CN105272836A - Method for preparing formaldehyde alcohol solution - Google Patents
Method for preparing formaldehyde alcohol solution Download PDFInfo
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- CN105272836A CN105272836A CN201410352601.9A CN201410352601A CN105272836A CN 105272836 A CN105272836 A CN 105272836A CN 201410352601 A CN201410352601 A CN 201410352601A CN 105272836 A CN105272836 A CN 105272836A
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- amylalcohol
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Abstract
The invention relates to a method for preparing a formaldehyde anhydrous alcohol solution and preparing a new formaldehyde alcohol solution from the prepared formaldehyde anhydrous alcohol solution, and particularly the method comprises that a formaldehyde aqueous solution and alcohol are subjected to azeotropic distillation in a distillation tower to prepare the formaldehyde anhydrous alcohol solution; the formaldehyde anhydrous alcohol solution is subjected to gas-liquid two phase separation in a flash tank to obtain formaldehyde gas and recycled alcohol; the formaldehyde gas and alcohol are subjected to countercurrent absorption in an absorption tower, to obtain the new formaldehyde alcohol solution.
Description
Technical field
The present invention relates to a kind of method being prepared formaldehyde anhydrous alcohol solution by formalin.
Background technology
Formaldehyde is a kind of important basic material in Organic Chemical Industry, is widely used in the industry-by-industries such as chemical industry, medicine, weaving, wood working, also can be used for preparing resol, urotropine, tetramethylolmethane etc. simultaneously, and its consumption is annual all in increase.Formaldehyde generally stores in form of an aqueous solutions and transports, and concentration is generally between 37% ~ 55%, commercially available based on 37%.Industrial general use be all the aqueous solution of formaldehyde, but along with development in recent years, some industrial combination only needing formaldehyde or formaldehyde and alcoholic solution, meanwhile also need to remove a large amount of water, this just makes the application of formalin, brings restriction.
Formaldehyde alcoholic solution be a kind ofly also apply less a kind of development of novel reagent in the world at present, but it has very large using value and development prospect.Such as formaldehyde methanol solution can mainly as the raw material of " methylating " urea or terpolycyantoamino-formaldehyde resin.Use formaldehyde methyl alcohol resin not only to make production of resins business no longer need separately to process methyl alcohol, decrease several times must from resin reaction device product the object of Separation of Water.German patent DE 10004562 (2001), introduces the dehydration film that a kind of polyvinyl alcohol of being studied by BASF Corp. of Germany is made, can by containing 20%-65% formaldehyde, 15%-60%C
1-C
5alcohols and 20%-65% water are condensed into containing 49%-70% formaldehyde, 20%-54%C
1-C
5the formaldehyde alcoholic solution of alcohols and 1%-35% water.We consider that formaldehyde is a kind of the simplest carbonyl compound that various polymerization very easily occurs simultaneously, therefore its storing condition has the Liquified gas tanker of self, especially at low temperatures, formalin has the tendency of polymerization, very easily form crystalline deposit, and then make formalin rotten and cannot use.And it is found that the solubleness of formaldehyde in methyl alcohol is larger, the methanol solution containing 55% formaldehyde also can not produce precipitation in room temperature placement, and its essence is exactly play a kind of effect of stopper.
And at present in world wide, the producer of manufacture formaldehyde alcoholic solution is little, Texas, USA is one of manufacturer uniquely few in number.In its formaldehyde methanol solution produced, formaldehyde accounts for 55%, and methyl alcohol accounts for 35%, also has the water of 10%.Therefore, this just prepares formaldehyde alcoholic solution for our R&D and production and brings opportunity.
Above context analyzer shows, formaldehyde alcoholic solution not only can bring very large economic worth, and the demand that simultaneously can solve chemical industry and every profession and trade formaldehyde alcoholic solution does not introduce water simultaneously, avoids the dehydration operation of follow-up complicated procedures of forming.Also play preservation formaldehyde simultaneously, prevent the object of rotten polymerization reaction take place.
