CN108821943A - A kind of method and process for refining removing the tertiary ammonium salt in polyhydroxy-alcohol substance - Google Patents
A kind of method and process for refining removing the tertiary ammonium salt in polyhydroxy-alcohol substance Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
The present invention provides a kind of methods of the organic acid tertiary ammonium salt in removal polyhydroxy-alcohol substance, the pH value of the polyhydroxy-alcohol substance aqueous solution containing tertiary ammonium salt is adjusted to 6-8, promote tertiary ammonium salt to convert to obtain free tertiary amine, be then in contact with inert gas, Desorption separation removes from liquid phase by it.Before above-mentioned reaction product is refined, increases the step of removing trimethylamine salt, the quality and yield of final products are improved, to be conducive to the raising of downstream product processing performance.
Description
Technical field
The present invention relates to fine chemistry industry production fields, and in particular to the side of the tertiary ammonium salt in removal polyhydroxy-alcohol substance
Method.
Background technique
Polyhydroxy-alcohol substance is a kind of important Organic chemical products, 1,3- dihydroxy butane therein, 2,2- diformazan
Base -1,3- propylene glycol, 1,1,1- tri- (methylol) propane, 1,1,1- tri- (methylol) ethane etc. are widely used in resin, apply
The functional materials fields such as material.Trimethylamine, triethylamine, N, N- dimethyl amine etc. can be used in the production of polyhydroxy-alcohol substance
The technology that trimethylamine is catalyzed aldehydes raw material condensation repeated hydrogenation is realized.Since the excess of trimethylamine in production process is deposited
Inevitably lead to the disproportionated reaction of a small amount of aldehydes raw material, generates corresponding organic acid and alcohol.By-product in dismutation
Object organic acid can further be reacted with trimethylamine generates ionic compound organic acid tertiary ammonium salt.Organic acid tertiary ammonium salt can follow object
Stream enters product purification unit, and may influence whether the quality of final products or the processing performance of yield or even downstream product.
In existing technical field, not yet the good method for removing organic acid tertiary ammonium salt this purpose is realized in discovery.Such as
United States Patent (USP) US4855515A discloses a kind of production method of neopentyl glycol, the copper chromite catalyst promoted using manganese,
Permission carries out in the presence of amine catalyst and water plus hydrogen.After hydrogenation, efflux must be with naoh treatment to be saponified polyhydroxy
The ester byproducts of base alcohol, and organic acid tertiary ammonium salt is neutralized, it is formed by sodium salt and is separated before rectifying with product, product mentions
Pure procedure is complex and costly.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of minimizing technologies of organic acid tertiary ammonium salt in polyhydroxy-alcohol substance.
The present invention provides a kind of methods of the organic acid tertiary ammonium salt in removal polyhydroxy-alcohol substance, including, adjusting contains
There is the pH value of polyhydroxy-alcohol substance aqueous solution of tertiary ammonium salt to 6-8, is then in contact with inert gas.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, it is calculated in mass percent, the polyhydroxy
Water content at least 10% in base alcohols material aqueous solution.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy alcohols object after adjusting pH value
When matter is in contact with inert gas, the temperature for controlling treatment process is higher than the boiling point of the trimethylamine under the conditions of processing pressure, no
The boiling point being lauched higher than relevant pressure.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the temperature for the treatment of process is 80-150
℃。
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy alcohols object after adjusting pH value
When matter is in contact with inert gas, the pressure for controlling treatment process is higher than the saturated vapor pressure that treatment temperature condition is lauched, not high
The saturated vapor pressure of trimethylamine under relevant temperature.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the pressure for the treatment of process is 0.1-
0.5MPa。
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the quality of tertiary amine in the inert gas
Content is less than 1.5%, and preferably smaller than 0.2%, more preferably 0%.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the inert gas refers to relative to more
Hydroxy alcohols substance is inert, is including but not limited to nitrogen, one of hydrogen, carbon monoxide, methane and ethane or several
The mixture of kind.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy alcohols object after adjusting pH value
The time that matter is in contact with inert gas is 1-48 hours, preferably 5-24 hours.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy alcohols object after adjusting pH value
Matter and inert gas counter current contacting.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, to the polyhydroxy alcohols containing tertiary ammonium salt
Acidic catalyst or basic catalyst are added in substance, to adjust its pH value to 6-8, as long as can also be added without catalyst can incite somebody to action
