CN104475144B - In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound - Google Patents
In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound Download PDFInfo
- Publication number
- CN104475144B CN104475144B CN201410714828.3A CN201410714828A CN104475144B CN 104475144 B CN104475144 B CN 104475144B CN 201410714828 A CN201410714828 A CN 201410714828A CN 104475144 B CN104475144 B CN 104475144B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- caesium
- intramolecular dehydration
- regeneration method
- phosphorus
- 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.)
- Active
Links
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses an in-situ regeneration method for a catalyst for intramolecular dehydration of an amino alcohol compound, and aims at solving the problem that the activity of an existing catalyst is lowered due to carbon deposition and phosphorus loss in a long-term use process. The method comprises the following steps: (1) roasting a deactivated catalyst in a tubular reacting furnace at 300-500 DEG C for 3-5 hours; (2) pumping a water solution of phosphorus and cesium inorganic matters into a catalyst bed which is in situ roasted and regenerated in the step (1), and recycling an effluent for 0.5-1 hour; and (3) carrying out in-situ roasting on the catalyst which is supplemented with phosphorus and cesium in the step (2) at 500-700 DEG C for 3-5 hours, so as to obtain a regenerated catalyst. The performance of the regenerated catalyst can restore into a fresh catalyst level; the service life of the catalyst is prolonged; and the use cost is also reduced. Therefore, the regeneration method disclosed by the invention is mainly applied to regeneration of a catalyst for preparation of ethylene imine through intramolecular dehydration of monoethanolamine.
Description
Technical field
The present invention relates to a kind of renovation process of decaying catalyst is and in particular to a kind of alkamine compound intramolecular takes off
In situ regeneration method after catalyst inactivation for the water.
Background technology
Amino alcohol is that a class has amino and the compound of hydroxyl difunctional structure, and chemical property is active, wherein amino
The aziridine type that a class has important use can be prepared by molecule inner dewatering reaction with the amino alcohol at ortho position for the hydroxyl
Compound.The catalyst that at present in world wide, such dehydration is used mainly with silicon dioxide as carrier, phosphorus is as activearm
Divide, alkali metal and/or alkaline-earth metal are prepared for auxiliary agent.Such catalyst is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of imines is although monoethanolamine conversion ratio and aziridine selectivity are all very high, but the process in its industrial applications
In still can run off and cause gradually to inactivate because of short-period used catalyst carbon deposition and life-time service catalyst phosphorus, caesium.
The general solution of industrial catalyst carbon distribution inactivation is decaying catalyst to be carried out burn carbon again using oxygen-containing gas
Raw.Phosphorus, caesium are run off and cause catalyst to inactivate, then needs to realize the regeneration of catalyst by mending the phosphorus losing and caesium.Example
As, a kind of renovation process of aziridine production catalyst of report such as tsuneki (applied catalysis a:
General331,2007,95～99), the method first passes through the phosphorus content measuring between fresh catalyst and decaying catalyst,
Calculate the loss amount of phosphorus, then decaying catalyst is loaded quartz ampoule, using heating by electric cooker, with lower boiling trimethyl phosphoric acid
Ester (tmp) supplements the phosphorus of decaying catalyst loss for raw material, finally carries out oxidation processes for oxidant to catalyst with air again,
Thus realizing the regeneration of decaying catalyst.
The renovation process of above-mentioned aziridine production catalyst, needs to take out catalyst from tubular reactor,
Regenerated in other catalyst regeneration vessel, also need to afterwards for the catalyst after regeneration to be incorporated into dehydration technique
In, complex operation, regeneration cost especially time cost is higher, is unfavorable for realizing the continuous prodution of aziridine.And, this
Patent applicant is also found that in actual operating process above-mentioned decaying catalyst does not only have phosphorus loss, and also caesium loss, only mends
Fill phosphorus, catalyst activity can not be completely recovered to previous level.
Content of the invention
In order to solve shortcomings and deficiencies of the prior art, the invention provides a kind of process is simple, suitable industrial operation
Alkamine compound intramolecular dehydration catalyst in situ regeneration method, to meet the needs of its industrial applications.
