CN105085188A - Synthesis method of pentaerythritol - Google Patents
Synthesis method of pentaerythritol Download PDFInfo
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- CN105085188A CN105085188A CN201510517557.7A CN201510517557A CN105085188A CN 105085188 A CN105085188 A CN 105085188A CN 201510517557 A CN201510517557 A CN 201510517557A CN 105085188 A CN105085188 A CN 105085188A
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- tetramethylolmethane
- acetaldehyde
- formaldehyde
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a synthesis method of pentaerythritol. The synthesis method comprises the following steps: (1) carrying out aldol condensation reaction on formaldehyde and acetaldehyde under the action of a weak base catalyst to generate trihydroxymethyl acetaldehyde; (2) after condensation reaction, carrying out distillation separation to separate out a formaldehyde, triethylamine and methanol mixed solution; (3) carrying out catalytic hydrogenation on a trihydroxymethyl acetaldehyde aqueous solution obtained after distillation by adopting a nickel catalyst; (4) distilling a pentaerythritol solution obtained after catalytic hydrogenation to recover methanol, and carrying out distillation recovery on methanol; and (5) carrying out evaporation, crystallization, centrifugation and drying on a distilled pentaerythritol solution to obtain a pentaerythritol finished product. Compared with the prior art, the synthesis method has the advantages that the pentaerythritol finished product has high purity and high yield, the side reaction is little, sodium salts are not generated, three wastes are few and the like.
Description
Technical field
The invention belongs to chemical production technical field, relate to a kind of processing method of shortening synthesis of pentaerythritol.
Background technology
Tetramethylolmethane is mainly used in coatings industry, can, in order to manufacture phthalic resin coating, the hardness of paint film, gloss and weather resistance can be made to be improved.It is also used as the required abietinic raw material such as colored paint, varnish and printing-ink, and can siccative oil processed, smolderability coating and aircraft oil etc.The fatty acid ester of tetramethylolmethane is efficient lubricant and plasticizer for polyvinyl chloride, and its epoxy derivative is then produce the non-raw material from raw tensio-active agent.Tetramethylolmethane easily and metal form complex compound, also use as Ethylene Diaminetetra Acetic Acid in detergent formulation.In addition, also for productions such as medicine, agricultural chemicals.Containing four equivalent methylols in tetramethylolmethane molecule, have the symmetry of height, what be therefore often used as polyfunctional compound produces raw material.Nitratedly can obtain trinitrol (pacifying very much, PETN) by it, be a kind of powerful explosive; Esterification can obtain pentaerythritol triacrylate (PETA), as coating.
In Production of pentaerythritol in the past, formaldehyde, acetaldehyde, when sodium hydroxide makees catalyzer, react, and reaction terminates rear quick acid neutralization, obtains tetramethylolmethane, sodium salt and a part of dipentaerythritol.This processing method produce at home in comparative maturity, but this method produce in steam consumption high, power consumption is higher, and raw material consumption is high, and side reaction is more in reaction, tetramethylolmethane content is low, and sewage is many and difficult, technical process is long, and manual labor amount is large, and the sodium salt added value of by-product is not high.
Summary of the invention
Object of the present invention is just to provide a kind of processing method of shortening synthesis of pentaerythritol, has the advantages such as tetramethylolmethane purity is high, yield is high, side reaction is few, do not produce sodium salt, the three wastes are few.
The object of the invention is to be achieved by the following technical programs: a kind of synthetic method of tetramethylolmethane, it is characterized in that, 1) there is aldol reaction in formaldehyde and acetaldehyde under the effect of weak base catalyst, generate trimethylol acetaldehyde, 2) condensation reaction carries out rectifying separation after terminating, isolate formaldehyde and triethylamine, methyl alcohol mixed liquor, 3) the trimethylol acetaldehyde aqueous solution by obtaining after rectifying adopts nickel catalyst to carry out shortening, 4) rectifying is carried out to the tetramethylolmethane solution after shortening and reclaim methyl alcohol, rectifying recovery is carried out to methyl alcohol, 5) the tetramethylolmethane solution after rectifying is through evaporation, crystallization, centrifugal, dry acquisition tetramethylolmethane finished product.
The further prioritization scheme of the present invention also has following characteristics:
The mol ratio of described formaldehyde, acetaldehyde, triethylamine is (5-6.2): 1:1.
In described step 1), weak base catalyst is triethylamine.
Before described step 1) aldol reaction, by dripping weak base catalyst control pH in formaldehyde between 7.8-8.2, after dropping acetaldehyde starts aldol reaction, in control reaction process, pH is between 8-9, and temperature of reaction is between 28 DEG C-30 DEG C.
In described step 3), nickel catalyst is Raney's nickel RTH-311 type catalyzer.
In described step 3), institute's hydrogenation is the hydrogen of purity more than 99.9%.
