CN102617285A - Method for generating trimethylolpropane by condensation of formaldehyde and n-butyl alcohol - Google Patents
Method for generating trimethylolpropane by condensation of formaldehyde and n-butyl alcohol Download PDFInfo
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- CN102617285A CN102617285A CN2012100616283A CN201210061628A CN102617285A CN 102617285 A CN102617285 A CN 102617285A CN 2012100616283 A CN2012100616283 A CN 2012100616283A CN 201210061628 A CN201210061628 A CN 201210061628A CN 102617285 A CN102617285 A CN 102617285A
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Abstract
The invention discloses a method for generating trimethylolpropane (TMP) by condensation of formaldehyde and n-butyl alcohol. The method comprises the following steps of: A) after the concentration of a formaldehyde solution in a condensation kettle reaches 9 to 14 percent, feeding sodium hydroxide into the condensation kettle, feeding n-butyl alcohol, adding formic acid to adjust pH value to be 6 to 7.5, and after reaction, obtaining a condensation solution from the condensation kettle; B) performing evaporation concentration on the condensation solution to obtain an evaporation concentration solution; C) extracting the evaporation concentration solution and a solvent to obtain an extract phase and a raffinate phase; and D) washing the extract phase by using water, and rectifying to obtain a trimethylolpropane finished product. The method guarantees that n-butyl alcohol is reacted completely, reduces production cost, guarantees the production of byproducts sodium formate and bi (trihydroxyl) and reduces environmental pollution; and multi-stage rectification is adopted, so that the quality of TMP is improved.
Description
Technical field
The invention belongs to chemical production technical field, relate in particular to the method that a kind of formaldehyde and propyl carbinol condensation generate TriMethylolPropane(TMP).
Background technology
TriMethylolPropane(TMP) (Trimethylolpropane; Hereinafter to be referred as TMP), be a kind of trihydroxy-alcohol that essential industry is worth that has, be used for the production of phthalic resin coating; Be mainly used in the production of urethane resin at present, also be used for synthetic multi-functional propenoate in addition.
The main raw material of preparation TMP is butyraldehyde-n, formaldehyde and sodium hydroxide, adopts intersection Cannizzaro (Cannizzaro) condensation method to produce, and reaction process roughly is divided into two stages; At first aldol condensation takes place in formaldehyde and butyraldehyde-n under alkaline catalysis, generates 2,2-dihydroxymethyl butyraldehyde; Then under alkaline catalysis, 2,2-dihydroxymethyl butyraldehyde continues with formaldehyde generation Cannizzaro reaction; Butyraldehyde-n is reduced to TriMethylolPropane(TMP); Formaldehyde then is oxidized to formic acid, and the caustic soda neutralization through the process katalysis generates the by product sodium formiate.
In above-mentioned production process, need to reduce consumption of raw materials, improve the quality of TriMethylolPropane(TMP) finished product, reduce the generation of pollutent.
Summary of the invention
The purpose of this invention is to provide the method that a kind of formaldehyde and propyl carbinol condensation generate TriMethylolPropane(TMP), can reduce consumption of raw materials, improve the quality of finished product.
Technical scheme of the present invention is: a kind of formaldehyde and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), comprise the steps:
A, make formaldehyde solution concentration in the condensation still reach 9-14% after, in the condensation still, drop into sodium hydroxide, drop into propyl carbinol again, after having fed intake, add formic acid and regulate pH value to 6-7.5, from the condensation still, obtain condensated liquid after the reaction completion;
Obtain evaporation concentration liquid after B, the condensated liquid evaporation concentration;
C, evaporation concentration liquid and solvent extracted obtain extraction phase and extracting phase;
D, extraction phase carry out rectifying and obtain the TriMethylolPropane(TMP) finished product after washing.
When the formaldehyde solution temperature in the said condensation still is 43～47 ℃, drop into sodium hydroxide to the condensation still.
The whole temperature that feeds intake of said condensation still remains on 50-52 ℃.