A kind of renovation process of alkamine compound intramolecular dehydration catalyst that the present invention provides, walks including following
Rapid:
(1) by decaying catalyst in pipe reaction stove oxygen-containing atmosphere in 300～500 DEG C of roasting temperature 3～5h；
(2) phosphorous, caesium inorganic matters aqueous solutions are squeezed into the beds after step (1) situ roasting regeneration, stream
Go out liquid and recycle 0.5～1h；
(3) original position at a temperature of 500～700 DEG C in oxygen-containing atmosphere of the catalyst after phosphorus and caesium will be supplemented in step (2)
Regenerated catalyst is obtained final product after roasting 3～5h.
Calcination atmosphere in described step (1) and (3) is oxygen-containing atmosphere, preferably nitrogen/oxygen mixture atmosphere, further preferably
Air atmosphere.
In described step (2), inorganic phosphor-contained thing includes various water miscible phosphoric acid and phosphate, preferably orthophosphoric acid or phosphoric acid
Ammonium salt；Described inorganic matters containing caesium are the various inorganic salts of caesium, preferably cesium nitrate or cesium carbonate.
The consumption of described orthophosphoric acid or ammonium phosphate salt is the 20%～30% of body fresh catalyst phosphorus content, its aqueous solution
Mass concentration be 0.05%～0.3%, preferably 0.1%～0.2%；The consumption of described cesium nitrate or cesium carbonate is that body is fresh
The 10%～20% of catalyst caesium content, the mass concentration of its aqueous solution is 0.05%～0.3%, preferably 0.1%～0.2%.
A kind of the consisting of of alkamine compound intramolecular dehydration catalyst of the present invention: siapbcscydoe, its
Middle si is silicon, and p is phosphorus, and cs is caesium, and y is alkaline-earth metal, and o is oxygen, and a, b, c, d, e are respectively the mol ratio of si, p, x, y and o, when
During a=1, b=0.01～0.1, preferably 0.02～0.03, c=0.01～0.1, preferably 0.02～0.03, d=0.001～
0.01, preferably 0.005～0.007, e-value depends on a, b, c, d.
Compared with prior art, the invention has the advantages that
The renovation process of existing alkamine compound intramolecular dehydration catalyst, only considered carbon distribution and phosphorus stream
Lose, and have ignored caesium and run off, the present invention is regenerated to decaying catalyst with the method mended using phosphorus, caesium after burning carbon, after regeneration
Its feed stock conversion of catalyst be 85%, recover to fresh catalyst level, aziridine selectivity is 92%, slightly above newly
The 91% of fresh catalyst, solves the mistake that catalyst causes during life-time service because of carbon distribution and active component phosphorus, caesium loss
The problem of living, extends the service life of alkamine compound intramolecular dehydration catalyst, the use reducing catalyst becomes
This.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
The evaluating apparatus of catalyst adopt fixed-bed tube reactor, and reactor size is 700mm × φ 40mm × 6mm.
Reaction is carried out at ambient pressure, 400 DEG C of reaction temperature, is passed through nitrogen to reduce feed partial pressure, nitrogen and single ethylene hydramine in reaction
The volume ratio of gas is 9:1, and in terms of standard state, total gas space velocity of reaction raw materials is 3200h-1.Catalyst packing is entered instead
Answer device, be heated to reaction temperature, fed by dosing pump, sample analysis after stable reaction 5h, analytical tool is gas chromatograph,
Hydrogen flame detector, db-35 chromatographic column, area normalization method.
Conversion ratio described in embodiment and selectivity are defined respectively as:
The chromatograph area percent of monoethanolamine in monoethanolamine conversion ratio (%)=1- product liquid；
The chromatograph area percent of aziridine after deduction monoethanolamine in aziridine selectivity (%)=reactant liquor.
