GB2435040A - Acetonitrile purification by the addition of phosphorus pentoxide, then water, and subsequent distillation - Google Patents
Acetonitrile purification by the addition of phosphorus pentoxide, then water, and subsequent distillation Download PDFInfo
- Publication number
- GB2435040A GB2435040A GB0602509A GB0602509A GB2435040A GB 2435040 A GB2435040 A GB 2435040A GB 0602509 A GB0602509 A GB 0602509A GB 0602509 A GB0602509 A GB 0602509A GB 2435040 A GB2435040 A GB 2435040A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acetonitrile
- mixture
- purification process
- purified
- vessel
- 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.)
- Granted
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 238000000746 purification Methods 0.000 title claims abstract description 24
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004821 distillation Methods 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims abstract description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- -1 acrylonitri!e Chemical compound 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010647 peptide synthesis reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/03—Mononitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An acetonitrile purification process comprises adding phosphorus pentoxide in an amount of from 0.05% to 0.1% by weight to a crude mixture containing impurities. Water is added to the mixture preferably in an amount of less than 0.004% by volume. The mixture is distilled and purified acetonitrile is recovered. The purified acetonitrile has a high level of purity. The purified acetonitrile may be further purified by adding potassium carbonate and potassium permanganate, and distilling the mixture.
Description
<p>"Acetonitrile Purification" The invention relates to a purification
process for purifying acetonitrile containing impurities such as ally! alcohol, acetone, water, oxazole, acrylonitri!e, methacrylonitrile and/or propionitri Ic.</p>
<p>Acetonitrile was first produced commercially in 1952. It is widely used in liquid-liquid extraction, selective recrystallisation and extractive distillation. Because of its favourable dielectric, solvent and optica! properties, it is also widely used in analytical chemistry, particularly in high performance liquid chromatography (HPLC), DNA and peptide synthesis, residue analysis, in UV and IR spectroscopy, and in liquid chromatography and mass spectroscopy (LCMS).</p>
<p>: *** In our UK-A-2249308 and UK-A-2322856 we have described processes for * *. 15 producing acetonitrile having a high level of purity in a cost efficient manner. S.*</p>
<p>As modern chemical and biological process techniques become ever more sophisticated and new techniques are developed there is a need to provide an improved cost efficient process for producing acetonitrile with high levels of purity.</p>
<p>.. : 20 **.* This invention is directed towards providing such an improved acetonitrile purification process.</p>
<p>Statements of Invention</p>
<p>According to the invention there is provided an acetonitrile purification process for the purification of an acetonitrile mixture containing impurities to produce purified acetonitrile, the process comprising the steps of: charging the acetonitrile mixture into a processing vessel; adding phosphorus pentoxide to the acetonitrile mixture in an amount of from 0.05% to 0.1% by weight of the mixture; adding water to the mixture; distilling the mixture in a distillation column; and recovering purified acetonitrile from the distillation column; and In one embodiment the phosphorous pentoxide is added to the acetonitrile mixture in an amount of from 0.06% to 0.08% by weight of the mixture.</p>
<p>Preferably water is added to the mixture in an amount of less than 0.004% by : s volume of the acetonitrile mixture. Se.. * 5 5'.</p>
<p>In one embodiment the process comprises the step of agitating the mixture in the * : processing vessel after addition of the phosphorous pentoxide. The mixture is preferably agitated by means of a stirring rod in the vessel. S..</p>
<p>In another aspect the process comprises the steps of: -** charging acetonitrile to be purified into a second vessel for delivery into the processing vessel; and delivering the acetonitrile from the second vessel into the processing vessel, on demand.</p>