The pH value of polyhydroxy-alcohol substance is adjusted to 6-8, to as far as possible convert the tertiary ammonium salt wherein contained to free
Tertiary amine, during being in contact with inert gas, the Desorption separation from liquid, to reach the mesh for removing tertiary ammonium salt therein
's.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the acidic catalyst includes but unlimited
Then the mixture of one or more of organic acid, inorganic acid, solid acid and molecular sieve；The basic catalyst includes but not
It is limited to be or mixtures thereof organic base, solid base.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy-alcohol substance is organic
The product of tertiary amine catalytic aldehyde condensation hydrogenation synthesis.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy-alcohol substance has such as
Structure shown in following formula (1),
Wherein R1, R2, R3, R4, R5, R6 are separately hydrogen, oxygen-containing group or the alkyl with 1-6 carbon atom；And
At least containing there are two and no more than four oxygen-containing groups in R1, R2, R3, R4, R5, R6, the oxygen-containing group is hydroxyl or methylol.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, the polyhydroxy-alcohol substance is organic
The product of tertiary amine catalytic aldehyde condensation hydrogenation synthesis, tertiary ammonium salt therein is largely organic acid tertiary ammonium salt, refers to polyhydroxy-alcohol
The reaction product of the tertiary amine catalyst used and byproduct organic acids in substance synthesis process.Organic acid refer in raw material and
The organic acid generated containing carbonyl material by disproportionation and oxidation reaction in resultants in reaction process, be also possible to bring into raw material has
Machine acid impurity.
Wherein, organic acid can be described with formula (2)：
Wherein R1′、R2′、R3' it is separately hydrogen, the methylol or tool of methylol, alkyl with 1-4 carbon atom
There is the alkyl of 1-4 carbon atom.
Tertiary amine catalyst is generally trimethylamine, has structure shown in formula (3),
Wherein R1″、R2″、R3It " is the alkyl with 1-2 carbon atom.
In the present invention, it is preferred to which azeotrope with water trimethylamine or azeotropic temperature are not lower than the tertiary amine of water boiling point.More preferably not
The trimethylamine of azeotrope with water.
In the method for tertiary ammonium salt in removal polyhydroxy-alcohol substance of the invention, treated, and liquid phase material product is sent into
Refined unit, further purification obtains purity acceptable product in refinement treatment unit.In order to keep treatment process
Temperature, the method that heating can be used are realized.In order to keep the pressure for the treatment of process, the method for introducing pressed gas can be used
It realizes.Inert gas can be disposable, and the recycling of gas circulator also can be used.
Industrially realize the present processes, the equipment of the technique unit used is the structures shape such as tank, tower, evaporator
The internals such as filler and heating tube can be used in equipment in the combination of one or more of formula, and filler can be regular or scattered heap
Metal or nonmetallic materials manufacture.The material selection of equipment has the stainless steel material of corrosion resistance.
The equipment of technique unit can be the tandem compound of one or several.
Materials stock is continually fed into and is discharged technique unit.If carrying out operation processing using tank, liquid material can be with
It is sent into equipment by the top of tank or middle part, the internals such as distributor or spraying nozzle can be used to scheme to increase the several of gas-liquid contact
Rate.Liquid material can send out equipment by the lower part of tank or middle part.Forced circulation pump can be used if necessary makes the lower part of tank
Material sends the top or middle part of equipment back to again, is fed again into equipment, intensive treatment effect.If carried out at operation using tower
Reason, liquid material can be sent into equipment by the top of tower, and the internals such as distributor or spraying nozzle reinforcing liquid can be used and exist
Distributing homogeneity in inner-tower filling material.Liquid material can send out equipment by the lower part of tank.
So that the lower part material of tank is sent the top of equipment back to again if desired, forced circulation pump can be used, is fed again into
In equipment, intensive treatment effect.
According to different feed states, the temperature of technique unit material system is maintained using heater and the method for strengthening heat preservation
Degree.
The gas continuously flowed is introduced using the mode for increasing supply gas pressure, it is real by the quantity for controlling to adjust discharge gas
Existing control system pressure is in desired index.If using tank carry out operation processing, gas material can by tank lower part, on
Portion or middle part are sent into equipment, and the internals such as distributor can be used to scheme the probability of increase gas-liquid contact.Gas material can be by
Equipment is sent out at the top of tank or middle part.If carrying out operation processing using tower, gas material can be sent into equipment by the lower part of tower
It is interior, the internals such as distributor can be used and strengthen distributing homogeneity of the gas in inner-tower filling material.Gas material can be by the upper of tank
Send out equipment in portion.
