CN103339094A - Method for producing hemiformal concentrate and method for producing formaldehyde gas - Google Patents
Method for producing hemiformal concentrate and method for producing formaldehyde gas Download PDFInfo
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- CN103339094A CN103339094A CN2012800063457A CN201280006345A CN103339094A CN 103339094 A CN103339094 A CN 103339094A CN 2012800063457 A CN2012800063457 A CN 2012800063457A CN 201280006345 A CN201280006345 A CN 201280006345A CN 103339094 A CN103339094 A CN 103339094A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/48—Preparation of compounds having groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
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Abstract
Provided is a method for producing a hemiformal concentrate that contains little water, wherein the amount of formaldehyde contained in water is reduced, said water being obtained by subjecting a reaction product containing a hemiformal and water to evaporative dehydration, and the amount of water contained in a hemiformal concentrate is reduced. A method for producing a hemiformal concentrate, wherein a reaction product containing a hemiformal and water is produced by having (A) an alcohol and (B) an aqueous formaldehyde solution react with each other and the reaction product is subjected to evaporative dehydration so as to be separated into (C) a hemiformal concentrate and (D) water. In this method, an alcohol which has a solubility in 100 g of water of 3.0 g or less at 20 DEG C and at 760 mmHg and a boiling point of 190 DEG C or more at 760 mmHg is used as the alcohol (A).
Description
Technical field
The present invention relates to the manufacture method of hemiformal enriched material and the manufacture method of formaldehyde gas.
Background technology
As the method for making aldehyde gas, known hemiformal (hemiformal) change method.This hemiformal method is undertaken by following step.At first, formalin and alcohol are reacted, obtain comprising the reaction product of water and hemiformal.Then, from the reaction product that comprises hemiformal and water, the water dehydration by evaporation is obtained the hemiformal enriched material.At last, with the thermolysis of hemiformal enriched material, obtain formaldehyde gas (for example, with reference to patent documentation 1).
In above-mentioned hemiformal method, comprise formaldehyde in the known water that is obtained by above-mentioned reaction product dehydration by evaporation.And, in this water the amount of contained aldehyde for a long time, the recovery of aldehyde needs very big cost.Therefore, the content of contained formaldehyde in the water behind the needs inhibition dehydration by evaporation.
In addition, also comprise water in the known hemiformal enriched material.When comprising water in the hemiformal enriched material, by also comprising water in the formaldehyde gas that the thermolysis of hemiformal enriched material is obtained.Even contained water is a small amount of in the formaldehyde gas, according to the purposes of formaldehyde gas, containing water also often becomes problem.Therefore, the amount of the water that also needs to suppress contained in the hemiformal enriched material.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 01-216950 communique
Summary of the invention
The problem that invention will solve
As the method for making formaldehyde gas, although the hemiformal method is useful method, the aspect that also exists the needs such as minimizing of the amount of water contained in the minimizing, hemiformal enriched material of the amount of formaldehyde contained in the water that is obtained by above-mentioned reaction product dehydration by evaporation to improve.
In addition, when changing over creating conditions that the amount that makes water contained in the hemiformal enriched material reduces in order to improve the problems referred to above, aldehyde amount contained in the water behind the dehydration by evaporation increases.In addition, when changing over creating conditions that the amount of aldehyde contained in the water that makes behind the dehydration by evaporation reduces, the amount of contained water increases in the hemiformal enriched material.Therefore, the amount that reduce the amount of water contained in the hemiformal enriched material, reduces aldehyde contained in the water behind the dehydration by evaporation simultaneously is very difficult.
The present invention makes in order to address the above problem, its purpose is, the reaction product dehydration by evaporation that will comprise hemiformal and water is provided and in the water that obtains the amount of contained formaldehyde reduced and the hemiformal enriched material in the method for the few hemiformal enriched material of the manufacturing water-content that reduced of the amount of contained water, and the hemiformal enriched material thermolysis that will obtain thus and make the method for formaldehyde gas.
For the scheme of dealing with problems
The inventor etc. further investigate repeatedly in order to overcome the above problems.Found that, by (A) alcohol is reacted with (B) formalin, generation comprises the reaction product of hemiformal and water, the reaction product dehydration by evaporation is separated into (C) hemiformal enriched material and (D) in the manufacture method of the hemiformal enriched material of water, make (A) alcohol that uses as raw material satisfy following condition, can address the above problem, thereby finish the present invention.More specifically, the invention provides following technical scheme.