Shortening synthesis of pentaerythritol provided by the present invention generates than sodium method in the past and has the following advantages: 1, comparatively sodium method Production of pentaerythritol, and tetramethylolmethane purity is high; 2, improve a yield, decrease subsequent recovery device, shorten technical process, improve working efficiency; 3, do not have sodium salt to produce in condensated liquid, decrease the technique that sodium salt is reclaimed; 4, avoid the generation of dipentaerythritol, decrease the generation of the by product such as tripentaerythritol and acetal simultaneously; 5, raw material consumption is reduced; 6, the generation of the three wastes is reduced.
Accompanying drawing explanation
Fig. 1 is process flow diagram provided by the invention.
Embodiment
Example one:
As shown in Figure 1, the invention provides a kind of processing method of shortening synthesis of pentaerythritol, its basic process steps is as follows: the formaldehyde, acetaldehyde, the triethylamine that 1) will configure, puts on request in condensation kettle and carries out aldol reaction generation trimethylol acetaldehyde condensated liquid; 2) condensation reaction terminates to carry out rectifying separation fast afterwards, make formaldehyde as far as possible the short period of time be present in triethylamine, avoid the generation of side reaction, rectifying goes out formaldehyde, triethylamine and a small amount of methyl alcohol, PARA FORMALDEHYDE PRILLS(91,95) and triethylamine carry out rectifying again, isolate formaldehyde and triethylamine, this formaldehyde and triethylamine return condensation reaction and again participate in reaction; 3) the trimethylol acetaldehyde aqueous solution obtained after rectifying carries out shortening, and shortening adopts nickel catalyst, and the condition of High Purity Hydrogen; 4) after shortening, to the rectifying of tetramethylolmethane solution, obtain tetramethylolmethane solution and evaporate; 5) evaporation concentration liquid is carried out crystallization, centrifugal, dry acquisition finished product.
Concrete actually operating is as follows: formaldehyde, acetaldehyde, triethylamine are prepared according to 5:1:1 mol ratio.First in condensation kettle, add formaldehyde, substep instills triethylamine, adjustment PH=7.8-8.0, then substep instills acetaldehyde, control PH=8 ~ 9 in reaction process, and temperature controls at 28-30 DEG C, and the reaction times is 1 hour.After reaction result, condensated liquid is pumped into rectifying tower, rectifying goes out light constituent, the aqueous solution obtaining trimethylol acetaldehyde passes into High Purity Hydrogen (purity more than 99.9%) in hydrogenation tower, adopts Raney's nickel RTH-311 type catalyzer to carry out catalytic hydrogenation reaction, obtains the tetramethylolmethane aqueous solution.Go out a small amount of methyl alcohol carrying out rectifying to this aqueous solution, obtain concentrated after the tetramethylolmethane aqueous solution.Evaporate this solution, crystallization, centrifugal, drying obtain tetramethylolmethane finished product, be 91.5% through detecting this tetramethylolmethane yield, tetramethylolmethane content reaches 95.2%.
Example two:
By formaldehyde, acetaldehyde, triethylamine is prepared according to 5.5:1:1 mol ratio, first in condensation kettle, add formaldehyde, substep instills triethylamine, adjustment PH=8.0-8.2, substep instills acetaldehyde again, control PH=8 ~ 9 in reaction process, temperature controls at 28-30 DEG C, reaction times is 1 hour, after reaction result, condensated liquid is pumped into rectifying tower, rectifying goes out light constituent, the aqueous solution obtaining trimethylol acetaldehyde passes into High Purity Hydrogen (purity more than 99.9%) in hydrogenation tower, Raney's nickel RTH-311 type catalyzer is adopted to carry out catalytic hydrogenation reaction, obtain the tetramethylolmethane aqueous solution, go out a small amount of methyl alcohol carrying out rectifying to this aqueous solution, obtain the tetramethylolmethane aqueous solution after concentrating, this solution is evaporated, crystallization, centrifugal, drying obtains tetramethylolmethane finished product, passing through and detecting this tetramethylolmethane yield is 92.1%, tetramethylolmethane content reaches 95.8%.
Example three:
By formaldehyde, acetaldehyde, triethylamine is prepared according to 5.8:1:1 mol ratio, first in condensation kettle, add formaldehyde, substep instills triethylamine, adjustment PH=8.0, substep instills acetaldehyde again, control PH=8 ~ 9 in reaction process, temperature controls at 28 DEG C, reaction times is 1 hour, after reaction result, condensated liquid is pumped into rectifying tower, rectifying goes out light constituent, the aqueous solution obtaining trimethylol acetaldehyde passes into High Purity Hydrogen (purity more than 99.9%) in hydrogenation tower, Raney's nickel RTH-311 type catalyzer is adopted to carry out catalytic hydrogenation reaction, obtain the tetramethylolmethane aqueous solution, go out a small amount of methyl alcohol carrying out rectifying to this aqueous solution, obtain the tetramethylolmethane aqueous solution after concentrating, this solution is evaporated, crystallization, centrifugal, drying obtains tetramethylolmethane finished product, passing through and detecting this tetramethylolmethane yield is 92.5%, tetramethylolmethane content reaches 96.2%.