The evaporation of said condensated liquid adopts the quadruple effect evaporation mode to carry out; Be that condensated liquid gets into first vaporizer and concentrates; Getting into second vaporizer again through spissated a part of condensated liquid further concentrates; A further spissated condensated liquid part gets into the 3rd vaporizer again and concentrates, and the part condensated liquid that the 3rd vaporizer concentrates out gets into the 4th vaporizer and concentrates back acquisition evaporation concentration liquid.
Through variable valve 35%～55% liquid concentrator in first vaporizer is sent into second vaporizer; 35%～55% liquid concentrator is sent into the 3rd vaporizer in second vaporizer; 35%～55% liquid concentrator is sent into the 4th vaporizer in the 3rd vaporizer, 35%～55% liquid concentrator extraction in the 4th vaporizer.
In the quadruple effect evaporative process of said condensated liquid, steam from the 4th vaporizer get into the back the 4th vaporizer with the condensated liquid heat exchange after get into successively again the 3rd vaporizer, second vaporizer and the 3rd vaporizer respectively with the 3rd vaporizer, second vaporizer and the 3rd vaporizer in the condensated liquid heat exchange.
Extraction phase after said evaporation concentration liquid and the solvent extraction is through level Four washing extraction.
Said extraction phase carries out level Four washing method of extraction:
After extraction phase gets into first extraction tank and the extracting phase counter-current extraction from second extraction tank; After the supernatant liquid of first extraction tank gets into second extraction tank and the extracting phase counter-current extraction from the 3rd extraction tank; After the supernatant liquid of second extraction tank gets into the 3rd extraction tank and the extracting phase counter-current extraction from the 4th extraction tank; The supernatant liquid of the 3rd extraction tank gets into the 4th extraction tank and soft water counter-current extraction, and the supernatant liquid of the 4th extraction tank is used for rectifying.
Said extracting phase is the sodium formiate mother liquor.
Said extraction phase rectifying is to separate through multistage rectification to obtain finished product TMP.
The method that said extraction phase carries out rectifying is:
A, extraction phase material get into first rectifying tower and carry out rectifying separation;
The material of extraction gets into second rectifying tower and carries out rectifying separation at the bottom of B, the first rectifying Tata;
The material of extraction gets into the 4th rectifying tower and carries out rectifying separation at the bottom of C, the second rectifying Tata, and the cat head material gets into the 3rd rectifying tower and carries out rectifying separation;
The material of extraction gets into the 5th rectifying tower and carries out rectifying separation, extraction finished product TriMethylolPropane(TMP) from tower at the bottom of D, the 4th rectifying Tata;
The material of extraction gets into the 6th rectifying tower and carries out rectifying separation at the bottom of E, the 5th rectifying Tata, gets into the rectifying once more of the 4th rectifying tower from the material of the 6th rectifying tower cat head extraction.
From the said second rectifying tower top extraction low-boiling point material, said low-boiling point material separates the raw material that obtains solvent and be used to prepare two three hydroxyls through the rectification under vacuum of the 3rd rectifying tower.
The material of extraction is used for two three hydroxyls of preparation at the bottom of said the 6th rectifying Tata.
Method of the present invention has guaranteed reacting completely of butyraldehyde-n, has reduced production cost, adopts multistage rectification, and the quality of TMP is improved, and has also guaranteed the production of sub product sodium formiate with two three hydroxyls simultaneously, has reduced environmental pollution.
Description of drawings
Fig. 1 is the schema that a kind of formaldehyde of the present invention and propyl carbinol condensation generate the method for TriMethylolPropane(TMP).
Fig. 2 is the process flow sheet of evaporation of the present invention.
Fig. 3 is the process flow sheet of extraction of the present invention.
Fig. 4 is the process flow sheet of rectifying of the present invention.
Embodiment
A kind of formaldehyde and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), and be as shown in Figure 1, comprises the steps:
A, condensation.In the condensation still, drop into concentrated formaldehyde and soft water, make the concentration of formaldehyde solution reach 9-14%, do not adjust if concentration reaches.The temperature regulating device of adjusting the condensation still simultaneously makes the temperature of formaldehyde solution reach 43～47 ℃; Begin to drop into alkali (sodium hydroxide) to the condensation still; Alkali was thrown butyraldehyde-n after feeding intake 3 minutes, and temperature regulating device (like interchanger) the control condensation still temperature curve of adjustment condensation still, the whole temperature that feeds intake are at 50-52 ℃, after insulation for some time; Add formic acid and regulate pH value to 6-7.5, after the reaction completion from condensation still extraction condensated liquid to the condensation liquid bath.The molecular ratio that feeds intake of formaldehyde, propyl carbinol and alkali is: 3.14-3.18: 1: 11-1.3.
Obtain evaporation concentration liquid after B, the condensated liquid evaporation concentration.
As shown in Figure 2; Condensated liquid in the condensation liquid bath 1 is squeezed into first vaporizer 4 through condensation liquid pump 2 through strainer 3 filtrations again concentrate after the under meter dominant discharge, materials part self circulation in first vaporizer 4, it is further concentrated that part gets into second vaporizer 5; Material part self circulation in second vaporizer 5; Part gets into the 3rd vaporizer 6 and further concentrates, material part self circulation in the 3rd vaporizer 6, and part gets into the 4th vaporizer 7 and further concentrates; Material part self circulation in the 4th vaporizer 7, part gets into next step extraction process.
With sending into second vaporizer 5 through spissated 35%～55% condensated liquid in first vaporizer 4, rest materials self circulates in first vaporizer 4 through recycle pump through variable valve; Send into the 3rd vaporizer 6 through spissated 35%～55% condensated liquid in second vaporizer 5, rest materials self circulates in second vaporizer 5 through recycle pump; Send into the 4th vaporizer 7 through spissated 35%～55% condensated liquid in the 3rd vaporizer 6, rest materials self circulates in the 3rd vaporizer 6 through recycle pump; Condensated liquid extraction through spissated 35%～55% in the 4th vaporizer 7 obtains evaporation concentration liquid entering subsequent processing, and rest materials self circulates in the 4th vaporizer 7 through recycle pump.
In the quadruple effect evaporative process of said condensated liquid, steam from the 4th vaporizer 7 get into the condensated liquid heat exchange after get into the 3rd vaporizer 6, second vaporizer 5 and the 3rd vaporizer 4 successively.It is thus clear that Fig. 2, heavy line is represented steam-pipe among the figure, and arrow is represented the flow direction of steam; Fine line is represented the liquid concentrator pipeline, and arrow is represented the flow direction of liquid concentrator; Dotted line is represented liquid concentrator self circulating line.
C, evaporation concentration liquid and solvent extracted obtain extraction phase and extracting phase;
Liquid concentrator in the 4th vaporizer 7 gets into extraction tank 8, and in the effect of stirring down and solvent, solvent is an isooctyl alcohol, gets into the separate chamber of extraction tank 8, insulation sedimentation layering, acquisition bottom extraction liquid through filter.The extracting phase here is the sodium formiate mother liquor.
D, extraction phase are through washing.
After the bottom extraction liquid gets into first extraction tank 9 and the extracting phase counter-current extraction from second extraction tank 10; After the supernatant liquid of first extraction tank 9 gets into second extraction tank 10 and the extracting phase counter-current extraction from the 3rd extraction tank 11; After the supernatant liquid of second extraction tank 10 gets into the 3rd extraction tank 11 and the extracting phase counter-current extraction from the 4th extraction tank 12; The supernatant liquid of the 3rd extraction tank 11 gets into the 4th extraction tank 12 and soft water counter-current extraction, and the supernatant liquid of the 4th extraction tank 12 is used for rectifying.As shown in Figure 3.Extracting phase then is the sodium formiate mother liquor.
Extraction phase after E, the washing extraction carries out rectifying and obtains TMP.
