CN1161332C - Solid acid catalyst for preparing hexanolactam - Google Patents
Solid acid catalyst for preparing hexanolactam Download PDFInfo
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- CN1161332C CN1161332C CNB011319488A CN01131948A CN1161332C CN 1161332 C CN1161332 C CN 1161332C CN B011319488 A CNB011319488 A CN B011319488A CN 01131948 A CN01131948 A CN 01131948A CN 1161332 C CN1161332 C CN 1161332C
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- China
- Prior art keywords
- titanium
- acid catalyst
- solid acid
- hexanolactam
- zirconium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a catalyst for preparing caprolactam, which mainly solves the problem that the activity and the selectivity of catalysts used in the prior art can not simultaneously reach high values, i.e. the yield of caprolactam as a target product is low. The catalyst perfectly solves the problem by the technical scheme that the catalyst is prepared by taking the composite oxide of zirconium and titanium as a carrier to carrying the oxide of boron. The catalyst can be used for the industrial production of caprolactam catalysts.
Description
Technical field
The present invention relates to a kind of solid acid catalyst that is used to prepare hexanolactam, particularly reset the solid acid catalyst of preparation hexanolactam about cyclohexanone-oxime gas phase Beckmann.
Background technology
Hexanolactam is one of important source material of synthon and synthetic materials, be mainly used in and make daiamid-6 fiber (nylon 6), resin and film, also be used as the raw material of medicine, coating, leatheroid, softening agent, and be used for chemosynthesis Methionin on a small quantity, at numerous areas such as weaving, plastics, fine chemistry industries purposes is widely arranged.The Beckmann rearrangement reaction of cyclohexanone-oxime is a most important technological process in the caprolactam production process, and the influence of quality product is played a crucial role.Current industrial production is to be catalyzer with the vitriol oil or oleum, and cyclohexanone-oxime is converted into hexanolactam vitriol through liquid phase Beckmann rearrangement reaction, and then makes with the ammonia neutralization.Though use the vitriol oil to have very high selectivity, produce the byproduct of ammonium sulfate that belongs to the poor efficiency chemical fertilizer in a large number simultaneously, and because the existence of the vitriol oil a series of problems such as conversion unit burn into contaminate environment and safety have been caused as catalyzer.
In order to overcome problems and the shortcoming that above-mentioned homogeneous phase Beckmann rearrangement reaction is brought, people have developed especially gas-solid phase of the heterogeneous rearrangement technology rearrangement reaction under the solid acid catalyst effect.Used catalyzer mainly contains oxide compound (comprising single oxide and composite oxides) and molecular sieve (comprising zeolite-type molecular sieves and non-zeolitic molecular sieves) etc.
Be entitled as to disclose in the U.S. Pat 3639391 (1972) of " method that the cyclic ketone oxime rearrangement prepares acid amides " and a kind ofly prepare corresponding amide by the ring-type ketoxime, particularly by the solid acid catalyst of preparing caprolactam with cyclohexanone-oxime, it is with Thorotrast (ThO
2) be carrier, the oxide compound of boron is an active ingredient.Though this catalyzer is to have higher initial activity under the reaction conditions of carrier gas at normal pressure, 320 ℃ of temperature of reaction, argon gas, the cyclohexanone-oxime transformation efficiency that reacted 1/2 hour is 99.1%, but its less stable, after reaction 5 hours, the cyclohexanone-oxime transformation efficiency just drops to 68.5%.
Be entitled as among the HOII P NL8204837 (1984) of " method that cyclohexanone-oxime is converted into hexanolactam with silica-based heterogeneous catalyst ", adopt the silica-based molecular sieve (SiO of boracic
2/ B
2O
3Mol ratio is 220) be catalyzer, at 340 ℃ of temperature of reaction, toluene solvant, N
2Under the reaction conditions for carrier gas, the initial conversion of cyclohexanone-oxime is 100%, but this selectivity of catalyst has only 58%.
Being entitled as the solid acid catalyst disclosed in European patent EP 0823422 A1 (1998) of " by the method for oxime system acid amides " is the SiO with special construction
2-Al
2O
3Compound, its Si/Al mol ratio is 20～1000, average pore radius is 20～100 dusts, still is undefined structure after 550 ℃ of roastings.Though this catalyzer is made solvent, N at methyl alcohol
2Have good active under the reaction conditions for 380 ℃ of carrier gas, temperature, react 44 hours cyclohexanone-oxime transformation efficiencys still greater than 99%, but its selectivity not ideal enough (＜80%).