Example four:
By formaldehyde, acetaldehyde, triethylamine is prepared according to 6.2:1:1 mol ratio, first in condensation kettle, add formaldehyde, substep instills triethylamine, adjustment PH=8.0, substep instills acetaldehyde again, control PH=8 ~ 9 in reaction process, temperature controls at 28 DEG C, reaction times is 1 hour, after reaction result, condensated liquid is pumped into rectifying tower, rectifying goes out light constituent, the aqueous solution obtaining trimethylol acetaldehyde passes into High Purity Hydrogen (purity more than 99.9%) in hydrogenation tower, Raney's nickel RTH-311 type catalyzer is adopted to carry out catalytic hydrogenation reaction, obtain the tetramethylolmethane aqueous solution, go out a small amount of methyl alcohol carrying out rectifying to this aqueous solution, obtain the tetramethylolmethane aqueous solution after concentrating, this solution is evaporated, crystallization, centrifugal, drying obtains tetramethylolmethane finished product, passing through and detecting this tetramethylolmethane yield is 92.9%, tetramethylolmethane content reaches 96.8%.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention; Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (6)
1. the synthetic method of a tetramethylolmethane, it is characterized in that, 1) there is aldol reaction in formaldehyde and acetaldehyde under the effect of weak base catalyst, generate trimethylol acetaldehyde, 2) condensation reaction carries out rectifying separation after terminating, isolate formaldehyde and triethylamine, methyl alcohol mixed liquor, 3) the trimethylol acetaldehyde aqueous solution by obtaining after rectifying adopts nickel catalyst to carry out shortening, 4) rectifying is carried out to the tetramethylolmethane solution after shortening and reclaim methyl alcohol, rectifying recovery is carried out to methyl alcohol, 5) the tetramethylolmethane solution after rectifying is through evaporation, crystallization, centrifugal, dry acquisition tetramethylolmethane finished product.
2. the synthetic method of a kind of tetramethylolmethane according to claim 1, it is characterized in that, the mol ratio of formaldehyde, acetaldehyde, triethylamine is (5-6.2): 1:1.
3. the synthetic method of a kind of tetramethylolmethane according to claim 1, it is characterized in that, in described step 1), weak base catalyst is triethylamine.
4. the synthetic method of a kind of tetramethylolmethane according to claim 1, it is characterized in that, before described step 1) aldol reaction, by dripping weak base catalyst control pH in formaldehyde between 7.8-8.2, after dropping acetaldehyde starts aldol reaction, in control reaction process, pH is between 8-9, and temperature of reaction is between 28 DEG C-30 DEG C.
5. the synthetic method of a kind of tetramethylolmethane according to claim 1, it is characterized in that, in described step 3), nickel catalyst is Raney's nickel RTH-311 type catalyzer.
6. the synthetic method of a kind of tetramethylolmethane according to claim 1, it is characterized in that, in described step 3), institute's hydrogenation is the hydrogen of purity more than 99.9%.
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| CN201510517557.7A CN105085188A (en) | 2015-08-22 | 2015-08-22 | Synthesis method of pentaerythritol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669371A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Production method of trimethylolethane |
| CN109369347A (en) * | 2018-12-10 | 2019-02-22 | 安徽金禾实业股份有限公司 | A kind of preparation method of tripentaerythritol |
| CN109485578A (en) * | 2018-11-15 | 2019-03-19 | 内蒙古圣氏化学股份有限公司 | The synthesis technology of 2- amino -1,3- propylene glycol |
| CN112479816A (en) * | 2020-11-30 | 2021-03-12 | 安徽金禾实业股份有限公司 | Continuous condensation method of pentaerythritol |
| CN113845403A (en) * | 2021-11-30 | 2021-12-28 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propylene glycol and pentaerythritol |
-
2015
- 2015-08-22 CN CN201510517557.7A patent/CN105085188A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669371A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Production method of trimethylolethane |
| CN109485578A (en) * | 2018-11-15 | 2019-03-19 | 内蒙古圣氏化学股份有限公司 | The synthesis technology of 2- amino -1,3- propylene glycol |
| CN109369347A (en) * | 2018-12-10 | 2019-02-22 | 安徽金禾实业股份有限公司 | A kind of preparation method of tripentaerythritol |
| CN112479816A (en) * | 2020-11-30 | 2021-03-12 | 安徽金禾实业股份有限公司 | Continuous condensation method of pentaerythritol |
| CN113845403A (en) * | 2021-11-30 | 2021-12-28 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propylene glycol and pentaerythritol |
| CN113845403B (en) * | 2021-11-30 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propanediol and pentaerythritol |
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