<p>In one embodiment the acetonitrile purification process comprises the step of charging the purified acetonitrile into the processing vessel to form a feedstock for a second stage processing. The second stage processing preferably comprises: -adding potassium carbonate and potassium permanganate to the feedstock in the processing vessel; distilling the mixture in the distillation column; and recovering the highly purified acetonitrile from the distillation column.</p>
<p>In one embodiment the potassium carbonate is added in an amount of from 0.02 to 0.08% by weight of the feedstock, preferably the potassium carbonate is added in an amount of from 0.04 to 0.06% by weight of the feedstock.</p>
<p>In one embodiment the potassium permanganate is added in an amount of from 0.002 to 0.004% by weight of the feedstock. * S. * S S S...</p>
<p>*..* 15 The invention also provides purified acetonitrile when produced by the purification *SS* process of the invention. S. S * S S * *.</p>
<p>The invention will be more clearly understood from the following description thereof given by way of example only with reference to accompanying drawing which is a schematic diagram of a processing system used in the process of the invention.</p>
<p>Referring to the drawing there is illustrated an apparatus used in the acetonitrile purification process of the invention. The apparatus comprises a first feed vessel 1 and a boiler feed vessel 2, both with a capacity of about 500 L. The boiler feed vessel 2 has a pair of heat exchanges 3, 4 and a stirring rod 5. The vapour generated in the boiler feed vessel 2 is delivered to the lower end of a distillation column 6 with a packing of raschig rings and having from 30 to 40 theoretical plates. Vapour from the distillation column 6 is condensed by passing cooling water through a coil 7 in a primary condenser 8. Refiux material from the primary condenser 8 is led along an outlet line 9 to a cooling condenser 20 and then to the holding vessels 16, 17.</p>
<p>Vapour which passes through the primary condenser 8 may be passed through a secondary condenser 10.</p>
<p>Product may be sampled through a sampling port 18, 19. The purified solvent depending on the solvent purity level, may be directed back to the feed vessel I and then returned to the boiler feed vessel 2. Alternatively, the solvent may be directed to one of two final product storage tanks 16, 17, which are fitted with sampling ports 18, 19.</p>
<p>In use, the feed vessel I is first charged with an acetonitrile mixture containing impurities. The boiler feed vessel 2 is also charged with the acetonitrile mixture.</p>
<p>Treatment chemicals (as described below) are then added to the boiler feed vessel 2.</p>
<p>The stirring rod 5 is turned on and is rotated at a speed of about 100 rpm. Steam is : : : then turned on to the heat exchanges 3, 4. The steam pressure is adjusted to about 20 psi. The acetonitrile in the boiler feed vessel 2 is heated to boiling point (81.6 C) and the solvent vapour passes through the distillation column 6. The solvent is refluxed * :* . back into the boiler feed vessel 2 for a period of about 45 minutes after reaching boiling point. A sample of the purified solvent is taken, and if the solvent has the *1 desired purity level, it is delivered to one of the product storage tanks 16, 17.</p>
<p>Generally, an initial quantity of about 10 litres delivered to the storage tanks is rejected to residue. The product is sampled through sampling ports 1 8, 19 and tested to ensure that it is of the desired purity. The process is continued and as solvent is distilled from the boiler feed vessel 2, the vessel 2 is fed with further raw material from feed vessel I so that the process can operate continuously. When the material in feed vessel 1 has been processed, distillation is continued until the level of acetonitrile in the boiler feed vessel system 2 drops to just above the top of the heat exchangers 3, 4. The batch is complete and steam is turned off. During the process an inert nitrogen atmosphere is maintained in the various vessels.</p>
<p>To produce acetonitrile with a range of purity grades, phosphorous pentoxide is the main treatment chemical added to the processing vessel 2.</p>
<p>Highly purified acetonitrile can be produced using the closed loop system of the invention by using the solvent purified as described above as a feedstock for a second stage purification process in which treatment chemicals potassium carbonate and potassium permanganate are added to the processing vessel 2. Processing is continued as described above.</p>