(condition)
(A) alcohol is hydrophobicity.Particularly, (A) solubleness of alcohol in 100g water is below the 3.0g under 20 ℃, the condition of 760mmHg.
(A) Chun boiling point is more than 190 ℃.
(1) a kind of manufacture method of hemiformal, it makes (A) alcohol react with (B) formalin, generation comprises the reaction product of hemiformal and water, previous reaction product dehydration by evaporation is separated into (C) hemiformal enriched material and (D) water, in the described manufacture method, aforementioned (A) alcohol solubleness in 100g water be below the 3.0g under 20 ℃, the condition of 760mmHg, and aforementioned (A) pure boiling point is being more than 190 ℃ under the condition of 760mmHg.
(2) according to the manufacture method of (1) described hemiformal enriched material, wherein, (A) alcohol is monohydroxy-alcohol, dibasic alcohol or the trivalent alcohol shown in the following general formula (I).
[Chemical formula 1]
(X in the general formula (I) is hydrogen atom or hydroxyl.In addition, R
1And R
2Be hydrogen atom, hydroxyl, carbon number more than 1 and 10 following alkyl or the carbon number 1 or more and hydroxyalkyls below 10, R
1And R
2Can be identical, also can be different.In addition, p, q, r are more than 0 and 10 following integers, and more than the p+q+r=3 and below 20.)
(3) according to the manufacture method of (1) or (2) described hemiformal enriched material, wherein, (A) blending ratio pure and (B) formalin is more than 0.3 and below 5.0 with the molar ratio computing of the hydroxyl in (A) alcohol and formaldehyde.
(4) according to the manufacture method of each described hemiformal enriched material in (1)～(3), wherein, (D) contained formaldehyde amount is below the 5.0 quality % with respect to the formaldehyde amount that supplies to the hemiformal reaction in the water.
(5) according to the manufacture method of each described hemiformal enriched material in (1)～(4), wherein, (C) contained amount of moisture is below the 1.0 quality % in the hemiformal enriched material.
(6) according to the manufacture method of each described hemiformal enriched material in (1)～(5), wherein, (D) contained (A) alcohol amount is below the 0.5 quality % in the water.
(7) a kind of manufacture method of formaldehyde, the hemiformal enriched material thermolysis that it will be obtained by each described manufacture method in (1)～(6).
The effect of invention
According to the present invention, can in the manufacturing of the aldehyde gas that utilizes the hemiformal method, reduce the amount of formaldehyde contained in the water that gone out by the mixture separation that comprises hemiformal and water, and reduce the amount by water contained in the isolated hemiformal enriched material of said mixture.Thus, can reduce the amount of water contained in the hemiformal enriched material, its result also can reduce the amount by water contained in the formaldehyde that this hemiformal enriched material thermolysis is obtained.
Description of drawings
Fig. 1 is the figure of a schematically illustrated example for the device of implementing the hemiformal method.
Embodiment
Below, embodiments of the present invention are elaborated.The present invention is not limited to following embodiment.
The present invention is the method for making the hemiformal enriched material, the method that reaches manufacturing formaldehyde, and the manufacture method of hemiformal enriched material of the present invention can preferably be applied to the hemiformal method as the aldehyde gas producing method.At first, after the summary of double formalizing method is carried out simple declaration, to the manufacture method of hemiformal enriched material of the present invention, and the manufacture method of formaldehyde describe.
＜hemiformal method＞
The schematically illustrated example for the device of implementing the hemiformal method of Fig. 1.As shown in Figure 1, this device possesses reactor 1, evaporating kettle 2 and splitter 3.In reaction vessel 1, carry out hemiformal and generate operation (S1), in evaporating kettle 2, carry out separation circuit (S2), in splitter 3, carry out formaldehyde gas and generate operation (S3).
Between reaction vessel 1 and the evaporating kettle 2, utilize tubular structure member (not shown) to be connected respectively between evaporating kettle 2 and the splitter 3.In addition, as described later, evaporating kettle 2 also is connected with for the tubular structure member of discharging (D) water.
Evaporating kettle 2 is for the water dehydration by evaporation being separated into (C) hemiformal enriched material and (D) position of water from reaction product.Vaporized in evaporating kettle 2 (D) water is extracted from the tubular structure member, and (C) the hemiformal enriched material is by being sent to splitter 3 in the tubular structure member that connects evaporating kettle 2 and splitter 3.In addition, also can use distillation tower to replace evaporating kettle 2.In addition, also can adopt and use the multistage distillation of multistage distillation tower etc. to handle.
