GB2212155A - Purification of nitriles - Google Patents
Purification of nitriles Download PDFInfo
- Publication number
- GB2212155A GB2212155A GB8825532A GB8825532A GB2212155A GB 2212155 A GB2212155 A GB 2212155A GB 8825532 A GB8825532 A GB 8825532A GB 8825532 A GB8825532 A GB 8825532A GB 2212155 A GB2212155 A GB 2212155A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resin
- phosphorus compound
- water
- weight
- dicyanobutene
- 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
Links
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 7
- 238000000746 purification Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 14
- -1 phosphorus compound Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 9
- JKBPBRLDGFKIIA-UHFFFAOYSA-N 2-propylidenepropanedinitrile Chemical compound CCC=C(C#N)C#N JKBPBRLDGFKIIA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000005538 phosphinite group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- ZQOHAQBXINVHHC-HNQUOIGGSA-N (e)-hex-2-enedinitrile Chemical compound N#CCC\C=C\C#N ZQOHAQBXINVHHC-HNQUOIGGSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- UGXIZSBWQYWVAH-UHFFFAOYSA-N bis(2-methylphenyl)phosphinous acid Chemical compound CC1=CC=CC=C1P(O)C1=CC=CC=C1C UGXIZSBWQYWVAH-UHFFFAOYSA-N 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C07C255/04—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing two cyano groups bound to the carbon skeleton
-
- 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
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/09—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton containing at least two cyano groups bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Trivalent phosphorus compounds are removed from nitriles by contact with a cation exchange resin which contains at most 10% by weight of water.
Description
Separation of Phosphorus Compounds
This invention relates to the separation of phosphorus compounds.
Trivalent phosphorus compounds are used as catalysts in chemical processes. In the hydrocyanation of butadiene to adiponitrile, phosphine catalyst components may be used. Also, phosphonites and phosphinites are used as catalyst components for the dimerisation of acrylonitrile to dicyanobutene. Suitable phosphinites and phosphonites for this process are of general 10 formula:
in which R1, R2 and R3 are individually hydrogen atoms or electron donating substituents which are free from active hydrogen atoms.
Suitable electron donating substituents are alkyl or alkoxy groups having for example 1 to 12 and preferably 1 to 3 carbon atoms, or R4RsN- groups having 1 to 10 and preferably 1 to 6 carbon atoms in the form of two alkyl substituents R4 and Rg. Preferably at least the group R2 is an electron donating substituent. Either R1 or R3 may form part of a fused alicyclic ring with R2. R is hydrogen or preferably an alkyl or cycloalkyl group for example having 1 to 12 and preferably 1 to 6 carbon atoms, and n and m are integers, each being either 1 or 2, provided that (m+n) equals 3. When n is 2, the substituents on each aromatic ring may be the same or different and when m is 2 the groups R may be the same or different.
By "electron-donating substituent" we mean a substituent of the aromatic nucleus which gives rise to a negative Hammett constant.
A discussion on Hammett constants and a table showing values for most common substituents is to be found in an article by Clark and
Perrin in Quarterly Reviews of the Royal Society of Chemistry, vol 18 1964 pp 295 - 320.
Examples of suitable substituents R1, R2 and R3 include alkoxy groups, eg methoxy, ethoxy, i-propoxy and t-butoxy; alkyl groups eg methyl, ethyl and propyl; and dialkyl amino groups, eg dimethylamino and diethylamino groups. Groups R1, R2 and R3 which do not contain active hydrogen atoms are preferred.
Suitable groups R include alkyl groups such as methyl, ethyl, isopropyl, neopentyl, 2-ethylhexyl; and cycloalkyl groups such as cyclohexyl.
In such chemical processes it may be desirable to separate phosphorus compounds from materials recovered from the reaction, for example streams containing the product. The trivalent phosphorus compounds may be converted into other trivalent or pentavalent compounds in such processes and it may be desirable to separate these as well as the trivalent phosphorus compounds.
We have found that such compounds may be very effectively removed from organic liquids which comprise a nitrile by contacting them with cation exchange resins, especially those bearing -S03H groups providing that the resin is substantially anhydrous. The nitrile is suitably a dinitrile and may be unsaturated. Several different nitrites may be present.
This invention therefore comprises a process of removing a trivalent phosphorus compound in which the phosphorus atom(s) is preferably linked to two or more preferably three organic groups from an organic liquid which comprises a nitrile containing it by contacting the liquid with a cation exchange resin which contains at most 10% by weight of water and is preferably substantially anhydrous.
Such resins are supplied 25commercially as wet beads containing for example about 50% water or as "dry" beads which contain about 3% water. A maximum of about 10% by weight of water may be present in the resin in our invention, but marked improvement in the process occurs at lower levels. Preferably at most 2%, more preferably at most 1% of water by weight is present. 30Desirably at most 0.2% by weight is present. It is desirable therefore to remove water from commercially available ion exchange resins and this may be accomplished by drying under vacuum or in dry gas for example air or an inert gas at a temperature of for example 60 to 1100C, preferably 70 to 100"C or by thorough treatment with an 35alcohol, for example by prolonged contact with a body of the alcohol or by thorough washing in a stream of alcohol.Suitable alcohols may have for example 1 to 8 and preferably 1 to 5 carbon atoms. If the phosphorus compound is to be removed from a non-alcohol-containing organic liquid the resin is preferably further contacted before such use with a non hydroxylic compound, for example a component of the organic liquid (other than the phosphorus compound) to displace the alcohol, thus preferably giving a resin substantially free from -OH group containing materials. However, if desired the alcohol-containing resin may be used without such an intermediate step.
We have also found that the resins may be regenerated and the phosphorus compound recovered by contacting the resin with an alcohol for example having 1 to 8 and preferably 1 to 6 carbon atoms or water.
If the resin is to be re-used it is preferred to regenerate with an alcohol, as if water is used residues of water must be removed from the resin before re-use.
Surprisingly, we have also found that, despite the strongly acidic nature of the resin which would be expected to catalyse the polymerisation of unsaturated compounds, it is possible to remove the phosphorus compounds even from organic liquids which comprise dicyanobutenes which may be produced by dimerising acrylonitrile.
In one form of the invention therefore a phosphorus compound as aforesaid is removed from an organic liquid which comprises a dicyanobutene, by contacting the liquid with an anhydrous ion exchange resin which comprises -S03H groups.
Removal of the phosphorus compound is preferably carried out especially when dicyanobutene is present at a low temperature (preferably below 800 C, and more preferably below 500C for example below 350C) and at a short residence time. The residence time is preferably at most 1 hour at 350C, at most 30 minutes at 500C and at most 10 minutes at 80"C.
This form of the invention is valuable in that removal of the phosphorus compound may be desirable in order to avoid deactivation of catalysts used in a subsequent hydrogenation stage in which dimers of acrylonitrile are converted into adiponitrile and/or hexamethylene diamine.
Palladium hydrogenation catalysts are particularly prone to poisoning by trivalent phosphorus compounds of formula
as defined previously, and these may be very effectively removed according to this invention.
Compounds which exist in tautomeric form between trivalent and pentavalent phosphorus forms are included herein as trivalent phosphorus compounds.
Examples 1. 50 g of a commercially available ion exchange resin sold under the trade name "Amberlyst" 15 comprising -S03H groups and containing about 3% of water by weight was dried under a vacuum of 10 mm of mercury at 1000C for 2 hrs leaving a water content of less than 0.5% by weight and was charged to a 1/2" diameter glass column. 1,4dicyanobutene (DCB) containing 5000 ppm tritolylphosphine was passed through the resin at a rate of 100 ml/hour at a temperature of 20 25"C. The effluent from the column contained ( 10 ppm tritolylphosphine. 650 ml of the DCB was passed through the column before the tritolylphosphine content of the effluent reached 10 ppm.
Repetition of the above experiment using untreated "Amberlyst" 15 resin containing 3% by weight of water allowed only 350 ml of the 1,4-dicyanobutene to be passed through before the tritolylphosphine content of the effluent reached 10 ppm.
2. 50 g of the dried ion exchange resin used in Example 1 was charged to a 1/2" diameter glass column. 1,4-dicyanobutene containing 1000 ppm isopropyl, bis-tolylphosphinite,
was passed through the resin before the effluent phosphinite content reached 5 ppm.
3. A crude stream comprising 1,4-dicyanobutene (92% by weight), higher oligomers of acrylonitrile (3% by weight) and 2,4dicyanobutene-1 and the phosphorus compounds below representing or derived from a catalyst used in its manufacture was hydrogenated using a Pd/charcoal catalyst at 1200C and 50 bars partial pressure of hydrogen.The catalyst was rapidly deactivated.
Compound P ppm tol P-OiPr 110 tol tol O / P-OiPr 80 tol tol 0 oli P-CH2CH2CN 70 tol tol P-OH 40 tol tol iPrOP-CH2CH2CN 30 iPrO tol / P-OH 20 iPrO -Unidentified 20 370 An identical crude stream was passed at a temperature of 20 to 250C through 100 g of an ion exchange resin sold commercially under the trade name "Amberlyst" 15 which had been dehydrated to below 0.5% by weight of water by successively washing with methanol and then acetonitrile in a 7/8" diameter glass column at a rate of 100 ml/h.
The effluent contained Cl ppm of elemental phosphorus. 1350 ml of dicyanobutene was passed through the resin before the phosphorus content of the effluent reached 1 ppm. This gave greatly improved catalyst stability in the hydrogenation step as previously described.
The resin was regenerated in the column by the following procedure: 1. 400 ml of methanol was passed through the resin to desorb the P compounds.
2. 400 ml of acetonitrile was then passed through the resin to displace residual methanol.
The resin was then re-used with similar results to those with the fresh resin.
4. 3.5 kg of Amberlyst 15 resin was charged to a 3" internal diameter stainless steel column. The resin was dehydrated by passing 15 litres of methanol in down-flow followed, after draining, by 50 l/h of dry N2 at 600C overnight in up-flow operation.
A crude stream of 1,4-dicyanobutene containing 190 ppm by weight of phosporus inothe form of P compounds as in example 3 was passed through the resin in up-flow at a rate of 3 kg/h. 90 kg of effluent containing c5ppm of elemental phosphorus was collected. This material gave greatly improved catalyst stability in hydrogenation tests lasting up to 500 hours using a Pd/charcoal catalyst at 1200C and 50 bars partial pressure of hydrogen.
In the above Examples no substantial polymerisation of dicyanobutene occurred.
ppm means parts per million by weight.
iPr means isopropyl.
tol means toluyl.
Claims (14)
1. A process in which a trivalent phosphorus compound is removed
from an organic liquid which comprises a nitrile by contacting the liquid containing the trivalent phosphorus compound with a cation exchange resin which contains at most 10% by weight of water.
2. A process as claimed in claim 1 in which the resin contains at most 1% water by weight.
3. A process as claimed in claim 1 or 2 in which the water content of the resin is reduced prior to use by drying in a vacuum or dry gas at a temperature in the range 60 to 110oC.
4. A process as claimed in claim 1 or 2 in which the water content of the resin is reduced before use by contacting it with an alcohol having 1 to 5 carbon atoms.
5. A process as claimed in any preceding claim in which the resin comprises - S03H groups.
6. A process as claimed in any preceding claim in which the phosphorus compound is a phosphonite or phosphinite of formula
in which m and n are each 1 or 2 and m + n = 3, R1 R2 and K3 are individually hydrogen atoms or electron donating substituents which are free from active hydrogen atoms and R is hydrogen or an alkyl or cycloalkyl group.
7. A process as claimed in any preceding claim which is carried out at a temperature of at most 50 C.
8. A process as claimed in any preceding claim in which the organic liquid comprises a dicyanobutene.
9 A process as claimed in claim 8 in which the dicyanobutene is hydrogenated to adiponitrile and/or hexamethylene do gamine after removal of the phosphorus compound.
10. A process as claimed in claim 9 in which the hydrogenation is carried out using a palladium catalyst.
11. A process as claimed in claim 1 carried out substancially as described in any of the examples.
12. Nitriles whenever purified by a process as claimed in any of claims 1 to 8 or 11.
13. Phosphorus compounds recovered by a process as claimed in any of claims 1 to 8 or 11.
14. Adiponitrile and/or hexamethylene diamine produced by a process according to claim 9, 10 or 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878726279A GB8726279D0 (en) | 1987-11-10 | 1987-11-10 | Separation of phosphorus compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8825532D0 GB8825532D0 (en) | 1988-12-07 |
| GB2212155A true GB2212155A (en) | 1989-07-19 |
| GB2212155B GB2212155B (en) | 1991-07-31 |
Family
ID=10626709
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB878726279A Pending GB8726279D0 (en) | 1987-11-10 | 1987-11-10 | Separation of phosphorus compounds |
| GB8825532A Expired - Fee Related GB2212155B (en) | 1987-11-10 | 1988-11-01 | Removal of phosphorus compounds from nitriles |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB878726279A Pending GB8726279D0 (en) | 1987-11-10 | 1987-11-10 | Separation of phosphorus compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB8726279D0 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0438638A1 (en) * | 1989-12-27 | 1991-07-31 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing norcamphane dicarbonitriles |
| WO1998011060A1 (en) * | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| WO1998011051A1 (en) * | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| RU2173202C1 (en) * | 1997-07-24 | 2001-09-10 | Родиа Шими | Method of removing organophosphorus compounds contained in gas or liquid |
| FR2850966A1 (en) * | 2003-02-10 | 2004-08-13 | Rhodia Polyamide Intermediates | Preparation of dinitrile compound, useful as chemical intermediate, from an unsaturated nitrile by hydrocyanation in the presence of an organometallic complex catalyst and a Lewis acid co-catalyst |
-
1987
- 1987-11-10 GB GB878726279A patent/GB8726279D0/en active Pending
-
1988
- 1988-11-01 GB GB8825532A patent/GB2212155B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0438638A1 (en) * | 1989-12-27 | 1991-07-31 | MITSUI TOATSU CHEMICALS, Inc. | Process for producing norcamphane dicarbonitriles |
| US5087722A (en) * | 1989-12-27 | 1992-02-11 | Mitsui Toatsu Chemicals, Inc. | Process for producing norcamphane dicarbonitriles |
| WO1998011060A1 (en) * | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| WO1998011051A1 (en) * | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| US6147247A (en) * | 1996-09-10 | 2000-11-14 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| US6207851B1 (en) | 1996-09-10 | 2001-03-27 | Basf Aktiengesellschaft | Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine |
| KR100550177B1 (en) * | 1996-09-10 | 2006-02-10 | 바스프 악티엔게젤샤프트 | Process for Simultaneously Preparing 6-Aminocapronitrile and Hexamethylenediamine |
| RU2173202C1 (en) * | 1997-07-24 | 2001-09-10 | Родиа Шими | Method of removing organophosphorus compounds contained in gas or liquid |
| FR2850966A1 (en) * | 2003-02-10 | 2004-08-13 | Rhodia Polyamide Intermediates | Preparation of dinitrile compound, useful as chemical intermediate, from an unsaturated nitrile by hydrocyanation in the presence of an organometallic complex catalyst and a Lewis acid co-catalyst |
| WO2004080924A3 (en) * | 2003-02-10 | 2004-10-28 | Rhodia Polyamide Intermediates | Method of producing dinitrile compounds |
| RU2286336C2 (en) * | 2003-02-10 | 2006-10-27 | Родиа Полиамид Интермедиэйтс | Method for preparing dinitrile compounds |
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8825532D0 (en) | 1988-12-07 |
| GB8726279D0 (en) | 1987-12-16 |
| GB2212155B (en) | 1991-07-31 |
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| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951101 |