CN102442890B - From the method that crude glycerine prepares polyglycereol - Google Patents
From the method that crude glycerine prepares polyglycereol Download PDFInfo
- Publication number
- CN102442890B CN102442890B CN201010501391.7A CN201010501391A CN102442890B CN 102442890 B CN102442890 B CN 102442890B CN 201010501391 A CN201010501391 A CN 201010501391A CN 102442890 B CN102442890 B CN 102442890B
- Authority
- CN
- China
- Prior art keywords
- polyglycereol
- crude glycerine
- acidifying
- thick
- soap
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to and a kind of use microwave radiation as heating element heater, the method for preparing polyglycereol from crude glycerine acceleration under the existence as the soap of catalyst. The method comprises the following steps: that (a) is by using microwave technology that to high temperature, the described crude glycerine heating containing soap is lasted certain response time, b the crude product of the acidifying obtained from step (b) by thick polyglycereol acidifying, and is centrifuged certain persistent period at specified temp at specified temp mineral acid by ().
Description
Technical field
The present invention relates to a kind of method for preparing polyglycereol from crude glycerine.
Background technology
Polyglycereol is standby usually by the hot Dehydration of glycerol, is wherein aggregated in atmospheric pressure and carries out at the high temperature of about 230 DEG C-270 DEG C. The method can complete when not using catalyst, but the yield of polyglycereol is at a fairly low.
Therefore, having been incorporated into various catalyst to help the formation of polyglycereol, and most-often used catalyst is base catalyst such as sodium hydroxide or potassium hydroxide, alkali carbonate is potassium carbonate such as, and aluminium oxide, and alkaline earth metal hydroxide such as calcium hydroxide.
Acidic catalyst is also used in the hot dehydration of glycerol, the mixture of described acidic catalyst such as sulphuric acid and glyceryl triacetate, hypophosphorous acid and sodium hydroxide and acid zeolite. It addition, clay such as brucite is also used to the hot dehydration of catalyzing glycerol.
There was reported solketal (solketal), (+)-2,3-Epoxy-1-propanol or glycerol carbonate as reactant when when being formed with the brucite polyglycereol when pyroreaction. It addition, use the fluoride salt of rubidium, caesium and potassium that (+)-2,3-Epoxy-1-propanol, glycerol carbonate and solketal are aggregated into polyglycereol. Additionally, line style and cyclic polyglycerols be all reported as beta-zeolite as catalyst when (+)-2,3-Epoxy-1-propanol, between glycerol carbonate and solketal reaction product.
In a kind of method for preparing polyglycereol also known in the art, the method includes: make glycerol, diglycerol or higher level polyglycereol react to prepare thick chlorhydrin/ether mixture at 90 DEG C to 170 DEG C with chloropropylene oxide, it is subsequently added into a certain amount of highly basic of the chlorinity of the combination being substantially equal at least chlorhydrin/ether mixture, with by mixture desalination, and reclaim glycerol, diglycerol and higher level polyglycereol fraction.
1-propenol-3 is the another kind of approach preparing polyglycereol. The method relates to the epoxidation of 1-propenol-3, wherein will form (+)-2,3-Epoxy-1-propanol, and be then followed by the polymerization of (+)-2,3-Epoxy-1-propanol. This is proved to the another kind of effective ways for preparing polyglycereol.
Although prepare the background technology in polyglycereol numerous and different the fact, it will therefore be apparent that synthesize polyglycereol and diglycerol from glycerol and there is some shortcomings. In shortcoming one is the persistent period of reaction, it was reported that major part prior art has the response time of minimum 5 hours to 72 hours, and technique is caused higher cost by this.It addition, major part prior art discloses the composition of end product (polyglycereol) still containing the remarkable amounts of glycerol that there is a need to additionally remove step.