In addition, the manufacture method of hemiformal enriched material of the present invention can be used for the dehydration by evaporation to the evaporating kettle 2 of reacting of above reactor 1.
The manufacture method of＜hemiformal enriched material＞
The manufacture method of hemiformal enriched material of the present invention possesses hemiformal and generates operation (S1) and separation circuit (S2).
[hemiformal generates operation (S1)]
It is the operation that (A) alcohol and (B) formalin are reacted that hemiformal generates operation (S1).Manufacture method of the present invention is characterised in that hemiformal generates the alcohol that is used as raw material in the operation (S1).
The alcohol that uses in this operation (S1) refers to satisfy the alcohol of following condition.
(A) alcohol is hydrophobicity.Particularly, the solubleness of alcohol in 100g water is below the 3.0g under 20 ℃, the condition of 760mmHg.
(A) Chun boiling point is being more than 190 ℃ under the condition of 760mmHg.
Alcohol is when be hydrophobicity, in the aftermentioned separation circuit, can be under 60 ℃～70 ℃ such low temperature easily with (C) hemiformal enriched material and (D) water sepn, therefore, can reduce the amount of water contained in (C) hemiformal enriched material.Herein, hydrophobicity refers to, the solubleness of alcohol in 100g water is below the 3.0g under 20 ℃, the condition of 760mmHg.
In addition, the boiling point of alcohol is more than 190 ℃ the time, does not almost sneak into unreacted and residual alcohol in (D) water behind the dehydration by evaporation.
So long as satisfy the alcohol of above-mentioned condition, particularly be that hydrophobicity and boiling point are the alcohol more than 190 ℃, just can be used as raw material.More specifically, can use the alcohol shown in the following general formula (I) (monohydroxy-alcohol, dibasic alcohol, trivalent alcohol).
[Chemical formula 2]
(X in the general formula (I) is hydrogen atom or hydroxyl.In addition, R
1And R
2Be hydrogen atom, hydroxyl, carbon number more than 1 and 10 following alkyl or the carbon number 1 or more and hydroxyalkyls below 10, R
1And R
2Can be identical, also can be different.In addition, p, q, r are more than 0 and 10 following integers, and more than the p+q+r=3 and below 20.)
X in the above-mentioned general formula (I) is hydrogen atom or hydroxyl.
R in the above-mentioned general formula (I)
1And R
2Be hydrogen atom, hydroxyl, carbon number more than 1 and 10 following alkyl or the carbon number 1 or more and hydroxyalkyls below 10.In addition, R
1And R
2Can be identical, also can be different.
More than 1 and 10 following alkyl, the alkyl of the alkyl of straight chain shape, a chain all can as carbon number.As the alkyl of straight chain shape, can methyl, ethyl, propyl group, butyl etc. be shown example.Alkyl as a chain can example illustrate sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl etc.
, can example illustrate: methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl-n-propyl, 2-hydroxyl-n-propyl, 3-hydroxyl-n-propyl, 1-hydroxyl-normal-butyl, 2-hydroxyl-normal-butyl, 3-hydroxyl-normal-butyl, 4-hydroxyl-normal-butyl, 5-hydroxyl-n-pentyl, 6-hydroxyl-n-hexyl etc. more than 1 and 10 following hydroxyalkyls as carbon number.
P, q, r are more than 0 and 10 following integers, and more than the p+q+r=3 and below 20.
Among the present invention, preferably use diethyl pentanediol, Rutgers 612, octanol.
As the diethyl pentanediol, can 2,4-diethyl-1 be shown example, 5-pentanediol, 2,3-diethyl-1,5-pentanediol, 1,4-diethyl-1,5-pentanediol, 1,5-diethyl-1,5-pentanediol etc.
As Rutgers 612, can 2-ethyl-1 be shown example, 3-hexylene glycol, 3-ethyl-1,3-hexylene glycol, 4-ethyl-1,3-hexylene glycol etc.
Among the above-mentioned alcohol, most preferably use 2,4-diethyl-1, the 5-pentanediol.
In addition, as the alcohol that uses among the present invention, can use the alcohol of making by usual method.In addition, also can buy commercially available product uses.