Above-mentioned several solid acid catalyst is used for cyclohexanone-oxime gas phase Beckmann rearrangement reaction, and its performance can't be satisfactory, and particularly active and selectivity often can't reach high value simultaneously, so can't satisfy industrial requirement.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the prior art, activity of such catalysts and selectivity can't reach high value simultaneously, thereby the yield of hexanolactam is lower, causes the defective of the loaded down with trivial details or wasting of resources of subsequent process, and a kind of new catalyzer that is used to prepare hexanolactam is provided.Use this catalyzer to have the high and good characteristics of hexanolactam selectivity of cyclohexanone-oxime transformation efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of solid acid catalyst that is used to prepare hexanolactam, form by following component in parts by weight:
A) molar fraction of titanium atom is 50～95 parts of 0.1～0.95 titanium oxide and zirconium white composite oxide carriers in the total atom number of titanium and zirconium; Be stated from the composite oxide carrier
B) oxide compound of boron is 5～50 parts.
In the technique scheme, the molar fraction preferable range of titanium atom is 0.25～0.9 in the total atom number of titanium and zirconium, more preferably scope is 0.5～0.75, is 70～90 parts in parts by weight composite oxide carrier consumption preferable range, and the oxide compound consumption preferable range of boron is 10～30 parts.
Preparation of catalysts method of the present invention by titanium and zirconium mixed oxide and boric acid through dipping or after mixing drying and high-temperature roasting (400～800 ℃) make.
Titanium and zirconium mixed oxide can adopt method preparations such as coprecipitation method, sluggish precipitation and sol-gel processing.Used raw material can be muriate such as TiCl
4, oxychlorination thing such as ZrOCl
2, nitric acid oxonium salt such as ZrO (NO
3)
2With vitriol such as Ti (SO
4)
2Deng.Precipitation agent can adopt ammoniacal liquor or urea etc.
The general preparation method of the composite oxide carrier of titanium and zirconium is that the salt solution mix with two or more is even then with the salt wiring solution-forming of each component.Under vigorous stirring, adding a certain amount of precipitation agent to the pH value of solution is 7～12.Through ageing, filtration, do not exist to there being harmful ion then with the distilled water repetitive scrubbing.Last drying, certain temperature (400～800 ℃) are descended roasting and are made.
Among the present invention, be carrier owing to adopted the composite oxides with titanium and zirconium, prepared boron oxide catalyzer not only has very high activity, and has very high selectivity simultaneously, thereby makes the yield of hexanolactam improve greatly.The high-performance that catalyzer of the present invention had is relevant with the character that the composite oxide carrier of titanium that is adopted and zirconium has uniqueness, the loading type boron oxide catalyzer of the composite oxide carrier of titanium and zirconium preparation thus, have more cyclohexanone-oxime the acid site that the Beckmann rearrangement reaction generates the required certain strength of hexanolactam takes place, thereby improved activity of such catalysts and selectivity greatly.The transformation efficiency of cyclohexanone-oxime is up to 100%, and the selectivity of product hexanolactam is up to 97.4% simultaneously, has obtained better technical effect.
The present invention uses the continuous flow fixed-bed micro-reactor to carry out the investigation of cyclohexanone-oxime gas phase Beckmann rearrangement reaction catalyst performance, and reactor inside diameter is 6 millimeters, and length is 300 millimeters, stainless steel.Adopt electrically heated, temperature is controlled automatically.Reactor bottom filling 40～60 purpose inert materials are as upholder, filling 0.8 gram catalyzer in the reactor, and filling 40～60 purpose inert materials in catalyzer top are made for the usefulness of raw material preheating and vaporization.The raw material cyclohexanone-oxime mixes with carrier gas, from top to bottom by beds, the Beckmann rearrangement reaction takes place, and generates purpose product hexanolactam and by products such as a spot of pimelinketone, cyclonene, 5-cyano group pentane, 5-cyano group-1-amylene and aniline.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get a certain amount of analytical pure titanium tetrachloride (TiCl
4) solution, under agitation slowly be added drop-wise in an amount of distilled water, obtain TiCl
4Water solution A.Take by weighing a certain amount of analytical pure zirconium oxychloride (ZrOCl
28H
2O), be dissolved in an amount of distilled water and obtain ZrOCl
2Aqueous solution B.A mixed mutually with B and be stirred well to evenly, obtain the mixed aqueous solution C of titaniferous, zirconium.Under violent stirring, solution C slowly is added drop-wise in an amount of ammonia soln, dropwising its pH value of back is 9, gained is deposited in kept at room temperature overnight, then with sedimentation and filtration also with the distilled water repetitive scrubbing to there not being chlorion (checking) with Silver Nitrate.The filter cake of washing back gained is after oven drying, 500 ℃ of high-temperature roastings of retort furnace, and it is standby that its 40～60 order is got in pulverizing.Making the titaniferous atomic mole fraction respectively by the consumption that changes titanium tetrachloride and zirconium oxychloride is 0.1,0.25,0.50,0.75,0.90 and 0.95 titanium and zirconium composite oxides carrier.