Prior art another disadvantage is that high-purity compound such as glycerol, chloropropylene oxide, (+)-2,3-Epoxy-1-propanol, glycerol carbonate and solketal as raw material polyglycereol prepare in use. The major part of these compounds costlinesses and their cost structure polyglycereol preparation cost. It addition, major part prior art needs certain point in preparation technology to introduce the catalyst in reactant. Catalyst also increases the preparation cost of polyglycereol to the introducing of reactant.
Therefore, it is an object of the present invention to provide a kind of method being prepared without the polyglycereol of residual glycerol within a short period of time. Another object of the present invention is to use the raw material of the relatively low-purity containing the catalyst being applicable to reaction. The present invention provides a kind of method preparing polyglycereol with relatively low preparation cost.
Summary of the invention
Therefore, the present invention provides a kind of method for preparing polyglycereol from crude glycerine, described method comprises the following steps: that (a) is by using microwave technology that to high temperature, the crude glycerine heating containing soap (soap) is lasted certain response time, b (), at specified temp mineral acid by thick polyglycereol acidifying, and the crude product of the acidifying obtained from step (b) is centrifuged certain persistent period at specified temp by (c).
The present invention comprises some new features and the combination of part, describes all sidedly and illustrates after them in rear attached explanation, it will be appreciated that when not necessarily departing from the scope of the present invention or sacrificing any advantage of the present invention, it is possible to carry out the various changes of details.
Detailed description of the invention
The present invention relates to the method for preparing polyglycereol from crude glycerine. Below, this specification will describe the present invention according to the preferred embodiments of the invention. It will be appreciated, however, that be limited to the preferred embodiments of the invention by describing merely to make the discussion of the present invention become convenient, and predict those skilled in the art and can design various change and equivalent when not necessarily departing from the scope of appended claim.
The present invention provides the existing methodical improvement preparing polyglycereol from glycerol. Improving by using lower quality (relatively inexpensive) raw material containing the catalyst suitable in this method to become apparent upon in the present invention. Preferably, lower quality raw material is derived from the crude glycerine of biodiesel factory. More specifically, crude glycerine originates from the by-product of the preparation of methyl ester (biodiesel).
It is preferred for the invention that, the composition deriving from the crude glycerine of biodiesel comprise the glycerol of 60 to 80%, 10 to 25% methanol and 10 to 15% soap. It is highly preferred that crude glycerine contain the glycerol of 80 to 90%, the methanol of 1 to 10% and at least 10% soap. Most preferably, crude glycerine contains only the glycerol of 85 to 90% and the soap of 10 to 15%. High carbinol content in crude glycerine will increase the response time being fully converted into by crude glycerine needed for polyglycereol, and this will cause higher preparation cost.
It is reported, the glycerol polymerization in order to form polyglycereol can carry out when not using catalyst, but reaction suffers the low yield of polyglycereol. Therefore, in the present invention, use catalyst to improve yield and the selectivity of product. The inventors discovered that, alkali-metal soap (soap) provides good yield and selectivity in preparing polyglycereol from glycerol. Disclose the soap that preferred crude glycerine contains 10 to 15% before the present inventor, and this soap plays the effect of catalyst for the hot dehydration of glycerol to polyglycereol.
Soap in crude glycerine is formed in the ester-exchange reaction between the triglyceride and the methanol that generate methyl ester (biodiesel), and wherein the free fatty in biodiesel raw material and ester exchange catalyst (sodium hydroxide or potassium hydroxide or Feldalat NM) react thus generating soap. In biodiesel preparation technology, soap and crude glycerine remove together as by-product.
Can find in crude glycerine but be not limited to the example of this soap is sodium or the laruate of potassium, myristate, palmitate, stearate, oleate and linoleate. Preferably, the soap in crude glycerine is sodium palmitate or enuatrol. In crude glycerine, the preferred amounts of soap is 0.1% to 15%, and it is highly preferred that in crude glycerine, the amount of soap is no less than 10%. Most preferably, in crude glycerine, the amount of soap is 10 to 15%. If crude glycerine contains the soap less than 10%, then crude glycerine will not reach 100% to the conversion ratio of polyglycereol.