Then, (B) formalin as another raw material is described.In the present invention, the content of the formaldehyde in (B) formalin is not particularly limited, but it is above and below the 80 quality % preferably to contain 1 quality %.
(A) blending ratio of alcohol and (B) formalin is preferably more than 0.3 with the molar ratio computing of the hydroxyl in (A) alcohol and formaldehyde and below 5.0.Being 0.3 when above, can reducing formaldehyde amount contained in (D) water, so preferred, is 5.0 when following, and the formaldehyde amount of reacting with (A) alcohol of per unit weight is many, has advantage at cost, so preferably.More preferably more than 0.5 and below 2.0.
In this operation (S1), above-mentioned (A) alcohol is reacted with (B) formalin.In reactor 1, drop into these materials, (A) alcohol and (B) formalin are reacted.Particularly, (A) alcohol reacts with (B) contained formaldehyde.Reaction product mainly comprises hemiformal, water, but also comprises unreacted alcohol, formaldehyde in the reaction product.
Reaction conditions is not particularly limited, can adopts with the same condition of the reaction conditions of the alcohol in the existing known hemiformal method and formalin.For example, temperature of reaction is preferably more than the room temperature (about 20 ℃) and below 90 ℃.In addition, the reaction times is according to the suitably settings such as the situation of carrying out of reaction.
[separation circuit (S2)]
To be the reaction product that comprises hemiformal and water (also comprising unreacted and residual alcohol, aldehyde) that will be sent to evaporating kettle 2 from reactor 1 be separated into (C) hemiformal enriched material and (D) operation of water by dehydration by evaporation to separation circuit (S2).In addition, (C) hemiformal enriched material side comprises unreacted and residual (A) alcohol, (C) hemiformal enriched material side and (D) water side both comprise formaldehyde.
(A) that use among the present invention alcohol is compared with employed alcohol all the time, is hydrophobicity, its result, in separation circuit (S2), can be under 60 ℃～70 ℃ such low temperature easily will (C) hemiformal enriched material and (D) water sepn.Therefore, can reduce the amount of formaldehyde contained in (D) water that distillates by evaporation.Therefore, can suppress for the cost that reclaims the contained formaldehyde of (D) water.
Especially, (D) amount of the formaldehyde in the water is 5 quality % when following with respect to the formaldehyde amount that supplies to the hemiformal reaction, can fully suppress the cost of formaldehyde contained in the recycle-water.
In addition, as mentioned above, (A) used in the present invention alcohol is hydrophobicity, its result, can be under 60 ℃～70 ℃ such low temperature easily with (C) hemiformal enriched material and (D) water sepn, therefore, can reduce contained amount of moisture in (C) hemiformal enriched material behind the separation circuit (S2).
Particularly, when using (A) alcohol as raw material, the amount that can make the water in (C) hemiformal enriched material is below the 1 quality %.
In addition, as mentioned above, (A) alcohol since boiling point very high, be more than 190 ℃, therefore, contain unreacted hardly and residual (A) alcohol in (D) water behind the dehydration by evaporation.When comprising alcohol in a large number in the evaporant, need (A) alcohol contained in the recycle-water, need very big cost.So long as manufacture method of the present invention as mentioned above, (D) contains (A) alcohol hardly in the water, therefore, just do not need for the very big cost that reclaims contained (A) alcohol of (D) water.
Actual conditions to dehydration by evaporation is not particularly limited, can be by dehydration by evaporation is carried out in decompression in the evaporating kettle 2 and adjustment temperature.Decompression in the evaporating kettle 2 can be used existing known decompression means.In addition, the temperature control in the evaporating kettle 2 also can be undertaken by existing known temperature control device.
In the present invention, the preferable range of the temperature in the evaporating kettle 2 is not particularly limited, is preferably more than 40 ℃ and below 80 ℃.Be below 40 ℃ the time, (C) amount of moisture in the hemiformal enriched material increases, ensuing operation and after may become problem, so not preferred.Be more than 80 ℃ the time, (D) contained formaldehyde amount increases in the water, causes the formaldehyde loss, thus not preferred, and, must make thermal source become LS (water vapour) from HW (warm water), cause power loss, so not preferred.More preferably more than 55 ℃ and below 75 ℃, more preferably more than 60 ℃ and below 70 ℃.In addition, during temperature when improving decompression dehydration, when the tendency that exists the formaldehyde amount in (D) water to increase, temperature when reducing decompression dehydration, the tendency that exists the amount of moisture in (C) hemiformal enriched material to increase.