Summary of the invention
The object of the invention to be to provide with formalin and alcohol as initial feed, prepares the method for formaldehyde anhydrous alcohol solution through various sepn process continuous print.Described alcohol is that described alcohol can refer to C
1-C
12monohydroxy-alcohol, it is represented by general formula R OH, and wherein R represents the group optionally replaced by one or more substituting group, and described group is selected from the alkyl of straight chain, side chain.
The present invention its specifically comprise three steps: first, be formalin (massfraction 0.1% ~ 60%) and C
3-C
8the process of anhydrous formaldehyde alcoholic solution is prepared in the rectifying in rectifying tower of any one alcohol; Secondly, anhydrous formaldehyde alcoholic solution is in the gas-liquid separation of flash tank; Finally, in absorption tower, C
1-C
12the absorption process of any one PARA FORMALDEHYDE PRILLS(91,95) in alcohol.
The present invention first with formalin (massfraction 0.1% ~ 60%) and alcohol for raw material, under the operating parameters conditions such as certain pressure, temperature, reflux ratio, in rectifier unit, carry out rectifying separation process obtains formaldehyde anhydrous alcohol solution; Then be raw material by the formaldehyde anhydrous alcohol solution prepared, under the operating parameters conditions such as certain pressure, temperature, gas-liquid two-phase separation is carried out in flash tank or still kettle, the formaldehyde gas steamed is passed in absorption tower, under the operational conditions such as certain pressure, temperature, carry out the process absorbed with the second alcohol.
Detailed description of the present invention
As mentioned above, formaldehyde anhydrous alcohol solution prepared by the present invention and prepare new formaldehyde alcoholic solution by formaldehyde anhydrous alcohol solution, it specifically comprises following step:
The first step, prepares formaldehyde anhydrous alcohol solution.After first being mixed with alcohol by a certain proportion of formalin, be driven in rectifying tower by pump, wherein alcohol serves the effect of entrainer.Because the alcohol added can form binary azeotrope with water, and azeotropic point is general all lower than the boiling point of formalin (massfraction 0.1% ~ 60%), control certain temperature and pressure, just azeotrope can be steamed from tower top, and after being separated by condenser, phase splitter, the liquid layer being rich in alcohol passes back into tower, and another water layer extraction, finally can obtain formaldehyde anhydrous alcohol solution by tower reactor.If not phase-splitting after the condensation of tower top azeotrope, then pacify certain reflux ratio and reflux, the overhead fraction of extraction can Separation and Recovery alcohol further.
Second step, the separation of formaldehyde anhydrous alcohol solution.The formaldehyde anhydrous alcohol solution prepared by the first step, enters into still kettle, controls certain pressure and temperature, and formaldehyde vaporization in formaldehyde alcoholic solution, just can realize the two-phase gas-liquid separation by formaldehyde and alcohol, tank deck obtains formaldehyde gas, obtains absolute alcohol liquid at the bottom of tank.Formaldehyde gas is passed into postorder flow elements, and alcohol can be got back in the first step rectifying tower, realizes the cyclical operation of solvent and Appropriate application.
3rd step, prepares new formaldehyde the second alcoholic solution.The formaldehyde gas steamed by still kettle, after entering into absorption tower, wherein mainly the second alcohol and formaldehyde gas contact absorption process.In order to ensure that two-phase can fully absorb, adopting gas-liquid two-phase countercurrent flow, and taking suitably to increase vapour-liquid ratio, expand the measures such as contact area, formaldehyde gas as much as possible is dissolved in alcohol.Finally obtain the formaldehyde alcoholic solution of high density.
The formalin that utilizes of the present invention is prepared in formaldehyde anhydrous alcohol solution and new formaldehyde alcoholic solution method for raw material, there are following one or more advantages: (1) raw material formalin (massfraction 0.1% ~ 60%) is more common, of many uses, running cost is low; (2) preparation technology is simple, and quality product is high, easy handling; (3) product of gained is easy to permanent preservation and never degenerates.