As shown in Figure 4; Will be from the next extraction phase material (containing TMP, solvent, less water etc.) of extraction process; In first rectifying tower 13, separate through rectification under vacuum; Cat head obtain purity be solvent more than 98% to solvent subsider 23, mainly contain TMP, lighting end and little solvent at the bottom of the tower and get into next procedure second rectifying tower 14 and further separate.(contain TMP from the material of first rectifying tower, 13 bottom extraction; Little solvent); Get into second rectifying tower 14 and further isolate low-boiling point materials such as solvent, lighting end, obtain low boilers at the top, getting into the 3rd rectifying tower 15 separates again; Obtain purity in second rectifying tower, 14 bottoms and be 90% TMP series material, get into the 4th rectifying tower 16 rectifying separation.The TMP series component materials of coming from second rectifying tower, 14 bottoms gets into the 4th rectifying tower 16 and carries out the rectification under vacuum separation; The light component product of cat head is delivered to light constituent accumulator tank 17 and is got back to the poor 18 barrellings take-away of light component storage, and the TMP work in-process that bottom product contains little solvent get into the 5th rectifying tower 19.The TMP series component materials of coming from the 4th rectifying tower 16 bottoms gets into the 5th rectifying tower 19 and carries out the rectification under vacuum separation; The material that cat head is adopted is sent into accumulator tank 24; The product at tower middle part is delivered to finished product medial launder 20 and is got back to finished product storage tank 21, and bottom product gets into the 6th rectifying tower 22.The serial component materials of coming at the bottom of the 5th rectifying tower 19 towers gets into the 6th rectifying tower 22 and carries out the rectification under vacuum Separation and Recovery; The product of cat head contains TMP60-90% and delivers to TMP accumulator tank 25 entering the 4th rectifying tower 16 rectifying once more, and bottom product mainly contains the raw material of double T MP and the two three hydroxyl workshop sections of three hydroxyl acetals conduct.The 3rd rectifying tower 15 will further separate in the 3rd rectifying tower 15 from the lighting end that the 14 top extraction of second rectifying tower come; Under vacuum condition; Cat head obtains solvent about 95% and gets into solvent subsider 23 and get back to extraction process and utilize again, and the tower bottom material uses as two three hydroxyl raw materials.
F, TMP packing
Liquid TMP in the finished product storage tank 21 is squeezed into the flaker room with pump tie the sheet drying, after crusher in crushing, obtain sheet and carry out the TMP packing again.
Claims (10)
1. formaldehyde and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), comprise the steps:
A, make the concentration of the formaldehyde solution in the condensation still reach 9-14% after, in the condensation still, drop into sodium hydroxide, drop into propyl carbinol again, after having fed intake, add formic acid and regulate pH value to 6-7.5, from the condensation still, obtain condensated liquid after the reaction completion;
Obtain evaporation concentration liquid after B, the condensated liquid evaporation concentration;
C, evaporation concentration liquid and solvent extracted obtain extraction phase and extracting phase;
D, extraction phase carry out rectifying and obtain the TriMethylolPropane(TMP) finished product after washing.
2. formaldehyde according to claim 1 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), it is characterized in that, when the formaldehyde solution temperature in the said condensation still is 43～47 ℃, drop into sodium hydroxide to the condensation still.
3. formaldehyde according to claim 1 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP); It is characterized in that; The evaporation of said condensated liquid adopts the quadruple effect evaporation mode to carry out, and promptly condensated liquid gets into first vaporizer and concentrates, and gets into second vaporizer again through spissated a part of condensated liquid and further concentrates; A further spissated condensated liquid part gets into the 3rd vaporizer again and concentrates, and the part condensated liquid that the 3rd vaporizer concentrates out gets into the 4th vaporizer and concentrates back acquisition evaporation concentration liquid.
4. formaldehyde according to claim 3 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP); It is characterized in that; Through variable valve 35%～55% liquid concentrator in first vaporizer is sent into second vaporizer; 35%～55% liquid concentrator is sent into the 3rd vaporizer in second vaporizer, and 35%～55% liquid concentrator is sent into the 4th vaporizer in the 3rd vaporizer, 35%～55% liquid concentrator extraction in the 4th vaporizer.
