CN107486236A - A kind of catalyst for producing the propylamine of 2 methyl 2 and its preparation method and application - Google Patents
A kind of catalyst for producing the propylamine of 2 methyl 2 and its preparation method and application Download PDFInfo
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- CN107486236A CN107486236A CN201610416961.XA CN201610416961A CN107486236A CN 107486236 A CN107486236 A CN 107486236A CN 201610416961 A CN201610416961 A CN 201610416961A CN 107486236 A CN107486236 A CN 107486236A
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- propylamine
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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Abstract
The invention provides a kind of catalyst for producing the propylamine of 2 methyl 2 and its preparation method and application, the catalyst is made up of composite molecular screen binder modification element, wherein composite molecular screen accounts for 65~90wt% in catalyst, binding agent accounts for 9.8~33wt%, and modifying element content is 0.2~2.0wt%.The aminating reaction activity of uniqueness is showed based on the synergy between composite molecular screen difference crystalline phase.Compared with prior art, the present invention has the characteristics of catalyst activity is high, reaction temperature is low, reaction pressure is low, purpose product is selectively high, greatly improves the economy of process.
Description
Technical field
The invention belongs to fine-chemical intermediate production technical field, and in particular to a kind of 2- methyl -2- propylamine of producing
Catalyst and its preparation method and application.
Background technology
2- methyl -2- propylamine is a kind of important chemical intermediate, is widely used in thiofide, agricultural chemicals, doctor
The numerous areas such as medicine, organic synthesis, surfactant.Traditional 2- methyl -2- propylamine production methods, usual reaction medium/anti-
Process or catalyst is answered strong acid, highly basic to be present, three waste discharge is more, and severe corrosion equipment, environmental pollution is more serious, in addition
Ritter methods production 2- methyl -2- propylamine process is also using the cyanide source of severe toxicity.The 2- metering systems developed in recent years are straight
The method for connecing amination production 2- methyl -2- propylamine has the advantages of atom economy and three-waste free discharge, but develops in advance direct
Amination method severe reaction conditions, feed stock conversion are low:As BASF techniques are carried out at supercritical conditions, reaction pressure reaches 30MPa,
And energy consumption high to equipment requirement is big;《Petrochemical industry》The catalyst that 2005,34 (10) 948~953 are reported is in used condition
Under, feed stock conversion is less than 3.1%;The direct aminatin method that other developers are reported equally exists reaction pressure height, raw material
The relatively low deficiency of conversion per pass.
The content of the invention
In view of the above problems, the present invention provides a kind of catalysis of metering system direct aminatin production 2- methyl -2- propylamine
Agent and its preparation method and application, compared with prior art, the present invention have high catalyst activity, reaction temperature and reaction pressure
Low, the characteristics of feed stock conversion and purpose product are selectively high, greatly improve the economy of process
The present invention provides a kind of catalyst for producing 2- methyl -2- propylamine, and the catalyst is by composite molecular screen-bonding
Agent-modifying element composition, composite molecular screen by weight percentage accounts for 65~90wt% wherein in catalyst, and binding agent accounts for 9.8~
33wt%, modifying element content are 0.2~2.0wt%;The composite molecular screen is the ten-ring or 12 with two phase structure
Yuan of rings composite molecular screen, the binding agent are aluminum oxide or silica, and the modifying element is rare earth element.
The composite molecular screen for have simultaneously EUO/MFI, EUO/MEL of two phase structure, MOR/MFI, MOR/MEL,
The one or more of MFI/MWW composite molecular screens, the composite molecular screen silica alumina ratio 30~120;Two in composite molecular screen
The part by weight of kind crystalline phase is 2:98~98:2.
A kind of preparation method of above-mentioned catalyst for producing 2- methyl -2- propylamine, comprises the following steps:
(1) composite molecular screen, modifying element precursor, binder precursor are pressed into its butt part by weight (65~90):(0.2
~2.0):The ratio of (9.8~33) is well mixed, and is added and is accounted for the extrusion aid of total butt weight 1.0~3.5%, accounts for total dry basis
Kneading is uniform after the expanding agent of amount 0~8.0% and the nitric acid for accounting for total butt weight 0~15.0%, extruded moulding, dries, 480~
560 DEG C are calcined 2~6 hours;
(2) by the use of ammonium salt/inorganic acid aqueous solution as exchanger, ion exchange is carried out to sample after shaping, 450~540 DEG C
Hydrogen type molecular sieve catalyst is made after 2~4 hours in roasting;
(3) it is small with water vapour/ammonia vapor processing 0.5~20 at a temperature of 450~560 DEG C by above-mentioned catalyst
When, during with AMMONIA TREATMENT, the mass percent concentration of ammoniacal liquor is 0.2~3%;
The modifying element precursor is La, Ce at least one nitrate or soluble-salt, and the binder precursor is
At least one of boehmite, Alumina gel, Ludox, sial complex sol;
The extrusion aid in sesbania powder, methylcellulose, starch, polyethylene glycol, polyvinyl alcohol at least one
Kind, its addition is the 1.0~3.5% of total butt weight;
The expanding agent is selected from least one citric acid, oxalic acid, maleic acid, malic acid, glycerine, stearic kind, and it adds
Enter amount and account for total butt weight 0~8.0%.
The catalyst is applied to metering system and ammonia direct aminatin production 2- methyl 2- propylamine, and its reaction condition is:Instead
Answer 180~280 DEG C of temperature, 1.0~15.0MPa, ammonia alkene (ammonia/metering system) mol ratio 1.0~6.0, alkene air speed 0.2~
2.5h-1。
The catalyst is preferably using reaction condition:210~270 DEG C of temperature, 2.0~12.0MPa, ammonia alkene (ammonia/
Metering system) mol ratio 1.5~4.0, alkene air speed 0.3~1.5.
The catalyst of metering system direct aminatin production 2- methyl -2- propylamine provided by the invention, has catalyst activity
High, reaction temperature and reaction pressure are low, and using technical scheme provided by the invention, raw material metering system one way feed stock conversion reaches
12~30%, purpose product 2- methyl -2- propylamine selectivity greatly improve the economy of process up to more than 99.5%.
Embodiment
Following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
The catalyst includes composite molecular screen, binding agent and modifying element composition, percentage by weight wherein in catalyst
90wt% is accounted for than EUO/MEL composite molecular screen, binding agent aluminum oxide accounts for 9.8wt%, and modifying element Ce contents are 0.2wt%;Institute
State molecular sieve silica alumina ratio 47, the ratio of two kinds of crystalline phases of EUO and MEL is 2 in composite molecular screen:98;
The preparation of the catalyst comprises the following steps:
(1) by compound EUO/MEL composite molecular screens, modifying element precursor, binder precursor its butt part by weight 90:
9.8:0.2 is well mixed, adds and accounts for the extrusion aid of total butt weight 3.0%, accounts for the expanding agent of total butt weight 2.5% and account for total
Kneading is uniform after the nitric acid of butt weight 8.0%, extruded moulding, dries, and 560 DEG C are calcined 2 hours;Wherein, the extrusion aid is
Sesbania powder, expanding agent are malic acid, and the binder precursor is boehmite.
(2) by the use of aqueous ammonium chloride solution as exchanger, ion exchange is carried out to sample after shaping, after 540 DEG C are calcined 2 hours
Hydrogen type molecular sieve catalyst is made;
(3) by above-mentioned catalyst, at a temperature of 480 DEG C, with steam treatment 3 hours, finished product catalyst;
The catalyst is applied to metering system and ammonia direct aminatin production 2- methyl 2- propylamine, in following reaction temperature
250 DEG C, 15.0MPa, under ammonia alkene (ammonia/metering system) mol ratio 3.0 and suitable space velocities, metering system conversion ratio>
25%, 2- methyl 2- propylamine selectivity>99.8%.
Embodiment 2
Remaining with embodiment 1, except that:The molecular sieve used is for EUO/MFI composite molecular screens, silica alumina ratio
120, two kinds of crystalline phase ratios are 30:70;Molecular sieve accounts for 65wt% by weight percentage in catalyst, and binding agent silica accounts for
33wt%, modifying element La content are 2.0wt%;The extrusion aid is methylcellulose, and addition 3.5%, expanding agent is lemon
Lemon acid, addition 8.0%, the binder precursor is Ludox;Roasting condition after the shaping is that roasting 6 is small at 480 DEG C
When, the roasting condition of sample is to be calcined 4 hours at 450 DEG C after exchange;The steam treatment condition is 520 DEG C, processing 2 is small
When, finished product catalyst;
Above-mentioned catalyst is applied to metering system and ammonia direct aminatin production 2- methyl 2- propylamine, in following reaction temperature
210 DEG C, 3.0MPa, under ammonia alkene (ammonia/metering system) mol ratio 2.0 and suitable space velocities, metering system conversion ratio>
12%, 2- methyl 2- propylamine selectivity>99.5%.
Embodiment 3
Remaining with embodiment 1, except that:The molecular sieve used is for MOR/MEL composite molecular screens, silica alumina ratio
30, two kinds of crystalline phase ratios are 2:98;Molecular sieve accounts for 90wt% by weight percentage in catalyst, and binding agent accounts for 9.8wt%, modified
Elements C e contents are 0.2wt%;The extrusion aid is starch, addition 1.5%, and expanding agent is oxalic acid, addition 2.0%, institute
It is sial complex sol to state binder precursor;The steam treatment condition is 560 DEG C, handled 1 hour, finished product catalysis
Agent;
Above-mentioned catalyst is applied to metering system and ammonia direct aminatin production 2- methyl 2- propylamine, in following reaction temperature
280 DEG C, 15.0MPa, air speed 0.5h-1Under the conditions of suitable ammonia alkene ratio, metering system conversion ratio>20%, 2- methyl 2- propylamine select
Selecting property>99.7%.
Embodiment 4
Remaining with embodiment 1, except that:The molecular sieve used is for MFI/MWW composite molecular screens, silica alumina ratio
35, two kinds of crystalline phase ratios are 95:5;Molecular sieve accounts for 85wt% in catalyst, and binding agent aluminum oxide accounts for 14wt%, modifying element Ce
Content is 1.0wt%;The extrusion aid is polyvinyl alcohol, addition 3.0%, and expanding agent is malic acid, addition 5.0%, institute
It is boehmite to state binder precursor;The steam treatment condition is 450 DEG C, handled 12 hours, finished product catalyst;
Above-mentioned catalyst is applied to metering system and ammonia direct aminatin production 2- methyl 2- propylamine, in following reaction temperature
260 DEG C, 13.0MPa, air speed 1.5h-1Under the conditions of suitable ammonia alkene ratio, metering system conversion ratio>18%, 2- methyl 2- propylamine select
Selecting property>99.8%.
Claims (7)
- A kind of 1. catalyst for producing 2- methyl -2- propylamine, it is characterised in that the catalyst by composite molecular screen-binding agent - Modifying element forms, and composite molecular screen by weight percentage accounts for 65~90wt% wherein in catalyst, and binding agent accounts for 9.8~ 33wt%, modifying element content are 0.2~2.0wt%;The composite molecular screen is ten-ring or twelve-ring composite molecular screen with two phase structure, and the binding agent is oxidation Aluminium or silica, the modifying element are rare earth element.
- 2. according to a kind of catalyst for producing 2- methyl -2- propylamine described in claim 1, it is characterised in that the compound molecule Sieve for while there is one kind of EUO/MFI, EUO/MEL, MOR/MFI, MOR/MEL, MFI/MWW composite molecular screen of two phase structure Or it is a variety of,The composite molecular screen silica alumina ratio 30~120;The part by weight of two kinds of crystalline phases is 2 in composite molecular screen:98~98: 2。
- 3. according to a kind of preparation method of catalyst for producing 2- methyl -2- propylamine described in claim 1 or 2, its feature exists In comprising the following steps:(1) composite molecular screen, modifying element precursor, binder precursor are pressed into its butt part by weight (65~90):(0.2~ 2.0):The ratio of (9.8~33) is well mixed, and is added and is accounted for the extrusion aid of total butt weight 1.0~3.5%, accounts for total butt weight 0 Kneading is uniform after~8.0% expanding agent and the nitric acid for accounting for total butt weight 0~15.0%, extruded moulding, dries, 480~560 DEG C roasting 2~6 hours;(2) by the use of ammonium salt/inorganic acid aqueous solution as exchanger, ion exchange, 450~540 DEG C of roastings 2 are carried out to sample after shaping Hydrogen type molecular sieve catalyst is made after~4 hours;(3) by above-mentioned catalyst, at a temperature of 450~560 DEG C, handled 0.5~20 hour, obtained with water vapour/ammonia vapor To the catalyst of production 2- methyl -2- propylamine;During with AMMONIA TREATMENT, the mass percent concentration of ammoniacal liquor is 0.2~3%.
- 4. according to a kind of preparation method of catalyst for producing 2- methyl -2- propylamine described in claim 3, it is characterised in that: The modifying element precursor is La, Ce at least one nitrate or soluble-salt, and the binder precursor is the thin water aluminium of plan At least one of stone, Alumina gel, Ludox, sial complex sol.
- 5. according to a kind of preparation method for the catalyst for producing 2- methyl -2- propylamine described in claim 3, it is characterised in that described The extrusion aid is selected from least one of sesbania powder, methylcellulose, starch, polyethylene glycol, polyvinyl alcohol, the expanding agent Planted selected from least one citric acid, oxalic acid, maleic acid, malic acid, glycerine, stearic.
- 6. according to a kind of application of catalyst for producing 2- methyl -2- propylamine described in claim 1, it is characterised in that described to urge Agent is using reaction condition:180~280 DEG C of temperature, 1.0~15.0MPa, ammonia alkene (ammonia/metering system) mol ratio 1.0 ~6.0,0.2~2.5h of alkene air speed-1。
- 7. according to a kind of application of catalyst for producing 2- methyl -2- propylamine described in claim 6, it is characterised in that described to urge Agent is preferably using reaction condition:210~270 DEG C of temperature, 2.0~12.0MPa, ammonia alkene (ammonia/metering system) mole Than 1.5~4.0,0.3~1.5h of alkene air speed-1。
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Citations (5)
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US5648546A (en) * | 1992-03-05 | 1997-07-15 | Akzo Nobel, N.V. | Method for manufacturing tert-butylamine |
CN1436597A (en) * | 2002-02-07 | 2003-08-20 | 中国石化上海石油化工股份有限公司 | Catalyst for direct amination of isobutene to prepare aminated tert-butyl amine |
CN101037389A (en) * | 2007-04-26 | 2007-09-19 | 华东理工大学 | Method for preparing organic amine by directly aminating low-carbon olefin |
CN102633647A (en) * | 2012-03-28 | 2012-08-15 | 浙江皇马科技股份有限公司 | Environment-friendly preparation method of tert-butylamine |
CN104418754A (en) * | 2013-08-26 | 2015-03-18 | 王荣发 | Method for producing tert-butylamine by direct catalytic amination of isobutene |
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2016
- 2016-06-13 CN CN201610416961.XA patent/CN107486236B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5648546A (en) * | 1992-03-05 | 1997-07-15 | Akzo Nobel, N.V. | Method for manufacturing tert-butylamine |
CN1436597A (en) * | 2002-02-07 | 2003-08-20 | 中国石化上海石油化工股份有限公司 | Catalyst for direct amination of isobutene to prepare aminated tert-butyl amine |
CN101037389A (en) * | 2007-04-26 | 2007-09-19 | 华东理工大学 | Method for preparing organic amine by directly aminating low-carbon olefin |
CN102633647A (en) * | 2012-03-28 | 2012-08-15 | 浙江皇马科技股份有限公司 | Environment-friendly preparation method of tert-butylamine |
CN104418754A (en) * | 2013-08-26 | 2015-03-18 | 王荣发 | Method for producing tert-butylamine by direct catalytic amination of isobutene |
Non-Patent Citations (1)
Title |
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史爱娥: ""叔丁胺合成技术研究进展"", 《化学工程师》 * |
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