Therefore the method preparing formaldehyde anhydrous alcohol solution and new formaldehyde alcoholic solution of formalin and alcohol that utilizes of the present invention has important actual application value, can be applied to industrial production.
Hereafter will the present invention will be described in detail in conjunction with the embodiments, but those skilled in the art should be appreciated that those skilled in the art are according to the open and technical knowledge that itself has of the present invention, can carry out some to the present invention and change or revise.Therefore, scope of the present invention is not limited to following embodiment, and should only be limited by claims.
Accompanying drawing explanation
Fig. 1 is by preparing the technological process block diagram of formaldehyde anhydrous alcohol solution and new formaldehyde alcoholic solution after a series of rectifying, flash distillation, absorption operation with formalin and alcohol, accompanying drawing is only used for block diagram of the present invention is described, only draw the necessaries of interpretation process, and the facility of other significant need, as omissions such as instrument, pump, valve, tundish.
Embodiment
Embodiment 1:
Mass ratio is n-Octanol and the formalin of 2:1, enter into rectifying tower, under 0.1MPa, the temperature of setting tower reactor is about 160 DEG C, azeotrope can be steamed from tower top, after being separated by condenser, phase splitter, the liquid layer being rich in alcohol passes back into tower, another water layer extraction, finally can obtain formaldehyde anhydrous alcohol solution by tower reactor.From the formaldehyde octanol solution that tower reactor obtains, then enter into still kettle, under 0.053MPa, realize the separation of gas-liquid two-phase, top obtains formaldehyde gas, and bottom obtains n-Octanol.Octanol is recyclable to be recycled.And the formaldehyde gas at top is directly passed in absorption tower, under 0.1MPa, enter at the bottom of tower, ethanol passes into from tower top, realizes the counter-current absorption of gas-liquid two-phase.Finally obtain formaldehyde ethanol, formaldehyde content can reach 48%.
Embodiment 2:
Mass ratio is Virahol and the formalin of 1:3, enters into rectifying tower, and under 0.1MPa, the reflux ratio of tower top is 3:1, and overhead extraction is containing isopropanol water solution, and tower reactor can obtain formaldehyde anhydrous alcohol solution.The formaldehyde aqueous isopropanol obtained from tower reactor enters into another rectifying tower, and under 0.056MPa, realize the separation of gas-liquid two-phase, top obtains formaldehyde gas, and bottom obtains Virahol.Virahol is recyclable to be recycled.And the formaldehyde gas at top is directly passed in absorption tower, under 0.1MPa, enter at the bottom of tower, butanols passes into from tower top, realizes the counter-current absorption of gas-liquid two-phase.Finally obtain formaldehyde butanol solution, formaldehyde content can reach 33%.
Embodiment 3:
Mass ratio is 2-Ethylhexyl Alcohol and the formalin of 1:1, enters into rectifying tower, under 1MPa, azeotrope can be steamed from tower top, after being separated by condenser, phase splitter, the liquid layer being rich in alcohol passes back into tower, another water layer extraction, finally can obtain formaldehyde anhydrous alcohol solution by tower reactor.The formaldehyde 2-Ethylhexyl Alcohol solution obtained from tower reactor is driven into still kettle by pump, and under 0.5MPa, realize the separation of gas-liquid two-phase, top obtains formaldehyde gas, and bottom obtains 2-Ethylhexyl Alcohol.2-Ethylhexyl Alcohol is recyclable to be recycled.And the formaldehyde gas at top is directly passed in absorption tower, at 0.2 mpa, enter at the bottom of tower, ethanol passes into from tower top, realizes the counter-current absorption of gas-liquid two-phase.Finally obtain formaldehyde ethanolic soln, formaldehyde content can reach 38%.