The preferred pressure condition is not particularly limited, in order in above-mentioned preferred temperature range, to carry out dehydration by evaporation, is preferably below the 100mmHg, is preferably below the 50mmHg especially.
The manufacture method of＜formaldehyde＞
The manufacture method of formaldehyde gas of the present invention will be by making formaldehyde by the hemiformal enriched material thermolysis that above-mentioned method for making obtains.Particularly, can adopt the existing known method that generates use splitter putting down in writing in the operation (S3) etc. as above-mentioned formaldehyde gas.
Embodiment
Below embodiment is shown and comparative example specifies the present invention, but the present invention is not limited to these embodiment.
＜material＞
Alcohol 1:2,4-diethyl-1,5-pentanediol (DEPD), the solubleness in 100g water (20 ℃, 760mmHg) 1.9g, 264 ℃ of boiling points (under the 760mmHg)
Alcohol 2:2-ethyl-1,3-hexylene glycol (EHD), the solubleness in 100g water (20 ℃, 760mmHg) 0.6g, 244 ℃ of boiling points (under the 760mmHg)
Alcohol 3:1-octanol (OcOH), the solubleness in 100g water (20 ℃, 760mmHg) 0.03 * 10
-3G, 194 ℃ of boiling points (under the 760mmHg)
Alcohol 4: Liquid Macrogol (PEG300), the solubleness in 100g water (20 ℃, 760mmHg) infinity, no boiling point (under the 760mmHg)
Alcohol 5: triethylene glycol (TEG), the solubleness in 100g water (20 ℃, 760mmHg) infinity, 287 ℃ of boiling points (under the 760mmHg)
Alcohol 6: hexalin (CHOL), the solubleness in 100g water (20 ℃, 760mmHg) 3.8g, 161 ℃ of boiling points (under the 760mmHg)
＜embodiment 1＞
(B) formalin and 2 that will comprise 50 quality % formaldehyde, 4-diethyl-1,5-pentanediol (DEPD) is that 1.3 mode is mixed with the mole number of the hydroxyl of DEPD and the ratio (mole number of the mole number/formaldehyde of the hydroxyl of DEPD) of the mole number of formaldehyde, carries out the hemiformal reaction under room temperature, the condition in 12 hours reaction times.After reaction is finished, to be fed to evaporating kettle continuously with the speed of 1000g/hr as the hemiformal mixed solution of reaction product, under 60～70 ℃ of temperature, working pressure 35mmHg, 70 minutes condition of mean residence time, carry out decompression dehydration (decompression dehydration is equivalent to dehydration by evaporation of the present invention), obtain (C) hemiformal enriched material.Formaldehyde amount (quality %) in (D) water that distillates by dehydration operation is measured by the volumetry of using S-WAT.In addition, (D) the alcohol amount in the water is measured by nuclear magnetic resonance analyser (NMR).(C) amount of moisture (quality %) in the hemiformal enriched material uses the karl Fischer moisture meter to measure.Measurement result is shown in table 1.Need to prove, in (D) water that distillates contained formaldehyde amount namely distillate HCHO amount and (D) water of distillating in contained alcohol amount namely distillate the alcohol amount and calculated according to following formula by analytical value.
Distillate HCHO amount (quality %)=(contained HCHO measures (g) in the water that distillates)/(the HCHO amount (g) of feed) * 100
Distillate alcohol amount (quality %)=(in the water that distillates contained alcohol amount (g))/(the alcohol amount (g) of feed) * 100
＜embodiment 2＞
Except using 2-ethyl-1,3-hexylene glycol (EHD) replaces outside the DEPD, by method similarly to Example 1, calculates the amount of moisture (quality %) that distillates in HCHO amount (quality %), (C) hemiformal enriched material, distillates alcohol amount (quality %).To calculate and the results are shown in table 1.
＜embodiment 3＞
Except using 1-octanol (OcOH) to replace the DEPD, by method similarly to Example 1, calculate the amount of moisture (quality %) that distillates in HCHO amount (quality %), (C) hemiformal enriched material, distillate alcohol amount (quality %).To calculate and the results are shown in table 1.
