CN1037700A - 2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product - Google Patents
2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product Download PDFInfo
- Publication number
- CN1037700A CN1037700A CN88102978A CN88102978A CN1037700A CN 1037700 A CN1037700 A CN 1037700A CN 88102978 A CN88102978 A CN 88102978A CN 88102978 A CN88102978 A CN 88102978A CN 1037700 A CN1037700 A CN 1037700A
- Authority
- CN
- China
- Prior art keywords
- isobutyric
- trimethylammonium
- pentanediol
- reaction
- manufacture method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is to provide a kind of suitability for industrialized production that is suitable for, adopting isobutyric aldehyde is that raw material produces 2,2,4-trimethylammonium-1, the isobutyric method of 3-pentanediol and joint product.Its specific embodiment is: aldol reaction, cross Cannizzaro reaction crystallization, centrifugation, and the thick glycol after the separation delivers to fusion and underpressure distillation produces 2,2,4-trimethylammonium-1,3-pentanediol; Filtrate footpath evaporation concentration after the separation, acidifying, sodium chloride crystal-separation-filtrate standing demix, isopropylformic acid distillation obtain isopropylformic acid.
Description
The invention belongs to the basic organic synthesis field in the chemical technique, a kind of 224-trimethylammonium-13-pentanediol and the isobutyric industrially preparing process of joint product particularly are provided.
The raw material that manufacture method adopted involved in the present invention is an isobutyric aldehyde.Just present, do not see to open report from actual production by the set out industrial making method of producing 224-trimethylammonium-13-pentanediol (abbreviation glycol) of isobutyric aldehyde, the report that has only laboratory preparation that can find, as United States Patent (USP) 2,829, in 169 be narration so substantially: make isobutyric aldehyde and dilute alkaline aqueous solution at 20 ℃ of generation aldol reactions standing demix then, isolated organic layer is neutralized to p with acetate or other lipid acid
H=4-6 removes unreacted isobutyric aldehyde (it is reusable that these reclaim isobutyric aldehydes) with the organic layer that obtains with the distillatory way, can obtain content during distillation and be 95～97% aldol, and distillation yield is 90%, with the aldol that obtains at 60～180 ℃, 7～70Kg/cm
2Situation under shortening make 224-trimethylammonium-13-pentanediol, catalyzer adopts is 5% Raney Ni.This method is in isobutyric aldehyde, and the total recovery of product is 80.4～82.2%.Aforesaid method be behind aldol condensation, obtain aldol again shortening make product, it needs high-tension apparatus and hydrogenation catalyst, and technology is comparatively complicated, and applying of its technology is restricted.
Task of the present invention is, provides a kind of and is suitable for that industrial production uses, and adopting isobutyric aldehyde is that raw material makes 224-trimethylammonium-13-pentanediol and the isobutyric method of joint product.
Task of the present invention is by finishing as the technological process in the accompanying drawing.
Be illustrated below in conjunction with the process drawing in the accompanying drawing:
1, aldol reaction:
Add entry and isobutyric aldehyde (92.4%) in reactor by a certain percentage, its ratio is about water: isobutyric aldehyde=1: 2(weight), and stir, cool off, then press the isobutyric aldehyde acid number and add liquid caustic soda, in temperature of reaction is under 15～60 ℃, keeps within 10 hours, and its reaction formula is:
2, cross Cannizzaro reaction:
After above-mentioned aldol reaction is finished, add water and liquid caustic soda in reactor, adopt steam to heat up, kept 1～10 hour under 50～95 ℃ of conditions, kept 1～5 hour under 90～95 ℃ of conditions, its reaction formula is:
3, crystallization:
Reaction solution is put into crystallizer, and cooling is also stirred, and keeps 10 hours under 5 ℃ of conditions.
4, centrifugation:
The crystallization feed liquid is at the uniform velocity put into the blue formula whizzer of awl, centrifugal work 90 minutes, gained solid material is thick glycol, can directly send in refining, its filtrate can be used for, produced isopropylformic acid and saltcake.
5, the fusion and the underpressure distillation of thick glycol:
The thick glycol that obtains after the centrifugation is packed in the molten-bath, adopt steam to make it fusion, use vacuum suction still kettle then, carry out underpressure distillation, collect the glycol fraction, 224-trimethylammonium-13-pentanediol gets product.
6, evaporation concentration:
The filtrate that obtains after the centrifugation is put into vaporizer, adopt the steam heating evaporation, when evaporated water reaches predetermined value, stop heating.
7, acidifying:
Concentrated solution is added in the acidifying still, under agitation add mineral acid, controlled temperature is below 40 ℃, and sampling is surveyed water layer pH2～3 and got final product, and feed liquid is put into the sodium chloride crystal machine.
8, sodium chloride crystal-centrifugal-filtrate is left standstill and layering:
Start stirring, acidifying still feed liquid is put into crystallizer, cooling was kept 8 hours at 0～20 ℃, start the blue formula whizzer of awl then the crystallization feed liquid is at the uniform velocity put into whizzer, centrifugation 90 minutes, filtrate is thick isopropylformic acid, deliver to distillation, the centrifugal particle that obtains is that saltcake can be directly as product.
9, isopropylformic acid distillation:
Thick isopropylformic acid is put into still kettle, and the liquid temperature is that 161 ℃ of cat head gas phases are more than 145 ℃ the time, can collect the isopropylformic acid finished product, carries out underpressure distillation then and collects the isopropylformic acid fraction.
The present invention not only provides the production technique of the 224-trimethylammonium-13-pentanediol that is suitable for suitability for industrialized production, and the industrial chemicals-high-quality isopropylformic acid joint product of outbalance have been obtained simultaneously, it is simple that this technology has equipment requirements, do not need high-tension apparatus, do not need hydrogen and hydrogenation catalyst, technology is simple, starts easily and be easy to promote.
Below the relevant actual conditions that relates in this technology is described:
(1), the catalyzer of aldol reaction (being liquid caustic soda) is alkali metal hydroxide, alkaline earth metal hydroxides and alkaline carbonate (as: sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood etc.).
(2), the aldol reaction temperature is 15～65 ℃, preferably is controlled at 30～35 ℃.
(3), the aldol reaction time is no more than 10 hours, is preferably 1.5～2.0 hours.
(4), to begin be 50～95 ℃ to the cross Cannizzaro reaction temperature, is preferably 65～70 ℃, the final reaction temperature should be mentioned 92～95 ℃.
(5), the cross Cannizzaro reaction time is 1～10 hour, is preferably 5 hours; Time when the reaction later stage is kept 92～95 ℃ is 1-5 hour, is preferably 2 hours.
(6), after cross Cannizzaro reaction finishes, reaction solution is used isopropylformic acid, acetate, sulfuric acid etc. and is neutralized to pH6～7, preferably adopts isopropylformic acid.
(7), to concentrate best concentration be 30～70% to the sodium methacrylate aqueous solution evaporate, is preferably 45～55%.
(8), the mineral acid that adopts in the acidization is preferably sulfuric acid.
(9), sodium methacrylate concentrates and to fold saltcake through the material after the acidifying in the sodium chloride crystal machine, its temperature is 0～20 ℃, is preferably in 0～5 ℃.
Claims (6)
1, a kind ofly make 224--trimethylammonium-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that by isobutyric aldehyde,
A, aldol reaction:
Ratio is about water: the water of isobutyric aldehyde=1: 2 (weight) and isobutyric aldehyde add in the reactor, after stirring, cooling off, add liquid caustic soda according to the isobutyric aldehyde acid number, are to keep under 15～65 ℃ in 10 hours in temperature of reaction,
B, cross Cannizzaro reaction:
After the above-mentioned reaction, in reactor, add entry and liquid caustic soda, adopt steam to heat up, under 50～95 ℃ of conditions, kept 1～10 hour, under 90～95 ℃ of conditions, kept 1～5 hour again,
C, crystallization:
Reaction solution is put into crystallizer, and cooling is also stirred, under 5 ℃ of conditions, kept 10 hours,
The d centrifugation:
The crystallization feed liquid is at the uniform velocity put into the blue formula whizzer of awl, centrifugal work 90 minutes, the thick glycol of solid material that obtains is sent into refining, and its filtrate being used to is produced isopropylformic acid,
E, thick glycol are packed in the molten-bath, adopt steam to make it fusion, then use vacuum suction still kettle, carry out underpressure distillation, collect glycol fraction--product,
F, evaporation concentration:
Filtrate after the centrifugation adds in the vaporizer, uses steam heating, steam to concentration be 30～70%,
G, acidifying:
Concentrated solution adds in the acidifying still, stirs down to add mineral acid, and controlled temperature is below 40 ℃, and the sodium chloride crystal machine is dropped into feed liquid in water layer pH2～3,
--centrifugal--filtrate of h, sodium chloride crystal is left standstill, layering:
Feed liquid enters crystallizer and starts stirring, and cooling was kept 8 hours at 0～20 ℃, and then feed liquid is at the uniform velocity put into the blue formula whizzer of awl in the crystallizer, centrifugal work 90 minutes, and filtrate is that thick isopropylformic acid is delivered to distillation, the centrifugal particle that obtains is a saltcake,
J, isopropylformic acid distillation:
Thick isopropylformic acid is put into still kettle, and the liquid temperature is that 161 ℃ of cat head gas phases are more than 145 ℃ the time, collects the isopropylformic acid finished product, carries out underpressure distillation then and collects the isopropylformic acid fraction.