Embodiment 4:
Take 4-methyl-3-enanthol and formalin that mass ratio is 5:2, under 5MPa, azeotrope can be steamed from tower top, after being separated by condenser, phase splitter, the liquid layer being rich in alcohol passes back into tower, and another water layer extraction, finally can obtain formaldehyde anhydrous alcohol solution by tower reactor.From the formaldehyde 4-methyl-3-enanthol solution that tower reactor obtains, be driven in still kettle by pump, under 0.3MPa, realize the separation of gas-liquid two-phase, top obtains formaldehyde gas, and bottom obtains 4-methyl-3-enanthol, recycling use.And the formaldehyde gas at top is directly passed in absorption tower, at 0.2 mpa, enter at the bottom of tower, nonyl alcohol passes into from tower top, realizes the counter-current absorption of gas-liquid two-phase.Finally obtain formaldehyde nonyl alcohol solution, formaldehyde content can reach 20%.
Embodiment 5:
Take the trimethyl carbinol and formalin that mass ratio is 1:2, after mixing, be pumped in rectifying tower, at 0.2 mpa, azeotrope can be steamed from tower top, after being separated by condenser, phase splitter, the liquid layer being rich in alcohol passes back into tower, another water layer extraction, finally can obtain formaldehyde anhydrous alcohol solution by tower reactor.From the formaldehyde t-butanol solution that tower reactor obtains, enter into still kettle, under 0.1MPa, realize the separation of gas-liquid two-phase, top obtains formaldehyde gas, and bottom obtains the trimethyl carbinol, recycling use.And the formaldehyde gas at top is directly passed in absorption tower, under 0.1MPa, enter at the bottom of tower, methyl alcohol passes into from tower top, realizes the counter-current absorption of gas-liquid two-phase.Finally obtain formaldehyde methanol solution, formaldehyde content can reach 53%.
Claims (14)
1. prepare a method for anhydrous formaldehyde alcoholic solution, it is characterized in that, add in formalin and can form the alcohol of azeotropic with water, by distillation, water-band is gone out, prepare the method for formaldehyde anhydrous alcohol solution.
2. prepare a method for formaldehyde alcoholic solution, it is characterized in that, after in the formaldehyde anhydrous alcohol solution obtained by 1, alcohol is separated with formaldehyde, formaldehyde adds the second alcohol, prepares the method for formaldehyde the second alcoholic solution.
3. the method for claim 1, is characterized in that, described formalin, is the formalin of massfraction at 0.1%-90%, also can be the formalin containing organic solvent.
4. the method for claim 1, it is characterized in that, described alcohol can refer to the monohydroxy-alcohol of C3-C8, it is represented by general formula R OH, wherein R represents the group optionally replaced by one or more substituting group, described group is selected from straight chain, the alkyl of side chain, described monohydroxy-alcohol is preferably propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, sec.-amyl alcohol, 3-amylalcohol, tertiary amyl alcohol, secondary primary isoamyl alcohol, hexanol, 4-methyl-2-amylalcohol, 2-hexanol, 2-ethyl butanol, 2-methyl amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, enanthol, 2-enanthol, 3-enanthol, cyclohexanemethanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 5-methyl-2-hexanol, 3, 5, 5-trimethyl hexanol.
5. method as claimed in claim 2, it is characterized in that, described the second alcohol can refer to the monohydroxy-alcohol of C1-C12, it is represented by general formula R OH, wherein R represents the group optionally replaced by one or more substituting group, described group is selected from straight chain, the alkyl of side chain, described monohydroxy-alcohol is preferably methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, sec.-amyl alcohol, 3-amylalcohol, tertiary amyl alcohol, secondary primary isoamyl alcohol, hexanol, 4-methyl-2-amylalcohol, 2-hexanol, 2-ethyl butanol, 2-methyl amyl alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-ethyl-3-amylalcohol, enanthol, 2-enanthol, 3-enanthol, cyclohexanemethanol, octanol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol, 5-methyl-2-hexanol, 3, 5, 5-trimethyl hexanol, nonyl alcohol, 2, 6-2,6-dimethyl-4-heptanol, 2-propyl group-1-heptanol, isodecyl alcohol, decyl alcohol, 2-hexyl decyl alcohol, undecyl alcohol, 5-ethyl-2-nonyl alcohol, lauryl alcohol.
6. the method for claim 1, is characterized in that, the ratio of formalin and alcohol feedstock quality between 1:50-50:1, the inlet amount of preferred 1:10-10:1.The formalin of charging when different content can be adjusted, prepare the anhydrous alcohol solution of the formaldehyde of different content.
7. as claim 1 or 3,4, the method described in 6, is characterized in that, described distillation, comprises various distillation means and distillation technique, is preferably rectifying tower, comprising various forms of rectifying tower, and preferred filler tower and tray column.The control condition of distillation comprises: tower top temperature is-20 DEG C-250 DEG C, if preferably rectifier column reflux is than between 1:100-100:1.
8. as claim 1 or 3,4,6, the method described in 7, is characterized in that, the control condition of described distillation comprises: after overhead fraction condensation, cooling, enter phase splitter, be divided into two liquid phases, be rich in the organic phase reflux of alcohol, be rich in the liquid phase extraction of water.
9. the method as described in claim as arbitrary in claim 1-8, is characterized in that, carries out under 0-20MPa absolute pressure, and under the absolute pressure of preferred 0.1-5MPa, in formalin, water and alcohol form azeotropic, obtain the anhydrous alcohol solution of formaldehyde.
10. method as claimed in claim 2, is characterized in that, being separated of alcohol and formaldehyde in described formaldehyde anhydrous alcohol solution, comprises various separation means and distillation technique, be preferably flash separation, will wherein steam by formaldehyde.
11. methods as described in claim 2 or 10, it is characterized in that, in described formaldehyde anhydrous alcohol solution after being separated of alcohol and formaldehyde, use the second alcohol to absorb formaldehyde, prepare formaldehyde the second alcoholic solution, preferred absorption tower comprises adverse current or and stream and various forms of contact absorption process.
12. methods as claimed in claim 2, is characterized in that, add the inlet amount of the second alcohol, can adjust according to different ratios, the mol ratio of itself and formaldehyde at 1:50-50:1, preferred 1:10-10:1.
13. methods as claimed in claim 2, is characterized in that, after in described formaldehyde anhydrous alcohol solution, alcohol is separated with formaldehyde, the alcohol separated, after reclaimer operation process, can be recycled by 1.
14. methods as described in claim 1-13, is characterized in that, process operation adopts continuous processing to carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410352601.9A CN105272836A (en) | 2014-07-24 | 2014-07-24 | Method for preparing formaldehyde alcohol solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410352601.9A CN105272836A (en) | 2014-07-24 | 2014-07-24 | Method for preparing formaldehyde alcohol solution |
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| CN105272836A true CN105272836A (en) | 2016-01-27 |
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| CN201410352601.9A Pending CN105272836A (en) | 2014-07-24 | 2014-07-24 | Method for preparing formaldehyde alcohol solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699536A (en) * | 2017-01-12 | 2017-05-24 | 湖北泰盛化工有限公司 | Preparation method of anhydrous formaldehyde alcohol solution and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB714821A (en) * | 1951-10-20 | 1954-09-01 | Celanese Corp | Concentrated formaldehyde solutions |
| GB1301533A (en) * | 1969-06-06 | 1972-12-29 | ||
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
-
2014
- 2014-07-24 CN CN201410352601.9A patent/CN105272836A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB714821A (en) * | 1951-10-20 | 1954-09-01 | Celanese Corp | Concentrated formaldehyde solutions |
| GB1301533A (en) * | 1969-06-06 | 1972-12-29 | ||
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699536A (en) * | 2017-01-12 | 2017-05-24 | 湖北泰盛化工有限公司 | Preparation method of anhydrous formaldehyde alcohol solution and device |
| CN106699536B (en) * | 2017-01-12 | 2023-03-31 | 湖北泰盛化工有限公司 | Preparation method and device of anhydrous formaldehyde alcohol solution |
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Application publication date: 20160127 |