CN1075810C - Titanium dioxide-catalysed cyclisation in the liquid phase of 6 -amino caproic acid nitrile to caprolactam - Google Patents
Titanium dioxide-catalysed cyclisation in the liquid phase of 6 -amino caproic acid nitrile to caprolactam Download PDFInfo
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- CN1075810C CN1075810C CN96194001A CN96194001A CN1075810C CN 1075810 C CN1075810 C CN 1075810C CN 96194001 A CN96194001 A CN 96194001A CN 96194001 A CN96194001 A CN 96194001A CN 1075810 C CN1075810 C CN 1075810C
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- titanium dioxide
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- 239000007791 liquid phase Substances 0.000 title claims abstract description 6
- -1 6 -amino caproic acid nitrile Chemical class 0.000 title abstract description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 3
- 239000010936 titanium Substances 0.000 title description 3
- 229910052719 titanium Inorganic materials 0.000 title description 3
- 229960002684 aminocaproic acid Drugs 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 125000005219 aminonitrile group Chemical group 0.000 claims description 12
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 239000003791 organic solvent mixture Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Production of cyclic lactams by the reaction of amino carboxylic acid nitriles with water, performed in the liquid phase in the presence of heterogeneous catalysts based on titanium dioxide with a rutile content in the range from 0.1 to 95 wt.% and an anatase content in the range from 99.9 to 5 wt.% in relation to the total titanium dioxide content.
Description
The present invention relates to a kind of in the presence of catalyzer the novel method by amino-nitrile and water prepared in reaction cyclic lactames.
US-A4628085 discloses under 300 ℃, on acidic silica gel, and in gas phase, the reaction of 6-aminocapronitrile and water.This reaction is carried out with the preparation hexanolactam quantitatively with 95% initial selectivity, but will find productive rate and optionally reduction rapidly.Described similar methods in US-A4625023, wherein the air-flow that comprises 6-aminocapronitrile, adiponitrile, ammonia, water and carrier gas of high dilution flows through on silica gel and a kind of copper/chromium/barium-titanyl compound catalytic bed.Obtain hexanolactam, its selectivity be 91% and transformation efficiency be 85%.Here find the rapid deactivation effect of catalyzer again.
US-A2301964 relates under 285 ℃, and in the aqueous solution, the 6-aminocapronitrile is converted into the uncatalyzed reaction of hexanolactam.Its productive rate is lower than 80%.
FR-A2029540 has described the homogeneous phase metal catalyst that uses from zinc and copper family with the method for 6-aminocapronitrile cyclisation as hexanolactam in the aqueous solution, the productive rate of resulting hexanolactam reaches 83%.Yet it is debatable removing catalyzer fully from required product hexanolactam, because hexanolactam and employed metal form title complex.
The purpose of this invention is to provide a kind of method by amino-nitrile and water prepared in reaction cyclic lactames, this method does not have above-mentioned defective.
We have found that and to realize purpose of the present invention like this, promptly in the presence of based on the heterogeneous catalyst of titanium dioxide, in liquid phase, react, wherein in the total content of titanium dioxide, the content of rutile is that the content of 0.1-95 weight % and anatase octahedrite is 99.9～5 weight % in the titanium dioxide.
Can know the preferred embodiment of the inventive method from dependent claims.
The raw material of Shi Yonging is an amino-nitrile in the method for the invention, preferably those of formula I
Here, n and m respectively are 0,1,2,3,4,5,6,7,8 and 9, and n+m's and be 3 at least preferably is 4 at least.
R
1And R
2Be the substituting group of any kind in principle, need only to guarantee that substituting group does not influence required cyclization.Preferred R
1And R
2Separate is C
1-C
6Alkyl or C
5-C
7Cycloalkyl or C
6-C
12Aryl
Particularly preferred raw material is a general formula
H
2N-(CH
2)
mThe amino-nitrile of-C ≡ N, here, the value of m is 3,4,5 or 6, particularly 5.When m=5, initial compounds is the 6-aminocapronitrile.
In the method for the invention, use heterogeneous catalyst that above-mentioned amino-nitrile and water are reacted to obtain cyclic lactames.
The amino-nitrile of use formula I obtains the cyclic lactames of corresponding general formula II
Here, n, m, R
1And R
2Has above-mentioned implication.Particularly preferred lactan be n be 0 and the value of m be 4,5 or 6, those of 5 (under one situation of back, obtaining hexanolactam) particularly.
Usually under 140～320 ℃, preferred 160～280 ℃ temperature, in liquid phase, carry out this reaction; Pressure is 1～250 crust normally, and preferably 5～150 crust it should be noted that reaction mixture mainly is in a liquid state under employed condition, that is to say not having under the situation of solid catalyst, and be liquid.Usually the residence time is 1～120, preferred 1～90 and preferred especially 1～60 minute.In certain situation, 1～10 minute the residence time proves fully enough.
