carbonate or gradually add
30 grams of 99% sodium formate, constantly has gas overflowing in course of reaction from the outlet of condenser pipe,
The gas is introduced into supporting absorption and separation process to be handled, ethylene oxide gas product is obtained
3.2 grams, content is 98%, obtains 2.9 grams of ketene dimer product, content is 98%；It is deposited in
Material in reactor can be applied mechanically directly 200 times as super basic catalyst.
Embodiment 6
A common electric stirring reactor with condenser pipe is chosen, input mass concentration is
51 grams of 99% sodium hydroxide and 99% 49 grams of potassium hydroxide, add water 10 grams, put into again
Common zinc powder or 30 grams of zeroth order titanium valve or Raney's nickel powder, start stirring, in open normal pressure and
Under conditions of more than 240 DEG C of temperature, 10 grams of pure CO are uniformly added dropwise2Or pure potassium carbonate is uniformly added dropwise
30 grams or pure 30 grams of sodium formate is uniformly added dropwise, at this moment constantly has gas from the outlet of condenser pipe
Body overflows, and is the mixture gas of acetylene and ethene, and the gas is introduced into next gas inhales
Knock off sequence, absorbed and separated, obtain 2.9 grams of acetylene gas, content is 98%, obtains second
2.1 grams of alkene gas, content is 98%；The material retained in the reactor is superpower as one kind
Base catalysis system can be applied mechanically directly 200 times.
Embodiment 7
The common electric stirring reactor of selection, input mass concentration is 30% and without other impurity
100 grams of calcium hydroxide water slurry, active 30 grams of titanium valve is put into again, starts stirring,
Under conditions of open normal pressure, 90 DEG C or so of temperature is controlled, 10 gram 99% of CO is slowly added into2
Or 30 gram 99% of carbonate or 30 gram 99% of formates are added, continuously stir reaction 48
Hour, then by unit processes such as conventional cooling, sedimentation, filtering, separation, obtain
4.3 grams of the glycolaldehyde dimer solid of white, content is 90%, and the ethylene glycol of by-product is retained
In the reactor, recyclable is product, and the oxygen of by-product is directly discharged into air.
Embodiment 8
The common electric stirring reactor with condenser pipe of selection, putting into mass concentration is
70% 100 grams of the overheat saturation KOH aqueous solution, starts stirring, open normal pressure and is keeping back
Under conditions of stream temperature, 10 gram 99% of CO is slowly added into2Or add 30 gram 99% of carbonic acid
Salt or the formates of 30 gram 99% of addition, continuous insulated and stirred are reacted 48 hours, Ran Houting
Stirring is stood, and is naturally cooling to room temperature, there is crystal precipitation, is filtered, and drying obtains trimerization first
4.9 grams of aldehyde dry product, content is 98%.
Claims (4)
1. one kind prepares metaformaldehyde and four polyformaldehyde and para-acetaldehyde and the methaldehyde and poly- second
The method of the cyclic ethers such as dialdehyde and glycolaldehyde dimer and oxirane, it is characterized in that from Zn/KOH
For catalyst, CO is chosen2Or the raw material or reagent that carbonate or formates are synthetic reaction；Its
Middle KOH represents metal hydroxides, including sodium hydroxide and potassium hydroxide and lithium hydroxide and hydrogen
Calcium oxide etc., Zn represents metal and non-metal simple-substance or their alloy, including zinc simple substance
With iron simple substance and titanium simple substance and carbon simple substance and sulphur simple substance and alumel and iron-carbon alloy etc..
2. with CO2Or carbonate or formates be Material synthesis metaformaldehyde and four polyformaldehyde and
Para-acetaldehyde and the methaldehyde and the cyclic ethers such as poly- glyoxal and glycolaldehyde dimer and oxirane
Method, include several steps of following sequence：
Selection common electric stirring reactor or filler tower reactor, and a reaction is installed
The circulating pump of material, while installing the filter of a duct type in the exit of the circulating pump；
The high concentration KOH aqueous solution and common zinc powder or active titanium valve of amount of calculation are put into the reactor
Or technique of activated ferrous powder with or activated carbon powder or their alloyed powder, or by these zero-valent metals with it is nonmetallic
And its their alloy is used as the filler in filler tower reactor；Start stirring and circulating pump,
Under conditions of open normal pressure, 138 DEG C -170 DEG C of temperature is controlled, amount of calculation is controlledly put into
CO2Or carbonate or formates, continuously stir or pump circulation 4-10 hours or so；Then take advantage of
Heat filtering, takes out crystal in crystallizing at room temperature 1-4 hours, then normal temperature filtering by filtrated stock, is
Contain para-acetaldehyde and poly- glyoxal in the mixture of metaformaldehyde and four polyformaldehyde, filtrated stock
Hydrate, can directly be applied mechanically, and can also be applied mechanically by separation Posterior circle；From pipelined filter
Take out the methaldehyde and other cyclic ether compounds for being insoluble in water；With solvent absorption from reactor
The gases such as the oxirane and ketenes of gas vent discharge；It is female that the KOH of coproduction is deposited in filtering
In liquid, the oxygen of by-product is discharged directly into air.
3. carbon dioxide or carbonate or formates prepare metaformaldehyde and four poly- first as one kind
Aldehyde and para-acetaldehyde and the methaldehyde and poly- glyoxal and glycolaldehyde dimer and oxirane etc.
The application of the raw material or reagent of cyclic ethers.
4. carbon dioxide or carbonate or formates prepare ketenes and acetylene and second as one kind
The application of the raw material or reagent of alkene and ketene dimer.
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| CN201610237450.1A CN107266412A (en) | 2016-04-09 | 2016-04-09 | CO2Or carbonate or formates and water are method and the application that raw material prepares the cyclic ethers such as metaformaldehyde |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524326A (en) * | 2012-07-03 | 2014-01-22 | 李坚 | Technical route for synthesizing oxalic acid, oxalate, ethylene glycol, methylal and ethylene glycol monomethyl ether by using CO2 or CO |
| CN103570528A (en) * | 2012-07-30 | 2014-02-12 | 李坚 | Method for preparing hydroxy acid and derivatives thereof, as well as propylene glycol, propanol, ethylene glycol and ethanol from CO or CO2 |
| CN103570485A (en) * | 2012-07-20 | 2014-02-12 | 李坚 | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO |
| CN104876818A (en) * | 2014-02-27 | 2015-09-02 | 李坚 | Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof |
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2016
- 2016-04-09 CN CN201610237450.1A patent/CN107266412A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524326A (en) * | 2012-07-03 | 2014-01-22 | 李坚 | Technical route for synthesizing oxalic acid, oxalate, ethylene glycol, methylal and ethylene glycol monomethyl ether by using CO2 or CO |
| CN103570485A (en) * | 2012-07-20 | 2014-02-12 | 李坚 | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO |
| CN103570528A (en) * | 2012-07-30 | 2014-02-12 | 李坚 | Method for preparing hydroxy acid and derivatives thereof, as well as propylene glycol, propanol, ethylene glycol and ethanol from CO or CO2 |
| CN104876818A (en) * | 2014-02-27 | 2015-09-02 | 李坚 | Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof |
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