Claim 4.8 gram boric acid to be dissolved in 16 ml waters, in this solution, add the above-mentioned prepared different carriers of 20 grams then, after oven drying, 600 ℃ of high-temperature roastings of retort furnace, obtain catalyst A, B, C, D, E, F respectively.
[comparative example 1]
The preparation method is that carrier makes catalyzer G and H respectively with single oxide titanium oxide or zirconium white respectively just with embodiment 1.
[embodiment 2]
With catalyst A, B, C, D, E, F, G and the H that embodiment 1 and comparative example 1 make, in continuous flow fixed bed minisize reaction evaluating apparatus, carry out the active investigation of cyclohexanone-oxime gas phase Beckmann rearrangement reaction respectively.The loadings of catalyzer: 0.8 gram; Temperature of reaction: 300 ℃; Pressure: 0.1MPa; Air speed: 0.33 hour-1 (in cyclohexanone-oxime weight); Carrier gas (high-purity N 2) flow: 30 ml/min.After catalyst loading is intact, be pre-treatment 60 minutes under the condition of 50 ml/min at 350 ℃, carrier gas flux earlier.Then with the benzole soln (5 weight %) of cyclohexanone-oxime through micro-fresh feed pump injecting reactor.Reaction product adopts ice-water bath cooling back to collect quantitative analysis on the HP4890 gas chromatograph.Evaluation result sees Table 1.
Table 1 activity of such catalysts and selectivity
| Catalyzer | The cyclohexanone-oxime transformation efficiency, % | The hexanolactam selectivity, % | ||
| 1 hour | 5 hours | 1 hour | 5 hours | |
| A | 100 | 70.8 | 79.7 | 78.8 |
| B | 100 | 91.8 | 91.7 | 84.2 |
| C | 100 | 98.4 | 97.4 | 96.5 |
| D | 100 | 98.8 | 90.4 | 86.1 |
| E | 100 | 99.1 | 89.3 | 86.7 |
| F | 100 | 92.3 | 84.3 | 83.5 |
| G | 100 | 87.4 | 81.5 | 81.0 |
| H | 100 | 86.1 | 81.9 | 82.4 |
The titaniferous atomic mole fraction that the present invention makes is the boron oxide catalyzer that 0.1～0.90 titanium and zirconium mixed oxide are carrier, has very high cyclohexanone-oxime transformation efficiency and hexanolactam selectivity simultaneously, and has stability preferably.
Claims (5)
1, a kind of solid acid catalyst that is used to prepare hexanolactam, form by following component in parts by weight:
A) molar fraction of titanium atom is 50～95 parts of 0.1～0.95 titanium oxide and zirconium white composite oxide carriers in the total atom number of titanium and zirconium; Be stated from the composite oxide carrier
B) oxide compound of boron is 5～50 parts.
2,, it is characterized in that the molar fraction of titanium atom in the total atom number of titanium and zirconium is 0.25～0.9 according to the described solid acid catalyst that is used to prepare hexanolactam of claim 1.
3,, it is characterized in that the molar fraction of titanium atom in the total atom number of titanium and zirconium is 0.5～0.75 according to the described solid acid catalyst that is used to prepare hexanolactam of claim 2.
4,, it is characterized in that in parts by weight composite oxide carrier consumption be 70～90 parts according to the described solid acid catalyst that is used to prepare hexanolactam of claim 1.
5,, it is characterized in that the oxide compound consumption in parts by weight boron is 10～30 parts according to the described solid acid catalyst that is used to prepare hexanolactam of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011319488A CN1161332C (en) | 2001-10-22 | 2001-10-22 | Solid acid catalyst for preparing hexanolactam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011319488A CN1161332C (en) | 2001-10-22 | 2001-10-22 | Solid acid catalyst for preparing hexanolactam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1413986A CN1413986A (en) | 2003-04-30 |
| CN1161332C true CN1161332C (en) | 2004-08-11 |
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ID=4671003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011319488A Expired - Fee Related CN1161332C (en) | 2001-10-22 | 2001-10-22 | Solid acid catalyst for preparing hexanolactam |
Country Status (1)
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG110097A1 (en) * | 2003-07-08 | 2005-04-28 | Sumitomo Chemical Co | Method for producing epsilon-caprolactam |
| CN109503483B (en) * | 2018-12-27 | 2021-12-14 | 中国天辰工程有限公司 | Catalyst for preparing caprolactam through liquid phase Beckmann rearrangement and preparation method thereof |
-
2001
- 2001-10-22 CN CNB011319488A patent/CN1161332C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1413986A (en) | 2003-04-30 |
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Granted publication date: 20040811 Termination date: 20111022 |