<p>The system facilitates closed loop processing of a batch of up to 1000L in a highly efficient manner. There is no loss of solvent during processing as there are no fugitive emissions and all residues are collected for re-working.</p>
<p>The purity of the solvent produced can be tailored to desired applications.</p>
<p>Example 1 -HPLC Grade For HPLC applications an acetonitrile mixture containing impurities the following additions are made to the material in the boiler feed vessel 2.</p>
<p>Phosphorous Pentoxide: 0.06% by weight of batch Water: 0.0025 % by volume of batch * 20 Processing is carried out as described above (steam pressure 20 psi) and yields a HPLC grade purified acetonitrile with the following typical specification: Average gradient peak height (mAU) .. .15 at 210 nm.</p>
<p>Water content (ppm) . . .80.</p>
<p>The HPLC grade solvent is used in applications where ranges 250-240 nm are required.</p>
<p>Example 2 -HPLC Gradient Grade To achieve acetonitrile solvent with a moderate level of performance at low wavelengths of between 210 nm and 200 nm, an acetonitrile mixture containing impurities is processed as describe above with the following additions to the material in the boiler feed.</p>
<p>Phosphorous Pentoxide: 0.07 % by weight of batch Water: 0.0025 % by volume of batch.</p>
<p>Processing is carried out as described above (steam pressure 20 psi) and yields a purified acetonitrile with the following typical specification: Average gradient peak height (mAU) .. .10 at 210 nm. * S. * S *</p>
<p>Water content (ppm)...80 S...</p>
<p>Example 3-Far UV Grade To achieve acetonitrile solvent of extremely high purity, an acetonitrile mixture containing impurities is processed as described above with the following additions to the material in the boiler feed vessel: *55S Phosphorous Pentoxide: 0.8% by weight of batch.</p>
<p>Water: 0.0025% by weight of batch.</p>
<p>The steam pressure is 20 psi.</p>
<p>The purified acetonitrile has the following typical specification: Average gradient peak height (mAU) ... 3.1 at 210 nm.</p>
<p>Water content (ppm) .... 60 Example 4 -Super Gradient Grade.</p>
<p>To achieve acetonitrile solvent with a relatively low water content which can operate below 200 nm, an acetonitrile mixture containing impurities is processed in a first stage as described above in Example 2. The partially purified acetonitrile from Example 2 is used as a feedstack for a second stage processing with the following additions to the material in the boiler feed vessel 2.</p>
<p>Potassium Carbonate: 0.05% by weight of batch.</p>
<p>Potassium Permanganate: 0.003% by weight of the batch.</p>
<p>The steam pressure is 12 psi. * *e * I S *5I*</p>
<p>The purified acetonitrile has the following typical specification: S...</p>
<p>Average gradient peak height (mAU) ....l.22 at 210 nm.</p>
<p>Water content (ppm)... 120 ::::. 20 The processing system of the invention for producing purified acetonitrile solvent has several advantages. Chemical treatment is minimised which has a considerable impact on input and waste management costs. Batch size, throughput, and energy inputs are optimised. There are also considerable reductions in waste and residue produced. New grades of acetonitrile can now be produced with enhanced purity levels.</p>
<p>The invention is not limited to the embodiments hereinbefore described which may be varied in detail.</p>
Claims (2)
- <p>Claims 1. An acetonitrile purification process for the purification ofan acetonitrile mixture containing impurities to produce purified acetonitrile, the process comprising the steps of: charging the acetonitrile mixture into a processing vessel; adding phosphorus pentoxide to the acetonitrile mixture in an amount of from 0.05% to 0.1% by weight of the mixture; adding water to the mixture; : : : :* distilling the mixture in a distillation column; and S... * S</p><p>*:*. recovering purified acetonitrile from the distillation column; and
