CN105949083A - Cyclohexanone ammoximation method - Google Patents
Cyclohexanone ammoximation method Download PDFInfo
- Publication number
- CN105949083A CN105949083A CN201610313124.4A CN201610313124A CN105949083A CN 105949083 A CN105949083 A CN 105949083A CN 201610313124 A CN201610313124 A CN 201610313124A CN 105949083 A CN105949083 A CN 105949083A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cyclohexanone
- hydrogen peroxide
- ammonia
- cyclohexanone oxamidinating
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention innovatively provides a cyclohexanone ammoximation method. The method comprises steps as follows: hydrogen peroxide, an inhibitor of hydrogen peroxide, cyclohexanone and a low-carbon alcohol aid are mixed in a certain proportion to form a mixed liquid, and the mixed liquid is sent to the top of an oximation reactor to be dispersed into 1-200 mu m fine particles; mixed gas of inert gas and ammonia gas is preheated and sent into the oximation reactor to be contacted with the dispersed fine particles, and the dispersed fine particles are further gasified; the gasified fine particles and ammonia gas are placed on a titanium-containing catalyst in the oximation reactor for a cyclohexanone ammoximation reaction, the reacted mixture is separated, and a product is obtained. The problems that a catalyst in the prior art is easily inactivated, follow-up separation is difficult, membrane blocking is serious, the effective utilization rate of hydrogen peroxide is lower and the like can be effectively solved, and the cyclohexanone ammoximation method has broad and good industrial prospect.
Description
Technical field
The invention belongs to organic chemicals catalytic synthetic techniques field, relates to one and utilizes titanium-containing catalyst to prepare ring
The method of hexanone oxime, illustrates further a kind of method being to prepare cyclohexanone-oxime about gas-solid phase cyclohexanone oxamidinating reaction.
Background technology
Cyclohexanone-oxime is important chemicals synthetic intermediate, and it can carry out synthesis of caprolactam by Beckmann rearrangement
(CPL), it is the key intermediate producing caprolactam.Caprolactam can generate nylon-6 by polymerization, and nylon-6 can enter
One step is processed into nylon fibre, engineering plastics and plastic sheeting etc..
At present industrialized production caprolactam has three kinds of process routes: (1) Ketohexamethylene-azanol production line, including tradition
Raschig process technique, DSM/HPO technique, BASF-NO reducing process, Inventa-NO reducing process, Allied isopropyl
Benzene/phenol process and caprolactam technology；(2) the hexamethylene photonitrosation technique of toray company；(3) meaning is big
The toluene technique of profit SNIA company.Wherein, Ketohexamethylene-azanol production line is still the most commonly used technology path.
In this production line, the preparation of cyclohexanone-oxime is the core process in whole caprolactam production process, all uses hexamethylene
The method that ketone reacts with certain hydroxylamine salt.The method technology maturation, but need to use expensive noble metal and special installation, work
Sequence is many, equipment is many, circulated material quantity is big, and raw material and energy consumption are big, and by-product and intermediate product are many.The method can produce simultaneously
Substantial amounts of corrosion and with serious pollution intermediate product, such as NOX、SOXDeng.Along with the enhancing of attention environmental protection consciousness,
People research and develop a kind of pollute less, method that environmentally friendly and technique simply produces cyclohexanone-oxime, have ten
Divide important realistic meaning.
Owing to HTS has very important effect in terms of organic compound selective oxidation, accordingly, as ring
The preparation method of hexanone oxime, it has been proposed that at titanium-silicon molecular sieve TS-1/H2O2Under system, ammonia and Ketohexamethylene is utilized to carry out
The oximes method preparing cyclohexanone-oxime.The method can prepare cyclohexanone-oxime by a direct highly selective of step, simplifies tradition
Technological process, reduces equipment investment, reduces three waste discharge, has eco-friendly technical advantage.
But, the method for existing preparing cyclohexanone oxime by ammoximation of cyclohexanone still suffers from following defect:
The most existing cyclohexanone-oxime preparation method is generally liquid phase reactor, and titanium-containing catalyst is chronically in strong basicity environment, nothing
Method avoids the framework silicon dissolution phenomena on catalyst, causes catalyst ineffective to run off, and shortens the service life of catalyst, shadow
Ring the stable operation of Ammoximation reaction system；
2. there is the shortcoming that resistance to mass tranfer is big in liquid and solid phase reaction, and the impact of catalyst diffusing phenomenon is serious；
3. it is the diffusing phenomenon effectively solving above-mentioned catalyst, the catalytic reaction condition kept, can be by titanium-containing catalyst
It is prepared as nanoscale, but, although this can ensure that suitable catalysis activity, but also bringing another technological deficiency, that is just
It is intended to, by catalyst liquid phase feed in slurry bed reactor is separated, the membrane separation device involved great expense to be used,
Increase later separation cost and stifled film phenomenon cannot be avoided；
4., in Ammoximation reaction, majority can arrange porous plate in the reactor and reach to efficiently separate the purpose of catalyst, but
Being that separating effect is the best, not only catalyst easily blocks orifice plate, and subsequent maintenance and replacing are caused very big inconvenience；
5. hydrogen peroxide effective rate of utilization is the highest.
Disadvantages described above becomes the technical bottleneck of preparing cyclohexanone oxime by ammoximation of cyclohexanone, becomes to need badly and solves the technical problem that.
Summary of the invention
The invention is for solving the problems of the prior art, it is provided that a kind of cyclohexanone oxamidinating process, overcomes existing skill
Catalyst easy in inactivation in art, the problems such as later separation is difficult, and stifled film is serious and hydrogen peroxide effective rate of utilization is relatively low, have wide
Fine industrial prospect.
A kind of cyclohexanone oxamidinating process that the invention provides, comprises the steps: hydrogen peroxide and inhibitor, ring
Hexanone and low-carbon alcohols auxiliary agent are mixed into mixed liquor by a certain percentage, and it is trickle that feeding oximation reaction device top is separated into 1～200 μm
Granule；By the charge heating of noble gas Yu ammonia, send into oximation reaction device and contact with the fine particle after dispersion, and
The fine particle after dispersion is made to gasify further；Fine particle after gasification and ammonia containing in being positioned over oximation reaction device
Carry out cyclohexanone oxamidinating reaction on titanium catalyst, after reacted mixture is separated, obtain product.
Wherein, described method also includes, the unreacted ammonia obtained after separating and noble gas return the mixed of gaseous mixture
Conjunction process the step preheated, thus realize the recycling of noble gas and the gaseous mixture of ammonia.
Wherein, the gaseous mixture of described noble gas and ammonia by purging or from bottom to top in the way of enter oximation reaction device, with
Reach fully contact with the fine particle after dispersion and carry out the purposes such as heat exchange.
Wherein, described oximation reaction device can be fixed bed, fluid bed, suspension bed, ebullated bed and moving bed, the most solid
Fixed bed, fluid bed.Described dispersive process can use Centrifugal dispersion device, high-pressure nozzle or ultrasonic disperser, the highest
Pressure shower nozzle and ultrasonic disperser.Wherein, high-pressure nozzle boosting inert gas pressure is 0.1～3.0MPa, preferably
0.1～0.8MPa.
Wherein, after oximation reaction device top sent into by described mixed liquor, 1～100 μm fine particles preferably it are separated into.
Wherein, described hydrogen peroxide can be commercially available, the solution of stabilisation, it is also possible to without stabilizing treatment, use
The anthraquinone weak solution produced nearby.Hydrogen peroxide suitable quality concentration is 1～50wt%.
Wherein, in the ammonia in described gaseous mixture, described mixed liquor cyclohexanone and described mixed liquor hydrogen peroxide mole
Than being (1.0～4.5): (1.0～2.0): 1, preferably (1.0～1.3): (1.0～1.5): 1.
Wherein, in described oximation reaction device, Ammoximation reaction temperature at 50～200 DEG C, preferably 90～140 DEG C, most preferably
120℃；Reaction pressure is normal pressure～3.0MPa, preferably normal pressure～0.6MPa.
Wherein, in described gaseous mixture, noble gas can be helium, argon, nitrogen, noble gas and the volume of ammonia
Ratio is 1: 10～100: 1, preferably 10: 1～60: 1.
Wherein, described hydrogen peroxide inhibitor refers to Stabilizing Hydrogen Peroxide structure and chemical property, prevents it from occurring further
The trace substance reduced side reaction, can be adsorption inhibitor, such as sodium silicate, magnesium silicate, polyacrylamide etc..
Can also be chelating type inhibitor, such as tertiary sodium phosphate, sodium tripolyphosphate, ATMP, EDTMP, DTPMP (many second
Alkene polyamines polyalkylene phosphonate) etc..Hydrogen peroxide inhibitor addition is 0.5～10000ppm, preferably 1～1000ppm.
Wherein, described catalyst is the catalyst of titaniferous, can be crystal (zeolite), it is also possible to be amorphous substance
Or its mixture.Crystal refers mainly to the various zeolite molecular sieves of titaniferous, opens up as having the MFI being similar to ZSM-5 zeolite
Flutter the titanium-containing zeolite (i.e. TS-1) of structure, be similar to the titanium-containing zeolite of MEL topological structure of ZSM-11 zeolite (i.e.
TS-2), and have β zeolite, modenite (natural or synthetic), ZSM-12, MCM-22, ZSM-48 knot
The molecular sieve containing titanium etc. of structure；Amorphous substance refers mainly to titaniferous, the random oxygen of mesopore molecular sieve and duct of duct rule
Compound, as with isomorphism titanium-containing materials and the silicon dioxide carried titanium dioxide such as MCM-41, SBA-15.Above-mentioned molecule
Sieve and zeolitic catalyst typically have Si: the Ti mol ratio of 10～500, preferably 10～200.And amorphous substance catalysis
Agent typically has corresponding to empirical formula (TiO2)X(SiO2)1-X, wherein X value is between 0.0001～0.5, preferably X value
It is 0.01～0.125.Further, described catalyst is the catalyst after catalyst raw powder or spraying, extrusion pelletize, catalysis
Agent mean diameter is 0.15～100 μm.
The invention provides the benefit that:
1. the present invention is gas-solid phase reaction, can realize catalyst and separate in situ with oximated product, thoroughly solve Traditional liquid phase
In Ammoximation reaction, catalyst separates the problem of difficulty with product, is substantially reduced later separation cost；
2. the present invention is gas-solid phase reaction, and interphase mass transfer effect is the best, can effectively solve because of urging that spreading effect causes
The problem of agent easy in inactivation；
3. compared with Traditional liquid phase Ammoximation process, it is to avoid the loss problem that catalyst causes due to the molten silicon of skeleton；Additionally,
The hydrogen peroxide of gaseous state has certain automatic cleaning action, can be cleaned catalyst surface area internal gutter in situ；Catalyst pores
Road is not easily blocked, and the life-span is longer；
4. the present invention is without using a large amount of low-carbon alcohols solvent, and solvent only need to participate in Ammoximation reaction with the auxiliary agent form of trace；
5. hydrogen peroxide effective rate of utilization is higher, substantially can reach more than 90%, and catalyst suitability is strong.
Accompanying drawing explanation
Fig. 1 is the flow chart of a kind of cyclohexanone oxamidinating process of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, this patent is further described.The embodiment of the present invention is the skill in order to make this area
Art personnel can be better understood from the present invention, but does not imposes any restrictions the present invention.
In instances, Ketohexamethylene, cyclohexanone-oxime, the tert-butyl alcohol are by gas chromatogram quantitative and qualitative analysis.
The concentration of hydrogen peroxide is measured with Indirect Iodine Method.
The concentration of ammonia is to be added to by the reactant liquor containing ammonia in the hydrochloric acid standard solution of excess, drips with standard solution of sodium hydroxide
The hydrochloric acid of fixed excess, with C.I. 13020. or bromophenol blue as indicator.
In instances, the calculation of each index is as follows:
The Ketohexamethylene of the Ketohexamethylene conversion ratio=mole of Ketohexamethylene mole-product cyclohexanone (charging)/charging mole
Number × 100%
Cyclohexanone-oxime selectivity=product cyclohexanone oxime mole/(charging Ketohexamethylene mole-product cyclohexanone mole
Amount) × 100%
Hydrogen peroxide conversion ratio=(hydrogen peroxide mole in charging hydrogen peroxide mole-product)/charging hydrogen peroxide mole
Hydrogen peroxide effective rate of utilization=for producing the dioxygen water yield/hydrogen peroxide total feed of cyclohexanone-oxime
In an embodiment, Ketohexamethylene conversion ratio is considered as catalysqt deactivation less than 90%.
Embodiment 1 (comparative example)
With reference to the reaction method disclosed in prior art (patent CN1432560A), designed, designed cyclohexanone oxamidinating is anti-
Answer flow process.Wherein, material rate is: hydrogen peroxide is 1.1: 1 with the mol ratio of Ketohexamethylene, ammonia and the mol ratio of Ketohexamethylene
It is 2.3: 1.Reaction condition is: temperature is 90 DEG C, and absolute pressure is 0.4MPa, and catalyst is the titanium silicon after compression molding
Molecular sieve 3g (40 mesh), reaction raw materials is 60 minutes with the time of contact of catalyst.Reacted serosity is centrifuged
Separating, the drying of isolated catalyst, roasting are also weighed.Reaction result such as table 1.
Table 1
Post catalyst reaction quality: 2.5g.
The present embodiment demonstrates in Traditional liquid phase Ammoximation reaction, there is the problem that product later separation is complicated, exists simultaneously
The catalyst loss problem that in alkaline environment, the molten silicon of skeleton causes, causes catalyst life shorter, hydrogen peroxide effective rate of utilization
The highest.
Embodiment 2
Maintain all response parameters and material rate in embodiment 1 constant.On fixed bed reactors, simply according to accompanying drawing 1
Flow process carry out cyclohexanone oxamidinating test, raw material mixed liquor process for dispersing is good pressure distribution, with nitrogen make noble gas carry
Gas, boost pressure is 0.1MPa, and nitrogen carrier gas is 10: 1 with the volume ratio of ammonia.Reaction result such as table 2.
Table 2
Post catalyst reaction quality: 3g.
The present embodiment successfully illustrates that, in oximes gas-solid phase reaction, product can separate in situ with catalyst, without catalyst
Loss problem, catalyst life significantly extends, and hydrogen peroxide effective rate of utilization is up to more than 90%.
Embodiment 3
Repeat embodiment 2, simply oximation reaction device is replaced by fluidized-bed reactor.Boost gas pressure is 0.6MPa,
Catalyst uses the TS-1 after mist projection granulating, itself and SiO in binding agent2Part by weight be 60: 40, particle size range is
20～120 μm, loaded catalyst is that 50g accounts for 80% in whole particle weight.Modulation reaction temperature is 120 DEG C,
Reaction pressure is normal pressure, and carrier gas made by helium, is 60: 1 with the volume ratio of ammonia.Reaction result such as table 3.
Table 3
Post catalyst reaction quality: 49.5g.
The basic free of losses of catalyst, catalyst life significantly extends, and hydrogen peroxide effective rate of utilization is up to more than 90%.
Embodiment 4
Repeating embodiment 2, modulation feedstock ratio is: the mol ratio of hydrogen peroxide and Ketohexamethylene is 1.15: 1, ammonia with
The mol ratio of Ketohexamethylene is 1.3: 1.Reaction condition is: temperature is 120 DEG C, and absolute pressure is 0.6MPa.Reaction result
Such as table 4.
Table 4
Post catalyst reaction quality: 3g.
Embodiment 5
Repeating embodiment 2, HTS 3g, Si/Ti that the HTS of compression molding simply changes into extruded moulding rub
That ratio about 33, accounts for 80% in whole particle weight.Reaction result such as table 5.
Table 5
Post catalyst reaction quality: 3g.
Embodiment 6
Repeat embodiment 2, simply the HTS of extruded moulding is changed into extruded moulding Ti-MOR catalyst.Described
The Si/Ti mol ratio of Ti-MOR catalyst is about 53, accounts for 80% in whole particle weight.Reaction result such as table 6.
Table 6
Post catalyst reaction quality: 3g.
Embodiment 7
Repeat embodiment 2, simply the HTS of extruded moulding is changed into extruded moulding TS-2 catalyst, its grain size
Being 1 μm, Si/Ti mol ratio is about 50, and TS-2 catalyst accounts for 80% in whole particle weight.Reaction result such as table
7。
Table 7
Post catalyst reaction quality: 3g.
Embodiment 8
Repeat embodiment 3, simply the HTS of spraying is changed into spray shaping Ti-MCM-41 catalyst, loadings
For 50g.The grain size of described Ti-MCM-41 catalyst is 1 × 2 × 50 μm, and Si/Ti mol ratio is about 33, at whole
Grain weight accounts for 80%.Reaction result such as table 8.
Table 8
Post catalyst reaction quality: 49.6g.
Embodiment 9
Repeating embodiment 3, fluidized-bed reactor simply changes into moving-burden bed reactor, HTS makes wear-resisting bead,
Loadings is 50g, and reaction temperature changes 200 DEG C into, and argon is noble gas, is 40: 1 with the volume ratio of ammonia.Reaction
Result such as table 9.
Table 9
Post catalyst reaction quality: 50g.
Embodiment 10
Repeat embodiment 2, but the most successively by the tert-butyl alcohol of 50ppm, methanol with Ketohexamethylene and hydrogen peroxide mixed liquor
Join in fixed bed reactors.Reaction result such as table 10.
Table 10
Post catalyst reaction quality: 3g.
Embodiment 11
Repeat embodiment 2, but now the hydrogen peroxide inhibitor of 50ppm is added with Ketohexamethylene and hydrogen peroxide mixed liquor
In fixed bed reactors.Reaction result such as table 11.
Table 11
Post catalyst reaction quality: 3g.
Embodiment 12
Repeat embodiment 2, maintain all response parameters and material rate constant, simply change into surpassing by raw material liq process for dispersing
Sound disperses.Reaction result such as table 12.
Table 12
Post catalyst reaction quality: 3g.
Claims (10)
1. a cyclohexanone oxamidinating process, comprises the steps: that hydrogen peroxide and inhibitor, Ketohexamethylene and low-carbon alcohols help
Agent is mixed into mixed liquor by a certain percentage, sends into oximation reaction device top and is separated into 1～200 μm fine particles；By indifferent gas
The charge heating of body and ammonia, the fine particle after sending into oximation reaction device and disperseing contacts, and make after dispersion trickle
Granule gasifies further；Fine particle after gasification and ammonia are carried out on the titanium-containing catalyst in being positioned over oximation reaction device
Cyclohexanone oxamidinating reacts, and obtains product after reacted mixture is separated.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that also include, after separating
Mixed process that the unreacted ammonia obtained and noble gas return gaseous mixture the step preheated.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that described noble gas and ammonia
The gaseous mixture of gas by purging or from bottom to top in the way of enter oximation reaction device.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that oxime sent into by described mixed liquor
After changing reactor head, it is separated into 1～100 μm fine particles.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that described hydrogen peroxide quality is dense
Degree is 1～50wt%.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that the ammonia in described gaseous mixture
The mol ratio of middle hydrogen peroxide is (1.0～4.5) with described mixed liquor for gas, described mixed liquor cyclohexanone: (1.0～2.0): 1,
Preferably (1.0～1.3): (1.0～1.5): 1.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that in described oximation reaction device,
Ammoximation reaction temperature at 50～200 DEG C, preferably 90～140 DEG C, most preferably 120 DEG C；Reaction pressure is normal pressure～3.0MPa,
Preferably normal pressure～0.6MPa.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that in described gaseous mixture, lazy
Property gas and ammonia volume ratio be 1: 10～100: 1, preferably 10: 1～60: 1.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that described hydrogen peroxide inhibitor
Addition is 0.5～10000ppm, preferably 1～1000ppm.
A kind of cyclohexanone oxamidinating process the most according to claim 1, it is characterised in that described catalyst is:
Molecular sieve or zeolitic catalyst, have Si: the Ti mol ratio of 10～500, preferably 10～200；Or
Amorphous substance catalyst, has corresponding to empirical formula (TiO2)X(SiO2)1-X, wherein X value between 0.0001～0.5 it
Between, preferably X value is 0.01～0.125.
Further, described catalyst is the catalyst after catalyst raw powder or spraying, extrusion pelletize, catalyst mean diameter
It is 0.15～100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610313124.4A CN105949083B (en) | 2016-05-11 | 2016-05-11 | A kind of cyclohexanone oxamidinating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610313124.4A CN105949083B (en) | 2016-05-11 | 2016-05-11 | A kind of cyclohexanone oxamidinating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105949083A true CN105949083A (en) | 2016-09-21 |
| CN105949083B CN105949083B (en) | 2018-01-05 |
Family
ID=56912322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610313124.4A Active CN105949083B (en) | 2016-05-11 | 2016-05-11 | A kind of cyclohexanone oxamidinating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949083B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694027A (en) * | 2016-12-30 | 2017-05-24 | 华东师范大学 | Preparation of transition metal catalyst for preparing oxime through oxidization of amine and application of transition metal catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432560A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Cyclohexanone oxamidinating process |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
| CN103360279A (en) * | 2012-03-30 | 2013-10-23 | 武汉优立克新材料科技有限公司 | Method for preparing cyclohexanone-oxime from cyclohexanone ammoximation |
-
2016
- 2016-05-11 CN CN201610313124.4A patent/CN105949083B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432560A (en) * | 2002-01-10 | 2003-07-30 | 中国石油化工股份有限公司 | Cyclohexanone oxamidinating process |
| CN103360279A (en) * | 2012-03-30 | 2013-10-23 | 武汉优立克新材料科技有限公司 | Method for preparing cyclohexanone-oxime from cyclohexanone ammoximation |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694027A (en) * | 2016-12-30 | 2017-05-24 | 华东师范大学 | Preparation of transition metal catalyst for preparing oxime through oxidization of amine and application of transition metal catalyst |
| CN106694027B (en) * | 2016-12-30 | 2019-02-01 | 华东师范大学 | A kind of amine oxidation prepares the preparation and its application of the transition-metal catalyst of oxime |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949083B (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Perego et al. | Production of titanium containing molecular sieves and their application in catalysis | |
| US20190232260A1 (en) | Supported Nano Sized Zeolite Catalyst for Alkylation Reactions | |
| CN102614911B (en) | One-step molding method of titanium silicalite molecular sieve | |
| CN104907009B (en) | A kind of reactor and the method for preparing expoxy propane using the reactor | |
| US8809588B2 (en) | Method for producing aromatic amines | |
| CN103360279B (en) | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone | |
| CN103012058A (en) | Solid acid catalyst and process for decomposition of cumene hydroperoxide | |
| CN109999896A (en) | One kind being applied to phenol selectivity and adds hydrogen preparing cyclohexanone effective catalyst and preparation method thereof | |
| CN104028314A (en) | Preparation method for molecular sieve catalyst | |
| CN106660938B (en) | The method for producing the diamines and polyamines of diphenylmethane series | |
| Wang et al. | Zeolite catalysts for green production of caprolactam | |
| CN105949083A (en) | Cyclohexanone ammoximation method | |
| CN103360344A (en) | Method for catalyzing propylene epoxidation | |
| CN100430350C (en) | Process for producing cyclohexene | |
| CN101229915A (en) | Method for producing hydrogen peroxide by anthraquinone process | |
| CN107001211B (en) | Process for preparing 2, 5-dichlorophenol | |
| US20110288355A1 (en) | Method for producing aromatic hydrocarbon and apparatus for producing aromatic hydrocarbon | |
| CN101541711B (en) | Method for producing alkylated aromatic compound and method for producing phenol | |
| CN103664477A (en) | Toluene shape-selective disproportionation method | |
| JP7360551B2 (en) | Catalyst and manufacturing method for producing vinyl chloride by decomposition of 1,2-dichloroethane | |
| EP1294481B1 (en) | Process for the regeneration of solid acid catalysts | |
| CN1284899A (en) | Moulded body comprising inert support and at least one porous oxidic caterial | |
| CN220610305U (en) | HPPO method epoxypropane reactor | |
| CN109516966B (en) | Method for oxidizing styrene by molecular oxygen | |
| CN103804331B (en) | A kind of synthetic method of difurfuryl methane diisocyanate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190122 Address after: No. 1 Jingjin Road, Beichen District, Tianjin City, 300400 Co-patentee after: FUJIAN TIANCHEN YAOLONG NEW MATERIAL LTD. Patentee after: China Tiancheng Engineering Corp. Co-patentee after: Tianjin Tianchen Green Energy Engineering Technology Research & Development Co., Ltd. Address before: No. 1 Jingjin Road, Beichen District, Tianjin City, 300400 Co-patentee before: Tianjin Tianchen Green Energy Engineering Technology Research & Development Co., Ltd. Patentee before: China Tiancheng Engineering Corp. |