The recycling of gas circulator can be used in the gas continuously flowed.The temperature of the gas continuously flowed is not less than work
Preheater heating before gas introduces can be used in temperature in skill unit.
Gas should pass through demister before leaving equipment.The gas of discharge recycles after washing absorption tower washing, purifying can be used
It uses.
Usual such material all contains sufficient amount of water, if the lazy weight of water, before raw material is sent into technique unit
It is homogeneously added into the water of needs.
Strengthen reaction effect if necessary to catalyst, requirement can be homogeneously added into before raw material is sent into technique unit
Liquid catalyst, solid catalyst needs are loaded into equipment in advance.
Treated, and material is sent into refined unit, and the substances such as organic acid esters are removed in refinement treatment unit, are further mentioned
It is pure to obtain the higher product of purity.
Technical solution of the present invention has the following advantages that：
The present invention provides a kind of method of the organic acid tertiary ammonium salt in removal polyhydroxy-alcohol substance, adjusting contains tertiary amine
The pH value of the polyhydroxy-alcohol substance aqueous solution of salt promotes tertiary ammonium salt to convert to obtain free tertiary amine to 6-8, then with indifferent gas
Body is in contact, and by it, Desorption separation is removed from liquid phase.In the minimizing technology of the application, moisture is usually contained to ensure tertiary amine
The conversion of salt.The present processes are suitable for the reaction product of trimethylamine catalysis aldehyde condensation hydrogenation synthesis, including but not limited to
1,3- dihydroxy butane, 2,2- dimethyl -1,3- propylene glycol, 1,1,1- tri- (methylol) propane, 1,1,1- tri- (methylol) second
The removal of trimethylamine salt in the polyhydroxy-alcohols substance such as alkane.Before above-mentioned reaction product is refined, increases and remove organic uncle
Amine salt the step of, the quality and yield of final products are improved, to be conducive to the raising of downstream product processing performance.
The present invention removes in the method for the organic acid tertiary ammonium salt in polyhydroxy-alcohol substance, is urged by addition acidity or alkalinity
Agent adjusts pH to 6-8, wherein and basic catalyst typically contains metal ion, is easy to be enriched in equipment or remains on liquid phase,
The heavy constituents such as high boiling esters therein are hydrolyzed, therefore, though it is able to achieve trimethylamine catalysis aldehyde condensation hydrogenation synthesis
The removal of organic acid tertiary ammonium salt in reaction product, but obtained product purity is not high.It is preferred that acidic catalyst is used, it is practical to grasp
Show the pH value for adjusting the reaction product of trimethylamine catalysis aldehyde condensation hydrogenation synthesis using acidic catalyst in work, has with removal
Machine acid tertiary ammonium salt, then carry out the product obtained after process for refining purity it is higher.
Specific embodiment
Process for refining in the following embodiments of the application is suitable for the essence of polyhydroxy-alcohol substances all in the prior art
Technique processed, for convenient for comparison, the process for refining that the following embodiments of the application use is under the reduced pressure of absolute pressure 45kPa
The process of column distillation processing product is distilled, destilling tower lower part is boiled using heater heating liquid phase material, used at the top of destilling tower
Condenser condense gaseous phase materials, top condensation material parts as reflux return tower in, partially as product send out equipment with
Outer collection, reflux ratio 0.8 are equipped with the devices such as column plate or filler and distributor, theoretical cam curve 45 in a distillation column.
Embodiment 1
N is detected, N-dimethyl amine is catalyzed in the reaction product of acetaldehyde condensation hydrogenation synthesis, contains 1,3- dihydroxy
Butane, acetic acid N, the N-ingredients such as dimethyl amine salt and water, wherein acetic acid N, N-dimethyl amine salt mass content is
1.05%, water 10.21%.Into the reaction product be added formic acid with adjust unitary fluid product pH value be 6.5, will be above-mentioned
Material is injected from the top of reactor tank, is discharged from the lower part of reactor tank, and flow is 5 kgs/hour, while nitrogen is from reactor tank
Lower part injection, from the top of reactor tank be discharged, flow be 0.84 cube m/h, control the intracorporal pressure of reactor tank be
0.2MPa, 110 DEG C of reaction temperature, nitrogen and material counter current contacting 48 hours in tank body, the liquid phase material being discharged by reactor tank
It is refined into destilling tower by aforementioned process for refining, is detected the mass content of 1,3-dihydroxy butane in its refined products
It is 99.6%.
Embodiment 2
In the reaction product synthesized through detection trimethylamine catalysis formaldehyde with isobutylaldehyde condensation hydrogenation, contain 2,2- dimethyl-
The ingredients such as 1,3-PD, formic acid front three amine salt, isobutyric acid front three amine salt and water, wherein formic acid front three amine salt, isobutyric acid front three
Amine salt and water quality content are 0.94%, 0.08% and 15.46%.Above-mentioned material is injected from the top of reaction tower, from reaction
The lower part of tower is discharged, and flow is 5 kgs/hour, the ZSM-5 hydrogen that the silica alumina ratio that filling diameter is 2.5mm in reaction tower is 250
Type molecular sieve loads height 500mm, and the pH value that material system in reaction tower is adjusted by the way that acetic acid is added into the reaction product is
6.Nitrogen is injected from the lower part of reaction tower, is discharged from the top of reaction tower, and flow is 0.84 cube m/h, control reaction
The intracorporal pressure of tower be 0.3MPa, 120 DEG C of reaction temperature, nitrogen and material counter current contacting 8 hours in reaction tower, by reaction tower
The liquid phase material of discharge enters destilling tower and is refined by aforementioned process for refining, is detected 2,2- dimethyl-in its refined products
The mass content of 1,3- propylene glycol is 99.5%.
Embodiment 3
In reaction product through detection triethylamine catalysis formaldehyde and n butyraldehyde aldolization hydrogenation synthesis, contain 1,1,1- tri- (hydroxyl
Methyl) ingredients such as propane, triethylammonium formate, n-butyric acie triethylamine salt and water, wherein triethylammonium formate, three second of n-butyric acie
The mass content of amine salt is respectively 2.56% and 0.97%, water 55.13%.It is whole to adjust that hydrochloric acid is added into the reaction product
The pH value of body product liquid is 6, and above-mentioned material is injected from the top of reaction tower, is discharged from the lower part of reaction tower, flow 5
Kg/hour, at the same nitrogen from the lower part of reaction tower inject, from the top of reaction tower be discharged, flow be 0.42 cubic metre/it is small
When, the control intracorporal pressure of reactor tank is 0.3MPa, and 120 DEG C of reaction temperature, nitrogen and material counter current contacting 8 in tank body are small
When, destilling tower is entered by the liquid phase material that reaction tower is discharged and is refined by aforementioned process for refining, is detected in its refined products
The mass content of 1,1,1- tri- (methylol) propane is 99.3%.
Embodiment 4
In the reaction product synthesized through detection trimethylamine catalysis formaldehyde with isobutylaldehyde condensation hydrogenation, contain 2,2- dimethyl-
The ingredients such as 1,3-PD, formic acid front three amine salt, isobutyric acid front three amine salt and water, wherein formic acid front three amine salt, isobutyric acid front three
The mass content of amine salt is respectively 1.43% and 0.26%, water 32.06%.It is whole to adjust that acetic acid is added into the reaction product
The pH value of body product liquid is 6.5, and above-mentioned material is injected from the top of reaction tower, is discharged from the lower part of reaction tower, flow
It is 5 kgs/hour, while the gaseous mixture that nitrogen and hydrogen are formed is injected from the lower part of reaction tower, is discharged from the top of reaction tower,
Its flow is 0.84 cube m/h, and the control intracorporal pressure of reactor tank is 0.4MPa, 140 DEG C of reaction temperature, nitrogen and material
Counter current contacting 5 hours in tank body enter destilling tower by the liquid phase material that reaction tower is discharged and are refined by aforementioned process for refining,
The mass content for being detected 2,2- dimethyl -1,3- propylene glycol in its refined products is 99.7%.
Embodiment 5
In reaction product through detection trimethylamine catalysis formaldehyde and n butyraldehyde aldolization hydrogenation synthesis, contain 2- ethyl -1,3-
The ingredients such as propylene glycol, formic acid front three amine salt, n-butyric acie front three amine salt and water, wherein 2- ethyl -1,3-PD, formic acid front three
Amine salt, n-butyric acie front three amine salt mass content be respectively 1.17% and 0.28%, water 45.60%.Into the reaction product
Be added the glycine betaine containing 100PPm N-methylmorpholine with adjust unitary fluid product pH value be 7.5, by above-mentioned material from
The top of reaction tower is injected, and is discharged from the lower part of reaction tower, and flow is 5 kgs/hour, while hydrogen, carbon monoxide and first
The gaseous mixture (trimethylamine containing 1.5wt%) that alkane is formed is injected from the lower part of reaction tower, is discharged from the top of reaction tower, flow
It is 0.42 cube m/h, the control intracorporal pressure of reactor tank is 0.5MPa, and 150 DEG C of reaction temperature, nitrogen and material are in tank body
Interior counter current contacting 12 hours enters destilling tower by the liquid phase material that reaction tower is discharged and is refined by aforementioned process for refining, through examining
The mass content for surveying 2- ethyl -1,3- propylene glycol in its refined products is 99.4%.