Comparative example
Preparation consists of si1.0p0.02cs0.02ba0.006o2.14Catalyst:
By elemental mole ratios, 25% acidic silicasol, three water ammonium phosphate, cesium nitrate and barium hydrogen phosphate are added in beaker,
Using the ultrasonic 8min of ultrasonic cleaner under room temperature, dry after 660 DEG C of roasting temperature 4h for 120 DEG C, add the acid of its quality 4%
Property Ludox and appropriate water, add the graphite of 3% mass after fully mediating, compressing, 120 DEG C dry after obtain final product dehydration
Use catalyst.This catalyst is used for the reaction of monoethanolamine intramolecular dehydration synthesizing ethylene imines, catalyst amount is 50ml,
Quality about 30g, monoethanolamine conversion ratio 85%, aziridine selectivity 91%.After continuously running 1000h, monoethanolamine converts
Rate 73%, aziridine selectivity 85%.
Embodiment 1
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 300 DEG C in air atmosphere
It is cooled to room temperature after burning 5h.Weigh 85% phosphate aqueous solution 0.21g, be made into 0.1% aqueous solution, squeeze into above-mentioned original position roasting regeneration
Beds afterwards, effluent recycle 30min after, in air atmosphere at 650 DEG C roasting 5h, obtain final product regeneration catalyzing
Agent.Catalyst after this is regenerated is used for the reaction of monoethanolamine intramolecular dehydration synthesizing ethylene imines, monoethanolamine conversion ratio
77%, aziridine selectivity 87%.
Embodiment 2
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 300 DEG C in air atmosphere
It is cooled to room temperature after burning 5h.Weigh cesium nitrate 0.18g, be made into 0.1% aqueous solution, squeeze into the catalysis after above-mentioned original position roasting regeneration
Agent bed, effluent recycle 30min after, in air atmosphere at 650 DEG C roasting 5h, obtain final product regenerated catalyst.Should
Catalyst after regeneration is used for the reaction of monoethanolamine intramolecular dehydration synthesizing ethylene imines, monoethanolamine conversion ratio 74%, second
Alkene imines selectivity 86%.
Embodiment 3
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 300 DEG C in air atmosphere
It is cooled to room temperature after burning 5h.Weigh 85% phosphate aqueous solution 0.21g, be made into 0.1% aqueous solution, add 0.18g cesium nitrate, fully
Squeeze into the beds after above-mentioned original position roasting regeneration after dissolving, after effluent recycles 30min, in air atmosphere in
At 650 DEG C, roasting 5h, obtains final product regenerated catalyst.Catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of imines, monoethanolamine conversion ratio 86%, aziridine selectivity 90%.
Embodiment 4
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 400 DEG C in air atmosphere
It is cooled to room temperature after burning 4h.Weigh ammonium dihydrogen phosphate 0.26g, be made into 0.15% aqueous solution, add 0.15g cesium carbonate, fully molten
Squeeze into the beds after above-mentioned original position roasting regeneration after solution, after effluent recycles 40min, in air atmosphere in
At 600 DEG C, roasting 4h, obtains final product regenerated catalyst.Catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of imines, monoethanolamine conversion ratio 83%, aziridine selectivity 91%.
Embodiment 5
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 500 DEG C in air atmosphere
It is cooled to room temperature after burning 3h.Weigh diammonium phosphate 0.36g, be made into 0.2% aqueous solution, add 0.36g cesium nitrate, fully dissolve
Squeeze into the beds after above-mentioned original position roasting regeneration afterwards, after effluent recycles 50min, in 700 in air atmosphere
Roasting 3h at DEG C, obtains final product regenerated catalyst.It is sub- that catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of amine, monoethanolamine conversion ratio 84%, aziridine selectivity 92%.
Embodiment 6
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 700 DEG C in air atmosphere
It is cooled to room temperature after burning 3h.Weigh three water ammonium phosphate 0.45g, be made into 0.1% aqueous solution, add 0.29g cesium carbonate, fully dissolve
Squeeze into the beds after above-mentioned original position roasting regeneration afterwards, after effluent recycles 60min, in 660 in air atmosphere
Roasting 4h at DEG C, obtains final product regenerated catalyst.It is sub- that catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of amine, monoethanolamine conversion ratio 85%, aziridine selectivity 92%.
Embodiment 7
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 700 DEG C in air atmosphere
It is cooled to room temperature after burning 3h.Weigh three water ammonium phosphate 0.37g, be made into 0.1% aqueous solution, add 0.28g cesium nitrate, fully dissolve
Squeeze into the beds after above-mentioned original position roasting regeneration afterwards, after effluent recycles 60min, in 660 in air atmosphere
Roasting 4h at DEG C, obtains final product regenerated catalyst.It is sub- that catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of amine, monoethanolamine conversion ratio 86%, aziridine selectivity 89%.
Embodiment 8
Decaying catalyst in comparative example, does not take out from tubular reactor, directly roasts at 700 DEG C in air atmosphere
It is cooled to room temperature after burning 3h.Weigh three water ammonium phosphate 0.55g, be made into 0.1% aqueous solution, add 0.23g cesium carbonate, fully dissolve
Squeeze into the beds after above-mentioned original position roasting regeneration afterwards, after effluent recycles 60min, in 660 in air atmosphere
Roasting 4h at DEG C, obtains final product regenerated catalyst.It is sub- that catalyst after this is regenerated is used for monoethanolamine intramolecular dehydration synthesizing ethylene
The reaction of amine, monoethanolamine conversion ratio 82%, aziridine selectivity 92%.
The renovation process of catalyst in comparative example and embodiment and performance are summarized in table -1.
The renovation process of catalyst and performance in table -1 comparative example and embodiment
Catalyst be can be seen that by upper table data and continuously run monoethanolamine conversion ratio and aziridine selection after 1000h
Property all occur in that different degrees of decline, to decaying catalyst only supplement phosphorus or only supplement caesium, catalyst performance all fail recover
To initial level, only supplement phosphorus and caesium, the performance of catalyst could be recovered to the level of fresh catalyst simultaneously.
Claims (6)
1. a kind of in situ regeneration method of alkamine compound intramolecular dehydration catalyst is it is characterised in that the method includes
Following steps:
(1) by decaying catalyst in pipe reaction stove oxygen-containing atmosphere original position roasting 3～5h at a temperature of 300～500 DEG C；
(2) phosphorous, caesium inorganic matters aqueous solutions are squeezed into the beds after step (1) situ roasting regeneration, effluent
Recycle 0.5～1h, obtain the catalyst after supplementing phosphorus and caesium；
(3) the catalyst original position roasting 3 at a temperature of 500～700 DEG C in oxygen-containing atmosphere after phosphorus and caesium will be supplemented in step (2)
Regenerated catalyst is obtained final product after～5h.
2. the in situ regeneration method of alkamine compound intramolecular dehydration catalyst according to claim 1, it is special
Levy and be that in described step (1) and (3), oxygen-containing atmosphere is nitrogen/oxygen mixture atmosphere or air atmosphere.
3. the in situ regeneration method of alkamine compound intramolecular dehydration catalyst according to claim 1, it is special
Levy and be that in described step (2), inorganic phosphor-contained thing includes phosphoric acid or water miscible phosphate, inorganic matters containing caesium are the inorganic salt of caesium.
4. the in situ regeneration method of alkamine compound intramolecular dehydration catalyst according to claim 3, it is special
Levy and be that described phosphate is ammonium phosphate salt, the inorganic salt of described caesium is cesium nitrate or cesium carbonate.
5. the in situ regeneration method of alkamine compound intramolecular dehydration catalyst according to claim 4, it is special
Levy and be that the consumption of described phosphoric acid or ammonium phosphate salt is the 20%～30% of body fresh catalyst phosphorus content, phosphoric acid or ammonium phosphate
The mass concentration of saline solution is 0.05%～0.3%, and the consumption of described cesium nitrate or cesium carbonate is body fresh catalyst caesium
The mass concentration of the 10%～20% of content, cesium nitrate or cesium carbonate aqueous solution is 0.05%～0.3%.
6. the in situ regeneration method of alkamine compound intramolecular dehydration catalyst according to claim 5, it is special
Levy be described phosphoric acid or saline solution of ammonium phosphate mass concentration be 0.1%～0.2%, described cesium nitrate or cesium carbonate water-soluble
The mass concentration of liquid is 0.1%～0.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410714828.3A CN104475144B (en) | 2014-11-28 | 2014-11-28 | In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410714828.3A CN104475144B (en) | 2014-11-28 | 2014-11-28 | In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104475144A CN104475144A (en) | 2015-04-01 |
| CN104475144B true CN104475144B (en) | 2017-02-01 |
Family
ID=52749825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410714828.3A Active CN104475144B (en) | 2014-11-28 | 2014-11-28 | In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104475144B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453796A (en) * | 2018-11-26 | 2019-03-12 | 西南石油大学 | It is a kind of to be dehydrated the catalyst and preparation method for generating aziridine for monoethanolamine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2010937A1 (en) * | 1989-02-27 | 1990-08-27 | Hideaki Tsuneki | Method for regeneration of catalyst for producing aziridine compounds |
| CN103816927B (en) * | 2013-12-18 | 2015-12-30 | 西安近代化学研究所 | A kind of catalyst for the synthesis of Ethylenimine, preparation method and application |
-
2014
- 2014-11-28 CN CN201410714828.3A patent/CN104475144B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 工业催化剂的再生方法;孙锦宜编著;《工业催化剂的失活于再生》;化学工业出版社出版;20060131;第36-41页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104475144A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103638956A (en) | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method | |
| CN102336736A (en) | Method for catalyzing and preparing annular carbonic ester by supported ionic liquid | |
| CN103521256B (en) | Molecular sieve catalyst for catalyzing and dehydrating glycerin to prepare acraldehyde and preparation method of molecular sieve catalyst | |
| CN107759441B (en) | Method for preparing 1-chloropropene by catalytic dehydrochlorination of 1, 2-dichloropropane | |
| CN104475144B (en) | In-situ regeneration method for catalyst for intramolecular dehydration of amino alcohol compound | |
| CN103285888A (en) | Catalyst used in preparation of acrylic acid through one-step oxidation of propylene and preparation method thereof | |
| CN107721810B (en) | Method for synthesizing extinguishing agent octafluorocyclobutane | |
| CN110038576A (en) | A kind of load type metal catalyst and its preparation method and application | |
| CN103816927B (en) | A kind of catalyst for the synthesis of Ethylenimine, preparation method and application | |
| CA1135711A (en) | Oxidation of butadiene to furan | |
| CN107311839B (en) | The fluoro- chlorine exchange system of gas phase for seven fluorine cyclopentene method | |
| CN104311404A (en) | Method for producing cinnamyl aldehyde | |
| CN105854916B (en) | A kind of palladium carbon catalyst and its preparation process of calcium carbonate cladding | |
| CN107473986A (en) | A kind of β aminopropionitriles recovery method | |
| CN103408434B (en) | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step | |
| CN112745267A (en) | Imidazolyl ionic liquid and application thereof | |
| US4185022A (en) | Furfuryl alcohol production process | |
| CN104610064A (en) | Process for preparing dimethyl carbonate through taking carbonate as catalyst by one-pot method | |
| CN106866583B (en) | A kind of preparation method of two (2- ethoxy) piperazines | |
| GB2518274A (en) | Catalyst for aldehyde production | |
| CN106944144B (en) | The preparation method of heteropoly acid ammonium type catalyst | |
| CN105646191B (en) | A kind of method for preparing fragrant dimethyl chloride | |
| CN114515600B (en) | Metal hetero element modified titanium nitride-polyaniline catalyst, preparation method and application thereof in synthesizing para-hydroxyanisole | |
| CN113754510B (en) | Method for preparing 1,3-butadiene | |
| JP4359447B2 (en) | Method for producing monohydroxyacetone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220805 Address after: 433000 Hubei province Xiantao Dujiatai Patentee after: HUBEI XIANLIN CHEMICAL CO.,LTD. Address before: 710065, No. eight, No. 168 East Road, Yanta District, Shaanxi, Xi'an Patentee before: XI'AN MODERN CHEMISTRY Research Institute |
|
| TR01 | Transfer of patent right |