The present invention also provides for the existing methodical another kind of improvement preparing polyglycereol from glycerol. By only just crude glycerine being fully converted into the response time that polyglycereol spends within the scope of 20 to 30 minutes so that the milestone (milestone) in the present invention improves and becomes apparent upon, and conventional method will take for 5 hours to 72 hours. This improves is caused by the use of microwave radiation, wherein in 900W microwave oven, under the existence as the soap of catalyst, by crude glycerine heating and by means of magnetic stirrer stirring. Crude glycerine to the preferred reaction time of the hot dehydration of polyglycereol accelerated for microwave is about 10 to 30 minutes. It is highly preferred that the response time is about 20 to 30 minutes, wherein crude glycerine can reach 95% to the conversion ratio of polyglycereol. Most preferably, the response time is 30 minutes, and wherein crude glycerine is 100% to the conversion ratio of polyglycereol.
It is preferred for the invention that temperature is in the scope of 200 DEG C to 290 DEG C, but more preferably in the scope of 250 DEG C to 270 DEG C. By adopting the temperature within the scope of this, it is possible to while still obtaining acceptable reaction rate, it is achieved there is the good conversion rate of minimum by-product. Most preferred reaction temperature is 270 DEG C, and reason is in that crude glycerine is 100% to the conversion ratio of polyglycereol. Particularly preferred aspect of the present invention is that described method carries out at atmospheric pressure, and is avoided the use of the high pressure equipment of costliness by such operation.
The thick polyglycereol prepared from crude glycerine still contains and will cause that product becomes the soap of solid. Soap in product can by removing crude product acidifying with phosphoric acid or other mineral acid any such as sulphuric acid, hydrochloric acid and nitric acid. For the amount of mineral acid of acidifying crude product in the scope of 1 to 3% (w/w). The final pH of acidizing product is in the scope of 4 to 6, it is preferable that in the scope of 4 to 5.
Then the crude product of acidifying is centrifuged. Before centrifuging process starts, the crude product of acidifying is heated to 60-80 DEG C. The crude product of acidifying is centrifuged at least 30 minutes at 1500 to 2000rpm. Fatty acid can be separated from product by centrifugal force with salt. After centrifuging process, the crude product of acidifying is divided into three layers. Upper strata is fatty-acid layer, and middle level is the polyglycereol of purification. Lower floor comprises the product of salt and absorption.
Polyglycereol sample high performance liquid chromatography (HPLC) of thick polyglycereol sample and purification is analyzed, and determines the composition of glycerin oligomer in every kind of polyglycereol sample. HPLC system is configured with evaporative light scattering detection instrument (EvaporativeLightScatteringDetector) (ELSD).Sample analysis is with being pre-filled with 10 ��m of HypersilNH225cm �� 4.6mmID post of amino (10 ��m of HypersilNH2amino) is 30 DEG C of realizations. Eluting uses acetonitrile (85%) and water (15%) to carry out with the flow velocity of 1ml/ minute. Use the software analysis chromatogram installed in a device to obtain peak area and retention time. Dissolve a sample in water (2%w/v) and by the solution of 20 �� l by automatic loop syringe (automaticloopinjector) injection.
Analyze result based on HPLC, when to the crude glycerine of soap containing 12% when carrying out microwave radiation 30 minutes for 270 DEG C, crude glycerine reaches 100% to the conversion ratio of polyglycereol. The following is by the HPLC typical case's composition of glycerin oligomer in the polyglycereol of purification analyzed:
The composition of glycerin oligomer
The unreacted glycerol of 0%-3.5%
The diglycerol of 52%-61%
The triglycerin of 25%-31%
Four glycerol of 11%-16%
The higher level polyglycereol of 0%-1%
According to HPLC chromatogram, when comparing with the standard oligomer of glycerol, there is the evidence of ring-type diglycerol that is little or that do not find in thick polyglycereol or polyglycereol. Therefore, it can advocate that the method prepares line style diglycerol and polyglycereol from selective glycerol.