＜comparative example 1＞
Except using Liquid Macrogol (PEG300) to replace the DEPD, by method similarly to Example 1, calculate the amount of moisture (quality %) that distillates in HCHO amount (quality %), (C) hemiformal enriched material, distillate alcohol amount (quality %).To calculate and the results are shown in table 1.
＜comparative example 2＞
Except using triethylene glycol (TEG) to replace the DEPD, by method similarly to Example 1, calculate the amount of moisture (quality %) that distillates in HCHO amount (quality %), (C) hemiformal enriched material, distillate alcohol amount (quality %).To calculate and the results are shown in table 1.
＜comparative example 3＞
Except using hexalin (CHOL) to replace the DEPD, by method similarly to Example 1, calculate the amount of moisture (quality %) that distillates in HCHO amount (quality %), (C) hemiformal enriched material, distillate alcohol amount (quality %).To calculate and the results are shown in table 1.
[table 1]
Distillate HCHO amount (quality %)=(contained HCHO measures (g) in the water that distillates)/(the HCHO amount (g) of feed) * 100
Distillate alcohol amount (quality %)=(in the water that distillates contained alcohol amount (g))/(the alcohol amount (g) of feed) * 100
By the result of the result of embodiment 1～3 and comparative example 1～3 obviously as can be seen, when (A) that raw material use hydrophobicity height and boiling point are high is pure, (C) amount of contained water reduces in the hemiformal enriched material, and contained formaldehyde amount in (D) water that can suppress to distillate by dehydration by evaporation.In addition, can confirm that (A) alcohol amount contained in (D) water that distillates is also few, does not need for the very big cost that reclaims (A) alcohol.
Can confirm that the temperature during decompression dehydration is about more than 60 ℃ and during the scope below 70 ℃, obtains effect of the present invention easily.
Description of reference numerals
1 reactor
2 evaporating kettles
3 splitters
Claims (7)
1. the manufacture method of a hemiformal, it is that (A) alcohol is reacted with (B) formalin, generation comprises the reaction product of hemiformal and water, described reaction product dehydration by evaporation is separated into (C) hemiformal enriched material and (D) manufacture method of the hemiformal enriched material of water
Described (A) alcohol solubleness in 100g water is below the 3.0g under 20 ℃, the condition of 760mmHg,
The boiling point of described (A) alcohol is being more than 190 ℃ under the condition of 760mmHg.
2. the manufacture method of hemiformal enriched material according to claim 1, wherein, (A) alcohol is monohydroxy-alcohol, dibasic alcohol or the trivalent alcohol shown in the following general formula (I),
[Chemical formula 1]
X in the general formula (I) is hydrogen atom or hydroxyl, in addition, and R
1And R
2Be hydrogen atom, hydroxyl, carbon number more than 1 and 10 following alkyl or the carbon number 1 or more and hydroxyalkyls below 10, R
1And R
2Can be identical, also can be different, in addition, p, q, r are more than 0 and 10 following integers, and more than the p+q+r=3 and below 20.
3. the manufacture method of hemiformal enriched material according to claim 1 and 2, wherein, (A) blending ratio of alcohol and (B) formalin is more than 0.3 and below 5.0 with the molar ratio computing of the hydroxyl in (A) alcohol and formaldehyde.
4. according to the manufacture method of each described hemiformal enriched material in the claim 1～3, wherein, (D) contained formaldehyde amount is below the 5.0 quality % with respect to the formaldehyde amount that supplies to the hemiformal reaction in the water.
5. according to the manufacture method of each described hemiformal enriched material in the claim 1～4, wherein, (C) contained amount of moisture is below the 1.0 quality % in the hemiformal enriched material.
6. according to the manufacture method of each described hemiformal enriched material in the claim 1～5, wherein, (D) contained (A) alcohol amount is below the 0.5 quality % in the water.