Generally, every mole amino-nitrile uses at least 0.01 mole, preferred 0.1～20 and 1～5 mole water particularly.
Advantageously, use 1～50 weight %, the particularly aqueous solution of the amino-nitrile of 5～50 weight %, preferred especially 5～30 weight % (solvent also is a reagent in this case) or the solution in water/solvent mixture.The example of the solvent that can mention is for example for example glycol ether and a Tetraglycol 99 of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol and polyvalent alcohol of alkanol, hydro carbons is sherwood oil, benzene,toluene,xylene for example, lactan is for example N-Methyl pyrrolidone, N-methyl caprolactam or N-ethyl hexanolactam of the lactan that replaces of pyrrolidone or hexanolactam or alkyl for example, and carboxylicesters, preferably have the ester of the carboxylic acid of 1～8 carbon atom.Ammonia also may reside in reaction.Certainly, mixture that also can be with an organic solvent.Particularly advantageously be the mixture of water and alcohols in some cases, wherein water/pure weight ratio is 1～75: 25～99, preferably 1～50: 50～99.
In the presence of titanium deoxide catalyst, carry out method of the present invention, wherein in the total content of titanium dioxide, the content of rutile is 0.1～95 weight % in the titanium dioxide, preferably the content of 1～90 weight % and anatase octahedrite be 99.9～5, preferred 99～10 weight %.
In preferred embodiment, in the fixed bed that uses extrudate or sheet form catalyzer, carry out this reaction, wherein the diameter of flap and extrudate 1～10mm preferably.
Use the titania powder that had institute's rutile that requires and anatase octahedrite content or use by the pure anatase ore bodies of pyrolysis or contain anatase octahedrite and rutile mixed form or the titania powder that obtains of the mixture of pure anatase octahedrite and rutile body mutually and prepare extrudate and flap according to the method for routine, wherein carry out pyrolysis until the ratio that reaches required anatase octahedrite and rutile in suitable temperature with under the residence time (these two is known to those skilled in the art, for example referring to Catalysis Today14 (1992) 225-242).
Corresponding powder is available on the market, for example the titania powder P25 of Degussa
The S150 of (rutile of 20-30 weight % and the anatase octahedrite of 80～70 weight %) and Finti-Kemira
And S140
(anatase octahedrites of each 100 weight %).
Titanium dioxide can be used with itself or as catalyst-loaded, it can be coated in this case on the machinery or chemically stable carrier that has high surface area usually.
Titanium dioxide can prepare by precipitating from the aqueous solution, for example by sulfate process or other method pyrolysis preparation method as the thin titania powder that can buy.
If desired, contain rutile/anatase titanium dioxide can for example aluminum oxide, zirconium white or cerium oxide mix mutually with other oxide compound.The method for preparing various oxide mixture has many available.Can prepare oxide compound like this or, for example pass through co-precipitation from solution by calcining the oxide precursor that can be converted into oxide compound.This causes employed two kinds of extraordinary dispersions of oxide compound usually.Oxide mixture or precursor mixture also can prepare by first kind of oxide compound of precipitation in the presence of for second kind of oxide compound of the form of suspension of fine dispersion particle or precursor or precursor.Another kind method comprises the mechanically mixing of oxide compound or precursor powder, and this mixture is used to prepare extrudate or flap as starting material in this case.
It is catalyst-loaded to adopt various method to prepare.Therefore, can the form of titanium dioxide with colloidal sol be coated on the carrier by simple dipping.Usually from catalyzer, remove the volatile component of colloidal sol by dry and calcining.Such colloidal sol of titanium dioxide can have been bought.
The another kind of possibility that applies the active titanic dioxide layer comprises hydrolysis or pyrolysis organic or inorganic compound.Therefore, can on ceramic monolith, apply a thin titanium dioxide layer by the alkoxide of hydrolysis titanium isopropylate or other titanium.Another kind of suitable compound is TiCl
4Suitable carriers is titanium dioxide itself or other steady oxide for example powder, extrudate or the flap of silicon-dioxide.Employed carrier can be macroporous so that improve the migration of material.These two falls in the above range mutually with anatase octahedrite importantly to note rutile during the pyrolysis of titanium dioxide.
Method of the present invention obtains cyclic lactames with high productive rate, good selectivity and stability of catalytic activity, particularly hexanolactam.
Embodiment
Embodiment 1～7
Under the pressure of 100 crust, make the water of 6-aminocapronitrile (ACN) and ethanolic soln flow through heating tubular reactor (the diameter 6mm that volume is 25ml; Length 800mm) in, wherein be filled with the titanium dioxide of sheet or extrudate form in the reactor, weight ratio is listed in the table.Leave the product stream of reactor by gc analysis.The result lists in the table equally.Table
1 2/3 weight parts are P25
Powder, all the other are DT51
Mixture.(Rh ne-Poulenc) 2 2/3 weight parts are P25
Powder, all the other are S150
Mixture.(Finti-Kemira) 3 rutile from Sachtleben are at 2 hours A=productive rates of 875 ℃ of following thermal treatment; The S=selectivity; The BET surface-area n.b.=undetermined that u=transformation efficiency BET=measures according to DIN66 131 methods
| Embodiment | Catalyzer | Form | Sulphate content [%] | Rutile [%] | Anatase octahedrite [%] | BET [m 2/g] | A | U | S |
| 1 | P25 | 3 mm extrudates | 0,01 | 93 | 7 | 15 | 92 | 95 | 97 |
| 2 | P25/DT51 1 | 3 mm extrudates | 0,5 | 18 | 82 | 41 | 90 | 98 | 93 |
| 3 | P25/S150 2 | 3 mm extrudates | 0,06 | 16 | 84 | 50 | 89 | 97 | 92 |
| 4 | P25 | 1,5 mm extrudate | n.b. | 20 | 80 | 48 | 91 | 99 | 93 |
| Comparing embodiment | |||||||||
| 5 | VKR611 3 | 1,5 mm extrudate | n.b. | 100 | 0 | 5 | 5 | 10 | 53 |
| 6 | DT51 | 4 mm extrudates | n.b. | 0 | 100 | 36 | 78 | 90 | 85 |
| 7 | S150 | 3 mm extrudates | 0,17 | 0 | 100 | 108 | 90 | 99 | 91 |
Claims (5)
- One kind in the presence of catalyzer in liquid phase the method by amino-nitrile and water prepared in reaction cyclic lactames, wherein in the presence of based on the heterogeneous catalyst of titanium dioxide, carry out this reaction, based on the total content meter of titanium dioxide, the content of rutile is that the content of 0.1-95 weight % and anatase octahedrite is 99.9-5 weight % in the titanium dioxide.
- 2. carry out under the temperature that is reflected at 140～320 ℃ according to the process of claim 1 wherein.
- 3. according to the method for one of claim 1 and 2, wherein use formulaH 2N-(CH 2) mThe amino-nitrile of-C ≡ N, here, m is 3,4,5 or 6.
- 4. according to the method for claim 3, wherein use the 6-aminocapronitrile as amino-nitrile.
- 5. according to the method for one of claim 1 and 2, wherein use the aqueous solution of amino-nitrile of a kind of 1～50 weight % or the solution in water/ORGANIC SOLVENT MIXTURES.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19517821A DE19517821A1 (en) | 1995-05-18 | 1995-05-18 | Process for the production of caprolactam |
| DE19517821.1 | 1995-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184467A CN1184467A (en) | 1998-06-10 |
| CN1075810C true CN1075810C (en) | 2001-12-05 |
Family
ID=7761968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194001A Expired - Fee Related CN1075810C (en) | 1995-05-18 | 1996-05-07 | Titanium dioxide-catalysed cyclisation in the liquid phase of 6 -amino caproic acid nitrile to caprolactam |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0815077A1 (en) |
| JP (1) | JPH11505230A (en) |
| KR (1) | KR19990014859A (en) |
| CN (1) | CN1075810C (en) |
| AU (1) | AU700098B2 (en) |
| BG (1) | BG102027A (en) |
| BR (1) | BR9608470A (en) |
| CA (1) | CA2218132A1 (en) |
| CZ (1) | CZ289460B6 (en) |
| DE (1) | DE19517821A1 (en) |
| EA (1) | EA199700402A1 (en) |
| HU (1) | HU220356B (en) |
| MX (1) | MX9708676A (en) |
| NO (1) | NO307964B1 (en) |
| NZ (1) | NZ308485A (en) |
| PL (1) | PL323389A1 (en) |
| SK (1) | SK154897A3 (en) |
| TR (1) | TR199701385T1 (en) |
| TW (1) | TW340840B (en) |
| WO (1) | WO1996036600A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890370A (en) * | 2010-08-05 | 2010-11-24 | 上海交通大学 | Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19738464A1 (en) * | 1997-09-03 | 1999-03-04 | Basf Ag | Use of moldings as a catalyst for the production of caprolactam |
| DE19738463C2 (en) * | 1997-09-03 | 1999-09-23 | Basf Ag | Process for the production of caprolactam |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2029540A (en) * | 1935-10-01 | 1936-02-04 | Porteous William | Trailer |
| US2301964A (en) * | 1941-09-12 | 1942-11-17 | Du Pont | Method of preparing lactams |
| FR2029540A1 (en) * | 1969-01-28 | 1970-10-23 | Asahi Chemical Ind | Epsilon caprolactam by one step synthesis |
| US4628085A (en) * | 1985-09-03 | 1986-12-09 | Allied Corporation | Use of silica catalyst for selective production of lactams |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4625023A (en) * | 1985-09-03 | 1986-11-25 | Allied Corporation | Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams |
| JP2969779B2 (en) * | 1990-05-01 | 1999-11-02 | 株式会社明電舎 | Shading image processing device |
| DE4339648A1 (en) * | 1993-11-20 | 1995-05-24 | Basf Ag | Process for the production of caprolactam |
-
1995
- 1995-05-18 DE DE19517821A patent/DE19517821A1/en not_active Withdrawn
-
1996
- 1996-05-02 TW TW085105277A patent/TW340840B/en active
- 1996-05-07 BR BR9608470A patent/BR9608470A/en unknown
- 1996-05-07 JP JP8534516A patent/JPH11505230A/en active Pending
- 1996-05-07 EA EA199700402A patent/EA199700402A1/en unknown
- 1996-05-07 NZ NZ308485A patent/NZ308485A/en unknown
- 1996-05-07 CA CA002218132A patent/CA2218132A1/en not_active Abandoned
- 1996-05-07 HU HU9801131A patent/HU220356B/en not_active IP Right Cessation
- 1996-05-07 AU AU58147/96A patent/AU700098B2/en not_active Ceased
- 1996-05-07 CZ CZ19973578A patent/CZ289460B6/en not_active IP Right Cessation
- 1996-05-07 MX MX9708676A patent/MX9708676A/en unknown
- 1996-05-07 SK SK1548-97A patent/SK154897A3/en unknown
- 1996-05-07 TR TR97/01385T patent/TR199701385T1/en unknown
- 1996-05-07 KR KR1019970708204A patent/KR19990014859A/en not_active Application Discontinuation
- 1996-05-07 CN CN96194001A patent/CN1075810C/en not_active Expired - Fee Related
- 1996-05-07 EP EP96919687A patent/EP0815077A1/en not_active Withdrawn
- 1996-05-07 PL PL96323389A patent/PL323389A1/en unknown
- 1996-05-07 WO PCT/EP1996/001891 patent/WO1996036600A1/en not_active Application Discontinuation
-
1997
- 1997-11-06 BG BG102027A patent/BG102027A/en unknown
- 1997-11-17 NO NO975268A patent/NO307964B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2029540A (en) * | 1935-10-01 | 1936-02-04 | Porteous William | Trailer |
| US2301964A (en) * | 1941-09-12 | 1942-11-17 | Du Pont | Method of preparing lactams |
| FR2029540A1 (en) * | 1969-01-28 | 1970-10-23 | Asahi Chemical Ind | Epsilon caprolactam by one step synthesis |
| US4628085A (en) * | 1985-09-03 | 1986-12-09 | Allied Corporation | Use of silica catalyst for selective production of lactams |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890370A (en) * | 2010-08-05 | 2010-11-24 | 上海交通大学 | Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof |
| CN101890370B (en) * | 2010-08-05 | 2012-05-30 | 上海交通大学 | Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9801131A3 (en) | 1999-05-28 |
| WO1996036600A1 (en) | 1996-11-21 |
| PL323389A1 (en) | 1998-03-30 |
| HUP9801131A2 (en) | 1998-08-28 |
| NO307964B1 (en) | 2000-06-26 |
| NO975268L (en) | 1997-11-17 |
| SK154897A3 (en) | 1998-07-08 |
| EA199700402A1 (en) | 1999-06-24 |
| CZ357897A3 (en) | 1998-04-15 |
| HU220356B (en) | 2001-12-28 |
| JPH11505230A (en) | 1999-05-18 |
| TR199701385T1 (en) | 1998-04-21 |
| BG102027A (en) | 1998-08-31 |
| CN1184467A (en) | 1998-06-10 |
| EP0815077A1 (en) | 1998-01-07 |
| DE19517821A1 (en) | 1996-11-21 |
| BR9608470A (en) | 1998-12-29 |
| MX9708676A (en) | 1998-02-28 |
| CA2218132A1 (en) | 1996-11-21 |
| TW340840B (en) | 1998-09-21 |
| CZ289460B6 (en) | 2002-01-16 |
| NO975268D0 (en) | 1997-11-17 |
| NZ308485A (en) | 2000-01-28 |
| KR19990014859A (en) | 1999-02-25 |
| AU5814796A (en) | 1996-11-29 |
| AU700098B2 (en) | 1998-12-24 |
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