In order to omparison purpose, by using conventional heating the identical crude glycerine heating of the soap containing 10% to 270 DEG C and to be kept 6 hours in this temperature, to determine the advantage using microwave radiation as heating element heater, wherein contrary with a few hours passing through to use conventional heating, the response time greatly foreshortens to several minutes. Analysis result shows, by using conventional heating methods, crude glycerine only can realize to 90% conversion ratio of polyglycereol after the reaction of 3 hours.
In order to omparison purpose, the enuatrol (soap) by 10% adds in pure glycerin, and mixture carries out respectively conventional heating and microwave heating 6 hours and 30 minutes at 270 DEG C. HPLC analyzes display, and by conventional heating, the pure glycerin of 90% can change into polyglycereol after the reaction of 3 hours. For the reaction adopting microwave heating to carry out, after the reaction of 30 minutes, the pure glycerin of 100% changes into polyglycereol. Therefore, this demonstrate that the soap of 10% is enough to change into the glycerol of 100% polyglycereol, and response time from a few hours can be foreshortened to 30 minutes by microwave heating.
Following example illustrate the present invention and promote that it is understood.
Embodiment 1
By containing the glycerol of 80%, the soap of 12% and 6% methanol biodiesel source crude glycerine (100g) load in 250ml round-bottomed flask. Then round-bottomed flask is placed in 900W microwave cavity. Then, microwave oven is controlled by the program, in 3 minutes, from environment, temperature is risen to 270 DEG C, and keeps this temperature again 27 minutes, begins to cool down the program end with labeled reactant afterwards. Total reaction time is 30 minutes. Then thick polyglycereol carries out high performance liquid chromatography (HPLC), and the composition of crude glycerine shows below. The yield of thick polyglycereol is 86%, and crude glycerine to the percent conversion of polyglycereol is 100%.
The composition of glycerin oligomer in thick polyglycereol
The soap of 16%
The diglycerol of 50%
The triglycerin of 22%
Four glycerol of 12%
Embodiment 2
Thick polyglycereol from embodiment 1 is removed the program of soap in crude product. While stirring crude product with magnetic stirrer, it is heated to 90 DEG C, and by the acidifying of pH value monitoring crude product. The initial pH of crude product is about 9, is added dropwise in crude glycerine by phosphoric acid, until the pH of crude glycerine reaches about 4.The crude product of acidifying is stirred for 30 minutes, afterwards the product of acidifying is transferred to centrifugal device. In acid condition, soap is hydrolyzed thus obtaining fatty acid, and sodium ion (Na+) form salt (sodium phosphate) with phosphoric acid. Centrifugal device is set in 60 DEG C, and the crude product of acidifying is centrifuged 30 minutes at 1600rpm. The product of acidifying is divided into 3 layers, and wherein middle level is the polyglycereol of purification. Then the polyglycereol of purification being carried out HPLC analysis, the composition of every kind of glycerin oligomer shows below. The composition of glycerin oligomer in purification polyglycereol
The diglycerol of 60%
The triglycerin of 26%
Four glycerol of 14%
Embodiment 3
With containing the glycerol of 70%, the soap of 10% and 20% the crude glycerine of methanol repeat the test in embodiment 1. Crude product is carried out the purifying procedure identical with described in embodiment 2. The following is the composition of the polyglycereol of purification. The yield of thick polyglycereol is 69%, and crude glycerine to the percent conversion of polyglycereol is 100%.
The composition of glycerin oligomer in the polyglycereol of purification
The diglycerol of 57%
The triglycerin of 27%
Four glycerol of 16%
Embodiment 4
By containing the glycerol of 80%, the soap of 12% and 6% methanol biodiesel source crude glycerine (100g) load in tri-mouthfuls of round-bottomed flasks of 250ml. Round-bottomed flask is connected with condenser to collect any distillation. By using conventional heating that to 270 DEG C, the content heating of round-bottomed flask is lasted 3 hours. Analyze crude product by HPLC, the following is the composition of crude product. After the reaction of 3 hours, crude glycerine is about 90% to the percent conversion of polyglycereol.