Embodiment 6
Through detect N, N- dimethyl amine be catalyzed acetaldehyde condensation hydrogenation synthesis reaction product in, containing 1,3-BDO,
The ingredients such as acetic acid N, N- dimethyl amine salt and water, wherein acetic acid N, N- dimethyl amine salt and water quality content are 1.05%
With 22.07%.Above-mentioned material is injected from the top of reaction tower, is discharged from the lower part of reaction tower, flow is 5 kgs/hour,
The Hydrogen Y molecular sieve that silica alumina ratio that diameter is 3.2mm is 250 is loaded in reaction tower, height 500mm is loaded, by the reaction
It is 7 that butyric acid is added in product and adjusts the pH value of material system in reaction tower.The gaseous mixture of hydrogen, carbon monoxide and methanogenesis from
The lower part of reaction tower is injected, and is discharged from the top of reaction tower, and flow is 0.28 cube m/h, and control reaction tower is intracorporal
Pressure is 0.1MPa, 80 DEG C of reaction temperature, nitrogen and material counter current contacting 24 hours in reaction tower, and the liquid being discharged by reaction tower
Phase materials enter destilling tower and are refined by aforementioned process for refining, through the mass content for detecting 1,3-BDO in its refined products
It is 99.0%.
Embodiment 7
N is detected, N- dimethyl amine is catalyzed in the reaction product that formaldehyde is synthesized with propionic aldehyde condensation hydrogenation, contains 1,1,1-
The ingredients such as three (methylol) ethane, formic acid N, N- dimethyl amine salt, propionic acid N, N- dimethyl amine salt and water, wherein formic acid
N, N- dimethyl amine salt, propionic acid N, N- dimethyl amine salt mass content be respectively 3.07% and 0.62%, water is
35.72%.Mass ratio 1 is added into the reaction product：50 sodium hydroxide and diatomite are to adjust the pH of unitary fluid product
Value is 8, and above-mentioned material is injected from the top of reaction tower, is discharged from the lower part of reaction tower, flow is 5 kgs/hour, simultaneously
Methane (N containing 0.2wt%, N- dimethyl amine) is injected from the lower part of reaction tower, is discharged from the top of reaction tower, and flow is
0.42 cube m/h, the control intracorporal pressure of reactor tank is 0.4MPa, and 140 DEG C of reaction temperature, nitrogen and material are in tank body
Counter current contacting 1 hour, destilling tower is entered by the liquid phase material that reaction tower is discharged and is refined by aforementioned process for refining, through detecting it
The mass content of N in refined products, N- dimethyl amine is 98.1%.
The effect for removing the method for the organic acid tertiary ammonium salt in polyhydroxy-alcohol substance to illustrate the invention, by above-mentioned implementation
The raw material that example 1-7 is used directly is refined, and the product index after purification is as shown in the table：
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (15)
1. a kind of method of the organic acid tertiary ammonium salt in removal polyhydroxy-alcohol substance, including, adjust the polyhydroxy containing tertiary ammonium salt
Then the pH value of base alcohols material aqueous solution is in contact to 6-8 with inert gas.
2. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 1, which is characterized in that with quality
Percentage meter, water content at least 10% in the polyhydroxy-alcohol substance aqueous solution.
3. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 2, which is characterized in that adjust pH
When polyhydroxy-alcohol substance after value is in contact with inert gas, the temperature for controlling treatment process is higher than under the conditions of processing pressure
The boiling point of trimethylamine, the boiling point being lauched not higher than relevant pressure.
4. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 3, which is characterized in that processed
The temperature of journey is 80-150 DEG C.
5. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 1 to 4, which is characterized in that
When polyhydroxy-alcohol substance after adjusting pH value is in contact with inert gas, the pressure for controlling treatment process is higher than treatment temperature item
The saturated vapor pressure that part is lauched, not higher than the saturated vapor pressure of trimethylamine under relevant temperature.
6. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 5, which is characterized in that processed
The pressure of journey is 0.1-0.5MPa.
7. the method for the tertiary ammonium salt in -6 any removal polyhydroxy-alcohol substances according to claim 1, which is characterized in that
The mass content of tertiary amine is less than 1.5% in the inert gas, and preferably smaller than 0.2%, more preferably 0%.
8. the method for the tertiary ammonium salt in -7 any removal polyhydroxy-alcohol substances according to claim 1, which is characterized in that
The inert gas is the mixture of one or more of nitrogen, hydrogen, carbon monoxide, methane and ethane.
9. the method for the tertiary ammonium salt in -8 any removal polyhydroxy-alcohol substances according to claim 1, which is characterized in that
The time that polyhydroxy-alcohol substance after adjusting pH value is in contact with inert gas is 1-48 hours, preferably 5-24 hours.
10. the method for the tertiary ammonium salt in -9 any removal polyhydroxy-alcohol substances, feature exist according to claim 1
In polyhydroxy-alcohol substance and inert gas counter current contacting after adjusting pH value.
11. the method for the tertiary ammonium salt in -10 any removal polyhydroxy-alcohol substances, feature exist according to claim 1
In addition acidic catalyst or basic catalyst into the polyhydroxy-alcohol substance containing tertiary ammonium salt, to adjust its pH value to 6-
8。
12. the method for the tertiary ammonium salt in removal polyhydroxy-alcohol substance according to claim 11, which is characterized in that described
Acidic catalyst is the mixture of one or more of organic acid, inorganic acid, solid acid and molecular sieve；The basic catalyst
For organic base and/or solid base.
13. the method for the tertiary ammonium salt in -12 any removal polyhydroxy-alcohol substances, feature exist according to claim 1
In the polyhydroxy-alcohol substance is the product that trimethylamine is catalyzed the synthesis of aldehyde condensation hydrogenation.
14. the method for the tertiary ammonium salt in -13 any removal polyhydroxy-alcohol substances, feature exist according to claim 1
In, the polyhydroxy-alcohol substance has the structure as shown in following formula (1),
Wherein R1、R2、R3、R4、R5、R6It is separately hydrogen, oxygen-containing group or the alkyl with 1-6 carbon atom；And R1、R2、
R3、R4、R5、R6In at least containing there are two and be no more than four oxygen-containing groups, the oxygen-containing group be hydroxyl or methylol.
15. a kind of process for refining of polyhydroxy-alcohol substance, which is characterized in that further include using claim 1- before refining
The step of 14 any methods remove the tertiary ammonium salt in polyhydroxy-alcohol substances.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855515A (en) * | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
| JPH0782192A (en) * | 1993-09-10 | 1995-03-28 | Mitsubishi Gas Chem Co Inc | Production of neopentyl glycol |
| CN1219527A (en) * | 1997-10-22 | 1999-06-16 | 广荣化学工业株式会社 | Producing method for trimethylolalkane |
| CN1220254A (en) * | 1997-10-22 | 1999-06-23 | 广荣化学工业株式会社 | Producing method for trimethylolalkane |
| CN105008317A (en) * | 2013-01-31 | 2015-10-28 | 伊斯曼化学公司 | Process for producing polyols |
| CN105073702A (en) * | 2013-01-31 | 2015-11-18 | 伊斯曼化学公司 | Preparation of hydroxy aldehydes |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
-
2018
- 2018-05-22 CN CN201810496739.4A patent/CN108821943A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855515A (en) * | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
| JPH0782192A (en) * | 1993-09-10 | 1995-03-28 | Mitsubishi Gas Chem Co Inc | Production of neopentyl glycol |
| CN1219527A (en) * | 1997-10-22 | 1999-06-16 | 广荣化学工业株式会社 | Producing method for trimethylolalkane |
| CN1220254A (en) * | 1997-10-22 | 1999-06-23 | 广荣化学工业株式会社 | Producing method for trimethylolalkane |
| CN105008317A (en) * | 2013-01-31 | 2015-10-28 | 伊斯曼化学公司 | Process for producing polyols |
| CN105073702A (en) * | 2013-01-31 | 2015-11-18 | 伊斯曼化学公司 | Preparation of hydroxy aldehydes |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
Non-Patent Citations (1)
| Title |
|---|
| 蓝仲薇等: "《有机化学基础》", 31 July 2008 * |
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