- 2. An acetonitrile purification process as claimed in claim I wherein phosphorous *::: : pentoxide is added to the acetonitrile mixture in an amount of from 0.06% to 0.08% by weight of the mixture. S...</p><p>3. An acetonitrile purification process as claimed in claim I or 2 wherein water is added to the mixture in an amount of less than 0.004% by volume of the acetonitri le mixture.</p><p>4. An acetonitrile purification process as claimed in any preceding claim comprising the step of agitating the mixture in the processing vessel after addition of the phosphorous pentoxide.</p><p>5. An acetonitrile purification process as claimed in claim 4 wherein the mixture is agitated by means of a stirring rod in the vessel.</p><p>6. An acetonitrile purification process as claimed in any of claims I to 5 comprising the steps of: -charging acetonitrile to be purified into a second vessel for delivery into the processing vessel; and delivering the acetonitrile from the second vessel into the processing vessel, on demand.</p><p>7. An acetonitrile purification process as claimed in any preceding claim comprising the step of charging the purified acetonitrile into the processing vessel to form a feedstock for a second stage processing.</p><p>:.:::. 8. An acetonitrile purification process as claimed in claim 7 wherein the second S...</p><p>***. 15 stage processing comprises: -S. * adding potassium carbonate and potassium permanganate to the feedstock in the processing vessel; S.. * a.</p><p>distilling the mixture in the distillation column; and S...</p><p>recovering highly purified acetonitrile from the distillation column.</p><p>9. An acetonitrile purification process as claimed in claim 8 wherein potassium carbonate is added in an amount of from 0.02 to 0.08% by weight of the feedstock.</p><p>10. An acetonitrile purification process as claimed in claim 8 or 9 wherein potassium carbonate is added in an amount of from 0.04 to 0.06% by weight of the feedstock.</p><p>11. An acetonitrile purification process as claimed in any of claims 8 to 10 wherein the potassium permanganate is added in an amount of from 0.002 to 0.004% by weight of the feedstock.</p><p>12. An acetonitrile purification process substantially as hereinbefore described with reference to the Figure and the examples.</p><p>13. Purified acetonitrile whenever purified by a process as claimed in any preceding claim. * a. * . * * *.* * . *4* . a * . S * a. * a. a. * S... * I **</p>
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0602509A GB2435040B (en) | 2006-02-08 | 2006-02-08 | Acetonitrile purification by the addition of phosphorus pentoxide, then water, and subsequent distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0602509A GB2435040B (en) | 2006-02-08 | 2006-02-08 | Acetonitrile purification by the addition of phosphorus pentoxide, then water, and subsequent distillation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0602509D0 GB0602509D0 (en) | 2006-03-22 |
| GB2435040A true GB2435040A (en) | 2007-08-15 |
| GB2435040B GB2435040B (en) | 2009-10-07 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0602509A Expired - Fee Related GB2435040B (en) | 2006-02-08 | 2006-02-08 | Acetonitrile purification by the addition of phosphorus pentoxide, then water, and subsequent distillation |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2435040B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531959A (en) * | 2012-02-17 | 2012-07-04 | 西安航洁化工科技有限责任公司 | Method for removing small amount of water contained in industrial acetonitrile |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2249308A (en) * | 1990-10-30 | 1992-05-06 | G K Analytical Sciences Limite | Purification of acetonitrile |
| GB2322856A (en) * | 1997-03-03 | 1998-09-09 | G K Analytical Sciences Limite | Purification of Acetonitrile |
-
2006
- 2006-02-08 GB GB0602509A patent/GB2435040B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2249308A (en) * | 1990-10-30 | 1992-05-06 | G K Analytical Sciences Limite | Purification of acetonitrile |
| GB2322856A (en) * | 1997-03-03 | 1998-09-09 | G K Analytical Sciences Limite | Purification of Acetonitrile |
Non-Patent Citations (5)
| Title |
|---|
| Anal. Chem., 1962, Vol. 34, pages 1139-1143 & Chemical Abstracts, abstr no 57:10513g-i. * |
| Anal. Chem., 1965, Vol. 37(11), pages 1447-1448 & Chemical Abstracts, abstr no 63:17108f-g. * |
| Chemicke Listy, 1978, Vol. 72(3), pages 306-309 & Chemical Abstracts, abstr no 88:179367. * |
| Chemicke Listy, 1989, Vol. 83(4), pages 435-436 & Chemical Abstracts, abstr no 111:224561. * |
| Pure and Applied Chemistry, 1967, Vol. 13(3), pages 427-435 & Chemical Abstracts, abstr no 67:11160. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531959A (en) * | 2012-02-17 | 2012-07-04 | 西安航洁化工科技有限责任公司 | Method for removing small amount of water contained in industrial acetonitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2435040B (en) | 2009-10-07 |
| GB0602509D0 (en) | 2006-03-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20130208 |