5. formaldehyde according to claim 4 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP); It is characterized in that; In the quadruple effect evaporative process of said condensated liquid, steam get into get into successively again after the 4th vaporizer and the 4th vaporizer condensated liquid heat exchange the 3rd vaporizer, second vaporizer and the 3rd vaporizer respectively with the 3rd vaporizer, second vaporizer and the 3rd vaporizer in the condensated liquid heat exchange.
6. formaldehyde according to claim 1 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), it is characterized in that said extraction phase is washed method of extraction and is:
After extraction phase gets into first extraction tank and the extracting phase counter-current extraction from second extraction tank; After the supernatant liquid of first extraction tank gets into second extraction tank and the extracting phase counter-current extraction from the 3rd extraction tank; After the supernatant liquid of second extraction tank gets into the 3rd extraction tank and the extracting phase counter-current extraction from the 4th extraction tank; The supernatant liquid of the 3rd extraction tank gets into the 4th extraction tank and soft water counter-current extraction, and the supernatant liquid of the 4th extraction tank is used for rectifying.
7. formaldehyde according to claim 6 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), it is characterized in that the method that said extraction phase carries out rectifying is:
A, extraction phase material get into first rectifying tower and carry out rectifying separation;
The material of extraction gets into second rectifying tower and carries out rectifying separation at the bottom of B, the first rectifying Tata;
The material of extraction gets into the 4th rectifying tower and carries out rectifying separation at the bottom of C, the second rectifying Tata, and the cat head material gets into the 3rd rectifying tower and carries out rectifying separation;
The material of extraction gets into the 5th rectifying tower and carries out rectifying separation, extraction finished product TriMethylolPropane(TMP) from tower at the bottom of D, the 4th rectifying Tata;
The material of extraction gets into the 6th rectifying tower and carries out rectifying separation at the bottom of E, the 5th rectifying Tata, gets into the rectifying once more of the 4th rectifying tower from the material of the 6th rectifying tower cat head extraction.
8. formaldehyde according to claim 7 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP); It is characterized in that; From the said second rectifying tower top extraction low-boiling point material, said low-boiling point material separates the raw material that obtains solvent and be used to prepare two three hydroxyls through the rectification under vacuum of the 3rd rectifying tower.
9. formaldehyde according to claim 7 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), it is characterized in that, the material of extraction is used for two three hydroxyls of preparation at the bottom of said the 6th rectifying Tata.
10. formaldehyde according to claim 1 and propyl carbinol condensation generate the method for TriMethylolPropane(TMP), it is characterized in that said extracting phase is the sodium formiate mother liquor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104728852A (en) * | 2015-03-27 | 2015-06-24 | 湖北三江化工有限责任公司 | Recovery system of trimethylolpropane waste gas |
| CN115677466A (en) * | 2022-11-11 | 2023-02-03 | 宁夏百川科技有限公司 | Preparation method of dimethylolbutyraldehyde |
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| CN1919815A (en) * | 2006-09-19 | 2007-02-28 | 天津市新天进科技开发有限公司 | Technological process for refining trimethylolpropane |
| CN101102986A (en) * | 2006-03-07 | 2008-01-09 | Lg化学株式会社 | Method for preparing trimethylolpropane |
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- 2012-03-09 CN CN2012100616283A patent/CN102617285A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101102986A (en) * | 2006-03-07 | 2008-01-09 | Lg化学株式会社 | Method for preparing trimethylolpropane |
| CN1919815A (en) * | 2006-09-19 | 2007-02-28 | 天津市新天进科技开发有限公司 | Technological process for refining trimethylolpropane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104728852A (en) * | 2015-03-27 | 2015-06-24 | 湖北三江化工有限责任公司 | Recovery system of trimethylolpropane waste gas |
| CN104728852B (en) * | 2015-03-27 | 2017-03-01 | 湖北三江化工有限责任公司 | A kind of recovery system of trimethylolpropane waste gas |
| CN115677466A (en) * | 2022-11-11 | 2023-02-03 | 宁夏百川科技有限公司 | Preparation method of dimethylolbutyraldehyde |
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Application publication date: 20120801 |