7. the manufacture method of a formaldehyde, the hemiformal enriched material thermolysis that it will be obtained by each described manufacture method in the claim 1～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-014398 | 2011-01-26 | ||
| JP2011014398A JP5698548B2 (en) | 2011-01-26 | 2011-01-26 | Method for producing hemi-formal concentrate and method for producing formaldehyde gas |
| PCT/JP2012/050843 WO2012102136A1 (en) | 2011-01-26 | 2012-01-17 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
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| CN103339094A true CN103339094A (en) | 2013-10-02 |
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| CN2012800063457A Pending CN103339094A (en) | 2011-01-26 | 2012-01-17 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
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| JP (1) | JP5698548B2 (en) |
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| WO (1) | WO2012102136A1 (en) |
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| JP2013151439A (en) * | 2012-01-24 | 2013-08-08 | Polyplastics Co | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
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| GB1071767A (en) * | 1963-09-23 | 1967-06-14 | Stamicarbon | Process for preparing concentrated formald chyde solutions |
| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| US3435077A (en) * | 1965-01-16 | 1969-03-25 | Huels Chemische Werke Ag | Process for the production of asymmetrical formals |
| US3436422A (en) * | 1966-04-11 | 1969-04-01 | Du Pont | Process for the purification of formaldehyde |
| JPH01216950A (en) * | 1988-02-26 | 1989-08-30 | Ube Ind Ltd | Purification of formaldehyde |
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| SE9502355L (en) * | 1995-06-29 | 1996-12-30 | Perstorp Ab | Cleavage of cycloalkyl ethers |
| CN1810753A (en) * | 2006-02-28 | 2006-08-02 | 上海华谊丙烯酸有限公司 | Acid zeolite catalyzed process to synthesize acetal (ketal) |
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2011
- 2011-01-26 JP JP2011014398A patent/JP5698548B2/en not_active Expired - Fee Related
-
2012
- 2012-01-17 CN CN2012800063457A patent/CN103339094A/en active Pending
- 2012-01-17 WO PCT/JP2012/050843 patent/WO2012102136A1/en active Application Filing
- 2012-01-20 TW TW101102431A patent/TW201245134A/en unknown
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| GB752163A (en) * | 1953-07-16 | 1956-07-04 | Du Pont | Preparation of purified formaldehyde |
| GB1071767A (en) * | 1963-09-23 | 1967-06-14 | Stamicarbon | Process for preparing concentrated formald chyde solutions |
| US3435077A (en) * | 1965-01-16 | 1969-03-25 | Huels Chemische Werke Ag | Process for the production of asymmetrical formals |
| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| US3436422A (en) * | 1966-04-11 | 1969-04-01 | Du Pont | Process for the purification of formaldehyde |
| JPH01216950A (en) * | 1988-02-26 | 1989-08-30 | Ube Ind Ltd | Purification of formaldehyde |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272836A (en) * | 2014-07-24 | 2016-01-27 | 中国石油大学(华东) | Method for preparing formaldehyde alcohol solution |
| CN104710292A (en) * | 2015-03-24 | 2015-06-17 | 江苏凯茂石化科技有限公司 | Method for refining anhydrous pure formaldehyde gas and process device |
| CN104725202A (en) * | 2015-03-24 | 2015-06-24 | 江苏凯茂石化科技有限公司 | Process device and method for production of poly methoxy dimethyl ether raw material |
| CN104725203A (en) * | 2015-03-24 | 2015-06-24 | 江苏凯茂石化科技有限公司 | Process device and method for synthesizing polymethoxyl dimethyl ether and deacidifying by formaldehyde gas |
| CN104725203B (en) * | 2015-03-24 | 2016-05-11 | 江苏凯茂石化科技有限公司 | Process unit and the method for the synthetic polymethoxy dimethyl ether of a kind of gas formaldehyde and depickling |
| CN104710292B (en) * | 2015-03-24 | 2017-06-06 | 江苏凯茂石化科技有限公司 | A kind of process for purification and process unit of anhydrous pure formaldehyde gas |
| CN106268247A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of catalytic absorption method of formaldehyde |
| CN107353188A (en) * | 2016-05-10 | 2017-11-17 | 北京旭阳科技有限公司 | A kind of method for preparing anhydrous gaseous formaldehyde |
| WO2021052328A1 (en) * | 2019-09-19 | 2021-03-25 | 山东辰信新能源有限公司 | Preparation method for polyoxymethylene dimethyl ether and mixture thereof |
| CN112574013A (en) * | 2019-09-27 | 2021-03-30 | 山东辰信新能源有限公司 | Preparation method of polymethoxy dimethyl ether (DMMn) |
| CN112898145A (en) * | 2021-03-22 | 2021-06-04 | 邢台旭阳科技有限公司 | Gas-phase formaldehyde extraction system |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201245134A (en) | 2012-11-16 |
| WO2012102136A1 (en) | 2012-08-02 |
| JP5698548B2 (en) | 2015-04-08 |
| JP2012153648A (en) | 2012-08-16 |
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