2, by the described 224-trimethylammonium of claim 1-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that: the liquid caustic soda that aldol reaction adopts is basic metal or earth metals oxyhydroxide and alkaline carbonate.
3, by the described 224-trimethylammonium of claim 1-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that: the temperature of aldol reaction is controlled at 30～35 ℃, and the reaction times is 1.5～2.0 hours.
4, by the described 224-trimethylammonium of claim 1-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that: temperature was controlled at 65～70 ℃ when cross Cannizzaro reaction began, reaction times is 5 hours, and latter temperature is controlled at 92～95 ℃, and the reaction times is 2 hours.
5, by the described 224-trimethylammonium of claim 1-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that: evaporating concentration process concentration steams most 45～55%.
6, by the described 224-trimethylammonium of claim 1-13-pentanediol and isobutyric manufacture method of joint product, it is characterized in that: the acid that acidization adopts is sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88102978A CN1037700A (en) | 1988-05-17 | 1988-05-17 | 2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88102978A CN1037700A (en) | 1988-05-17 | 1988-05-17 | 2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037700A true CN1037700A (en) | 1989-12-06 |
Family
ID=4832383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102978A Pending CN1037700A (en) | 1988-05-17 | 1988-05-17 | 2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037700A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143879A (en) * | 2019-04-29 | 2019-08-20 | 南京师范大学 | A kind of by-product that p-nitroacetophenone preparation generates carries out the device and method of recycling |
-
1988
- 1988-05-17 CN CN88102978A patent/CN1037700A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143879A (en) * | 2019-04-29 | 2019-08-20 | 南京师范大学 | A kind of by-product that p-nitroacetophenone preparation generates carries out the device and method of recycling |
| CN110143879B (en) * | 2019-04-29 | 2022-07-12 | 南京师范大学 | Device and method for recycling by-products generated in preparation of p-nitroacetophenone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1030764C (en) | Method of manufacturing ferulic acid | |
| CN105418624A (en) | Process for the production of anhydrosugar alcohols | |
| CA2745256C (en) | Process for the preparation of a monovalent succinate salt | |
| RU2221768C2 (en) | Method for preparing alkyne diols possibly comprising alkyne monoalcohols | |
| CN111004162B (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| CN1800193A (en) | 2-deoxidized glucose preparation method | |
| CN100343220C (en) | Technology of preparing hdyroxy acetic acid | |
| CN1037700A (en) | 2,2,4-trimethylammonium-1, the isobutyric manufacture method of 3-pentanediol and joint product | |
| CN117229136A (en) | Preparation method of azelaic acid | |
| EP0924179A1 (en) | Process for the preparation of benzyl alcohol | |
| JP3549767B2 (en) | Method for producing monoethyl potassium malonate | |
| CN1087062A (en) | Decomposition process for ammonium chloride | |
| CN1107143A (en) | Improved process for the manufacture of cyclopropylniitrile | |
| CN115819221B (en) | Preparation method of (R) -2-hydroxymethyl propionic acid and (S) -2-hydroxymethyl propionic acid | |
| EP0314959B1 (en) | Selective hydrolysis | |
| CN1315775C (en) | Method for producing 2,2,2-trifluoroethanol | |
| NZ201412A (en) | Preparation of 4-aminobutyramide | |
| CN1074435A (en) | By the method that makes mixture of higher aliphatic alcohols in the sugar-cane wax | |
| US4731475A (en) | Method for preparing solid p-disodium hydroxybenzoate | |
| EP0002297B1 (en) | Process for the preparation of dl-phenyl-glycine amide | |
| CN1059201C (en) | Method for purifying tertiary amine | |
| CN1070194A (en) | Process for synthesizing methamidophos | |
| CN1037763C (en) | Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid | |
| GB2055814A (en) | Process for preparing ???-aryl propionic acids | |
| US4190592A (en) | Process for splitting the L-(-)-α-phenylethylamine salt of D-(-)-α-azidophenylacetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |