CN107486236B - Catalyst for producing 2-methyl-2-propylamine and preparation method and application thereof - Google Patents
Catalyst for producing 2-methyl-2-propylamine and preparation method and application thereof Download PDFInfo
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- CN107486236B CN107486236B CN201610416961.XA CN201610416961A CN107486236B CN 107486236 B CN107486236 B CN 107486236B CN 201610416961 A CN201610416961 A CN 201610416961A CN 107486236 B CN107486236 B CN 107486236B
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- 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
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- 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 catalyst for producing 2-methyl-2-propylamine, a preparation method and an application thereof, wherein the catalyst consists of a composite molecular sieve, a binder and a modified element, wherein the composite molecular sieve accounts for 65-90 wt% of the catalyst, the binder accounts for 9.8-33 wt% of the catalyst, and the content of the modified element is 0.2-2.0 wt% of the catalyst. Based on the synergistic effect of different crystal phases of the composite molecular sieve, the composite molecular sieve shows unique amination activity. Compared with the prior art, the method has the characteristics of high catalyst activity, low reaction temperature, low reaction pressure and high selectivity of target products, and the economical efficiency of the process is greatly improved.
Description
Technical Field
The invention belongs to the technical field of fine chemical intermediate production, and particularly relates to a catalyst for producing 2-methyl-2-propylamine, and a preparation method and application thereof.
Background
2-methyl-2-propylamine is an important chemical intermediate, and is widely applied to various fields of rubber vulcanization accelerators, pesticides, medicines, organic synthesis, surfactants and the like. In the traditional production method of 2-methyl-2-propylamine, strong acid and strong base exist in a reaction medium/reaction process or a catalyst, the emission of three wastes is more, equipment is seriously corroded, and the environmental pollution is serious, and in addition, a virulent cyanide raw material is also used in the process of producing the 2-methyl-2-propylamine by the Ritter method. The method for producing 2-methyl-2-propylamine by directly aminating 2-methylpropene developed in recent years has the advantages of atom economy and no three-waste discharge, but the previously developed direct aminating method has harsh reaction conditions and low raw material conversion rate: if the BASF process is carried out under the supercritical condition, the reaction pressure reaches 30MPa, the requirement on equipment is high, and the energy consumption is high; under the conditions used by the catalyst reported in petrochemical 2005,34(10) 948-953, the conversion rate of the raw material is less than 3.1%; direct amination processes reported by other developers also suffer from high reaction pressures and low per pass conversion of the starting material.
Disclosure of Invention
Aiming at the defects, the invention provides the catalyst for producing the 2-methyl-2-propylamine by directly aminating the methyl propylene and the preparation method and the application thereof
The invention provides a catalyst for producing 2-methyl-2-propylamine, which consists of a composite molecular sieve, a binder and a modified element, wherein the composite molecular sieve accounts for 65-90 wt% of the catalyst, the binder accounts for 9.8-33 wt% of the catalyst and the modified element accounts for 0.2-2.0 wt% of the catalyst; the composite molecular sieve is a ten-membered ring or twelve-membered ring composite molecular sieve with a two-phase structure, the binder is alumina or silica, and the modified element is a rare earth element.
The composite molecular sieve is one or more of EUO/MFI, EUO/MEL, MOR/MFI, MOR/MEL and MFI/MWW composite molecular sieves with two-phase structures, and the silicon-aluminum molar ratio of the composite molecular sieve is 30-120; the weight ratio of the two crystalline phases in the composite molecular sieve is 2: 98-98: 2.
The preparation method of the catalyst for producing the 2-methyl-2-propylamine comprises the following steps:
(1) uniformly mixing a composite molecular sieve, a modified element precursor and a binder precursor according to the dry basis weight ratio of (65-90): (0.2-2.0): 9.8-33, adding an extrusion aid accounting for 1.0-3.5% of the total dry basis weight, a pore-expanding agent accounting for 0-8.0% of the total dry basis weight and nitric acid accounting for 0-15.0% of the total dry basis weight, uniformly kneading, extruding, forming, drying and roasting at 480-560 ℃ for 2-6 hours;
(2) taking an ammonium salt/inorganic acid aqueous solution as an exchanger, carrying out ion exchange on the molded sample, and roasting at 450-540 ℃ for 2-4 hours to prepare a hydrogen type molecular sieve catalyst;
(3) treating the catalyst with steam/ammonia water steam at 450-560 ℃ for 0.5-20 hours, wherein the mass percentage concentration of the ammonia water is 0.2-3% when the catalyst is treated with the ammonia water;
the precursor of the modifying element is at least one nitrate or soluble salt of La and Ce, and the precursor of the binder is at least one of pseudo-boehmite, aluminum sol, silica sol and silicon-aluminum composite sol;
the extrusion aid is at least one selected from sesbania powder, methyl cellulose, starch, polyethylene glycol and polyvinyl alcohol, and the addition amount of the extrusion aid is 1.0-3.5% of the total dry basis weight;
the pore-expanding agent is at least one of citric acid, oxalic acid, maleic acid, malic acid, glycerol and stearic acid, and the addition amount of the pore-expanding agent accounts for 0-8.0% of the total dry basis weight.
The catalyst is applied to the direct amination of methyl propylene and ammonia to produce 2-methyl-2-propylamine, and the reaction conditions are as follows: the reaction temperature is 180-280 ℃, the pressure is 1.0-15.0 MPa, the molar ratio of ammonia to propylene is 1.0-6.0, and the space velocity of olefin is 0.2-2.5 h-1。
The catalyst is preferably used under reaction conditions of: the temperature is 210-270 ℃, the pressure is 2.0-12.0 MPa, the molar ratio of ammonia to alkene (ammonia gas/methyl propylene) is 1.5-4.0, and the space velocity of alkene is 0.3-1.5.
The catalyst for producing the 2-methyl-2-propylamine by directly aminating the methacrylic acid has high catalyst activity and low reaction temperature and reaction pressure, and by adopting the technical scheme provided by the invention, the conversion rate of the raw material methacrylic acid per pass reaches 12-30%, the selectivity of the target product 2-methyl-2-propylamine reaches more than 99.5%, and the economical efficiency of the process is greatly improved.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
The catalyst comprises a composite molecular sieve, a binder and a modifying element, wherein the EUO/MEL composite molecular sieve accounts for 90wt% of the catalyst, the binder alumina accounts for 9.8 wt% of the catalyst, and the modifying element Ce accounts for 0.2 wt% of the catalyst; the silicon-aluminum molar ratio of the molecular sieve is 47, and the proportion of two crystal phases of EUO and MEL in the composite molecular sieve is 2: 98;
the preparation of the catalyst comprises the following steps:
(1) uniformly mixing the EUO/MEL composite molecular sieve, the modified element precursor and the binder precursor according to the dry basis weight ratio of 90:9.8:0.2, adding an extrusion aid accounting for 3.0 percent of the total dry basis weight, a pore-expanding agent accounting for 2.5 percent of the total dry basis weight and nitric acid accounting for 8.0 percent of the total dry basis weight, uniformly kneading, extruding, forming, drying and roasting at 560 ℃ for 2 hours; wherein the extrusion aid is sesbania powder, the pore-expanding agent is malic acid, and the binder precursor is pseudo-boehmite.
(2) Taking ammonium chloride aqueous solution as an exchanger, carrying out ion exchange on the formed sample, and roasting at 540 ℃ for 2 hours to prepare a hydrogen type molecular sieve catalyst;
(3) treating the catalyst with steam at 480 ℃ for 3 hours to obtain a finished catalyst;
the catalyst is applied to direct amination of methyl propylene and ammonia to produce 2-methyl-2-propylamine, and the conversion rate of the methyl propylene is more than 25 percent and the selectivity of the 2-methyl-2-propylamine is more than 99.8 percent under the conditions of the following reaction temperature of 250 ℃, 15.0MPa, the mol ratio of ammonia to propylene (ammonia gas/methyl propylene) of 3.0 and proper space velocity.
Example 2
The rest is the same as example 1, except that: the adopted molecular sieve is an EUO/MFI composite molecular sieve, the mole ratio of silicon to aluminum is 120, and the ratio of two crystal phases is 30: 70; the catalyst comprises 65 wt% of molecular sieve, 33wt% of binder silicon oxide and 2.0wt% of modified element La; the extrusion aid is methyl cellulose, the adding amount of the extrusion aid is 3.5 percent, the pore-expanding agent is citric acid, the adding amount of the pore-expanding agent is 8.0 percent, and the binder precursor is silica sol; roasting the molded sample for 6 hours at 480 ℃, and roasting the exchanged sample for 4 hours at 450 ℃; the steam treatment condition is 520 ℃, and the finished catalyst is prepared after the treatment for 2 hours;
the catalyst is applied to direct amination of methyl propylene and ammonia to produce 2-methyl 2-propylamine, and the conversion rate of the methyl propylene is more than 12 percent and the selectivity of the 2-methyl 2-propylamine is more than 99.5 percent under the conditions of the following reaction temperature of 210 ℃, 3.0MPa, the mol ratio of ammonia to propylene (ammonia gas/methyl propylene) of 2.0 and proper space velocity.
Example 3
The rest is the same as example 1, except that: the adopted molecular sieve is MOR/MEL composite molecular sieve, the mole ratio of silicon to aluminum is 30, and the ratio of two crystal phases is 2: 98; the catalyst comprises 90wt% of molecular sieve, 9.8 wt% of binder and 0.2 wt% of modified element Ce; the extrusion aid is starch, the adding amount of the extrusion aid is 1.5%, the pore-expanding agent is oxalic acid, the adding amount of the pore-expanding agent is 2.0%, and the binder precursor is silicon-aluminum composite sol; the steam treatment condition is 560 ℃, and the finished catalyst is prepared after 1 hour of treatment;
the catalyst is applied to the direct amination of the methyl propylene and ammonia to produce the 2-methyl 2-propylamine, and the reaction temperature is 280 ℃, the pressure is 15.0MPa, and the space velocity is 0.5h-1And proper ammine ratio, the conversion rate of the methyl propylene>20%, 2-methyl-2-propylamine selectivity>99.7％。
Example 4
The rest is the same as example 1, except that: the adopted molecular sieve is an MFI/MWW composite molecular sieve, the mole ratio of silicon to aluminum is 35, and the ratio of two crystal phases is 95: 5; in the catalyst, the molecular sieve accounts for 85 wt%, the binder alumina accounts for 14 wt%, and the content of the modified element Ce is 1.0 wt%; the extrusion aid is polyvinyl alcohol, the adding amount of the extrusion aid is 3.0 percent, the pore-expanding agent is malic acid, the adding amount of the pore-expanding agent is 5.0 percent, and the binder precursor is pseudo-boehmite; the steam treatment condition is 450 ℃, and the finished catalyst is prepared after the treatment for 12 hours;
the catalyst is applied to the direct amination of methyl propylene and ammonia to produce 2-methyl 2-propylamine, and the reaction temperature is 260 ℃, the reaction pressure is 13.0MPa, and the space velocity is 1.5h-1And proper ammine ratio, the conversion rate of the methyl propylene>Selectivity to 18%, 2-methyl-2-propylamine>99.8％。
Claims (5)
1. The application of the catalyst for producing the 2-methyl-2-propylamine is characterized in that the catalyst consists of a composite molecular sieve, a binder and a modified element, wherein the composite molecular sieve accounts for 65-90 wt%, the binder accounts for 9.8-33 wt% and the modified element accounts for 0.2-2.0 wt% of the catalyst in percentage by weight;
the composite molecular sieve is one or more of EUO/MFI, EUO/MEL, MOR/MFI, MOR/MEL and MFI/MWW composite molecular sieves with two-phase structures, and the silicon-aluminum molar ratio of the composite molecular sieve is 30-120; the weight ratio of two crystalline phases in the composite molecular sieve is 2: 98-98: 2, the binder is alumina or silica, and the modifying element is a rare earth element;
the catalyst is used under the reaction conditions that: the temperature is 180-280 ℃, the pressure is 1.0-15.0 MPa, the molar ratio of ammonia gas to methyl propylene is 1.0-6.0, and the space velocity of olefin is 0.2-2.5 h-1。
2. A process for the preparation of a catalyst for the production of 2-methyl-2-propylamine, which is used as described in claim 1, comprising the steps of:
(1) uniformly mixing a composite molecular sieve, a modified element precursor and a binder precursor according to the dry basis weight ratio of (65-90): (0.2-2.0): 9.8-33, adding an extrusion aid accounting for 1.0-3.5% of the total dry basis weight, a pore-expanding agent accounting for 0-8.0% of the total dry basis weight and nitric acid accounting for 0-15.0% of the total dry basis weight, uniformly kneading, extruding, forming, drying and roasting at 480-560 ℃ for 2-6 hours;
(2) taking an ammonium salt/inorganic acid aqueous solution as an exchanger, carrying out ion exchange on the molded sample, and roasting at 450-540 ℃ for 2-4 hours to prepare a hydrogen type molecular sieve catalyst;
(3) treating the catalyst with steam/ammonia water steam at 450-560 ℃ for 0.5-20 hours to obtain the catalyst for producing 2-methyl-2-propylamine; when the ammonia water is used for treatment, the mass percentage concentration of the ammonia water is 0.2-3%.
3. A process for the preparation of a catalyst for the production of 2-methyl-2-propylamine, which is used as claimed in claim 2, wherein: the precursor of the modifying element is La soluble salt, Ce soluble salt or a mixture of the La soluble salt and the Ce soluble salt, and the precursor of the binder is at least one of pseudo-boehmite, alumina sol, silica sol and silicon-aluminum composite sol.
4. The method for preparing a catalyst for the production of 2-methyl-2-propylamine used as claimed in claim 2, wherein the extrusion aid is at least one selected from sesbania powder, methylcellulose, starch, polyethylene glycol and polyvinyl alcohol, and the pore-expanding agent is at least one selected from citric acid, oxalic acid, maleic acid, malic acid, glycerol and stearic acid.
5. Use of a catalyst for the production of 2-methyl-2-propylamine according to claim 1, characterised in that it is used under the reaction conditions: the temperature is 210-270 ℃, the pressure is 2.0-12.0 MPa, the molar ratio of ammonia gas to methyl propylene is 1.5-4.0, and the space velocity of olefin is 0.3-1.5 h-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 |
-
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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| "叔丁胺合成技术研究进展";史爱娥;《化学工程师》;20060630;第28-31页 * |
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