The composition of glycerin oligomer in thick polyglycereol
The glycerol of 10%
The diglycerol of 30%
The triglycerin of 40%
Four glycerol of 20%
Embodiment 5
The test in embodiment 1 is repeated with the pure glycerin of the enuatrol as catalyst containing 10%. Analyze thick product by HPLC, the composition of thick product is presented herein below. The yield of thick polyglycereol is 89%, and crude glycerine to the percent conversion of polyglycereol is 100%.
The composition of glycerin oligomer in thick polyglycereol
The diglycerol of 65%
The triglycerin of 35%
Embodiment 6
The test in embodiment 4 is repeated with the pure glycerin of the enuatrol as catalyst containing 10%. By using conventional heating that to 270 DEG C, the content heating of round-bottomed flask is lasted 3 hours. Analyze crude product by HPLC, the following is the composition of crude product. After the reaction of 3 hours, pure glycerin is about 90% to the percent conversion of polyglycereol.
The composition of glycerin oligomer in thick polyglycereol
The glycerol of 10%
The diglycerol of 32%
The triglycerin of 28%
Four glycerol of 30%.
Claims (10)
1. the method for preparing polyglycereol from crude glycerine, described method comprises the following steps:
A described crude glycerine heating containing soap is lasted certain response time to high temperature by using microwave technology by ();
(b) at specified temp mineral acid by thick polyglycereol acidifying; With
C the crude product of the acidifying obtained from step (b) is centrifuged certain persistent period at specified temp by (),
The soap content of wherein said crude glycerine is 10 to 15%, the glycerol content of described crude glycerine is 60 to 90%, the methanol content of described crude glycerine is 5 to 20%, described reaction carries out 20 to 30 minutes the temperature of 230 to 290 DEG C, described thick polyglycereol by mineral acid acidified to pH4 6, and by the thick polyglycereol of described acidifying the temperature of 60 to 80 DEG C centrifugal at least 30 minutes of 1500 to 2000rpm.
2. method according to claim 1, wherein said crude glycerine originates from the by-product of triglyceride and the Exchange Ester Process of alcohol.
3. method according to claim 1, wherein said soap is sodium salt or the potassium salt of the fatty acid comprising 8 to 22 carbon atoms (C8 to C22) in chain length.
4. method according to claim 1, wherein thermal source is the microwave radiation produced by microwave device.
5. method according to claim 1, wherein said reaction carries out at atmospheric pressure.
6. method according to claim 1, wherein said mineral acid selects the group of free phosphoric acid, sulphuric acid and nitric acid composition.
7. method according to claim 1, wherein at 90 DEG C by described thick polyglycereol acidifying.
8. method according to claim 1, is wherein centrifuged the thick polyglycereol of described acidifying at 60 DEG C.
9. method according to claim 1, is wherein centrifuged the thick polyglycereol of described acidifying 30 to 60 minutes.
10. method according to claim 1, wherein the degree of polymerization of crude glycerine changes from n=2 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010501391.7A CN102442890B (en) | 2010-09-30 | 2010-09-30 | From the method that crude glycerine prepares polyglycereol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010501391.7A CN102442890B (en) | 2010-09-30 | 2010-09-30 | From the method that crude glycerine prepares polyglycereol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102442890A CN102442890A (en) | 2012-05-09 |
| CN102442890B true CN102442890B (en) | 2016-06-08 |
Family
ID=46005876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010501391.7A Expired - Fee Related CN102442890B (en) | 2010-09-30 | 2010-09-30 | From the method that crude glycerine prepares polyglycereol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102442890B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518765A1 (en) * | 1991-06-12 | 1992-12-16 | Organisation Nationale Interprofessionnelle Des Oleagineux- Onidol | Process for the preparation of polyglycerols and polyglycerol esters |
| EP0719752A1 (en) * | 1994-12-29 | 1996-07-03 | Institut Francais Du Petrole | Process for producing polyglycerols and polyglycerol esters |
| WO2004065343A2 (en) * | 2002-12-23 | 2004-08-05 | Aldivia, S.A. | Polycondensation method employing dielectric heating, in particular for the production of polyglycerols and similar |
| WO2007049950A2 (en) * | 2005-10-26 | 2007-05-03 | Malaysian Palm Oil Board | A process for preparing polymers of polyhydric alcohols |
-
2010
- 2010-09-30 CN CN201010501391.7A patent/CN102442890B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518765A1 (en) * | 1991-06-12 | 1992-12-16 | Organisation Nationale Interprofessionnelle Des Oleagineux- Onidol | Process for the preparation of polyglycerols and polyglycerol esters |
| EP0719752A1 (en) * | 1994-12-29 | 1996-07-03 | Institut Francais Du Petrole | Process for producing polyglycerols and polyglycerol esters |
| WO2004065343A2 (en) * | 2002-12-23 | 2004-08-05 | Aldivia, S.A. | Polycondensation method employing dielectric heating, in particular for the production of polyglycerols and similar |
| WO2007049950A2 (en) * | 2005-10-26 | 2007-05-03 | Malaysian Palm Oil Board | A process for preparing polymers of polyhydric alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102442890A (en) | 2012-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101896474B (en) | Prepare the method for ketal and acetal | |
| BRPI0903506B1 (en) | A METHOD OF SYNTHESIS OF ALCOHOL FOR THE SYNTHESIS OF BUTANOL FROM ETHANOL ?? | |
| CN109415290B (en) | Method for producing acrylic acid from lactic acid or derivatives thereof in liquid phase | |
| CN106866366B (en) | Method for removing dihydric alcohol or polyhydric alcohol impurities in ethylene glycol and increasing yield of ethylene glycol | |
| CN102442890B (en) | From the method that crude glycerine prepares polyglycereol | |
| CN101935270B (en) | Process of producing polyglycerol from crude glycerol | |
| CN105566253A (en) | Method for synthesizing chloropropylene oxide from glycerin | |
| US8816132B2 (en) | Process of producing polyglycerol from crude glycerol | |
| CN109400469B (en) | Method for producing long-chain fatty acid and glycerol triacetate from grease | |
| EP0060365A2 (en) | Process for producing gamma-vinyl-gamma butyrolactone | |
| JPS649299B2 (en) | ||
| CN102584588A (en) | Method using catalysis transesterification to prepare n-amyl acetate cinnamate | |
| CN104478715B (en) | The preparation method of compound | |
| CN116063183B (en) | Synthesis method of cyclopropylamine | |
| CN103342688A (en) | Method for preparing furfural by one-step selective catalytic cracking | |
| CN109456838B (en) | Method for producing biodiesel and glycerol triacetate | |
| CN112374979B (en) | Preparation method of erythro-eleostearic acid | |
| JP6097278B2 (en) | Method for producing 3-alkoxy-3-methyl-1-butanol | |
| Teng et al. | Microwave assisted solvent-free catalytic transesterification of glycerol to glycerol carbonate | |
| CN101805241A (en) | New method for preparing fluoro-substituted indene compound | |
| US2822402A (en) | Preparation of 1, 1-dimethoxycyclo-hexane | |
| CN102584587A (en) | Method using catalysis transesterification to prepare n-butyl acetate cinnamate | |
| CN105130745A (en) | Method of producing sec-butyl alcohol | |
| CN102603528A (en) | Method for preparing n-amyl cinnamate by transesterification reaction catalyzed by ionic liquid | |
| CN104844501B (en) | A kind of synthetic method of tetramethyl piperidine alcohol ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160608 Termination date: 20190930 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |