CN107141225A - A kind of polyetheramine synthetic method - Google Patents
A kind of polyetheramine synthetic method Download PDFInfo
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- CN107141225A CN107141225A CN201710482849.0A CN201710482849A CN107141225A CN 107141225 A CN107141225 A CN 107141225A CN 201710482849 A CN201710482849 A CN 201710482849A CN 107141225 A CN107141225 A CN 107141225A
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- catalyst
- polyetheramine
- fixed bed
- synthetic method
- bed device
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
Abstract
The invention discloses a kind of synthetic method of polyetheramine, comprise the following steps：PPG is passed through the first fixed bed device and the second fixed bed device for being loaded with Ni Cu Cr catalyst successively with ammonia, heats compressive reaction, obtains the product polyetheramine；Using above-mentioned technical proposal, reacted using segmented device, it is possible to increase polynary alcohol conversion, and improve primary amine selectivity, increased volume space velocity, increase production capacity, reduce energy consumption.
Description
Technical field
The present invention relates to a kind of method by PPG polyetheramine.
Background technology
Polyetheramine is the polyalkylene oxide hydrocarbon compound that a class is blocked by amino or secondary amino group, according to molecular weight, functional group
Quantity can be divided into a variety of series of products.Specific molecular structure determines its distinctive property and special application, and they are extensive
Applied to polyurethane/polyurea, epoxy curing agent, the field such as surfactant.By selecting different polyoxyalkyl knots
Structure, can adjust a series of performances such as reactivity, toughness, viscosity and the hydrophily of polyetheramine, and amido is supplied to polyetheramine
The possibility reacted with multiple compounds.Its special molecular structure imparts the excellent combination property of polyetheramine, at present business
The polyetheramine of change includes simple function, difunctionality, trifunctional, a series of products of the molecular weight from 230 to 5000.Polyureas spray,
Large-scale composite material is made and the various fields such as epoxy curing agent are widely applied.Polyetheramine can be used as epoxy
The high-performance curing agent of resin, the composite for producing high intensity, high tenacity；As the key component of polyurea materials,
The water-proof system of the concrete structures such as high-speed rail bridge, bridge spanning the sea, dam, large stadium has many application examples, and shows
Excellent performance；With relatively low viscosity, during applied to epoxide terrace or anticorrosive paint, it is possible to reduce solvent load, drop
Low system viscosity；As epoxy curing agent, there is splendid toughness and fatigue performance after being fully cured, in adhesive and
It is widely used in structure glue；With extremely shallow colourity and preferably anti-yellowing property, available for ornaments manufacture.
United States Patent (USP) US3236895 is reported, ATPE, reaction are prepared first by radium Buddhist nun's Raney nickel ammonolysis polyether Glycols
235~255 DEG C of temperature, 14.0~17.0MPa of pressure, and add appropriate solvent (absolute ethyl alcohol or hexamethylene), the conversion of report
Rate only has 40%~50%.
Deutsche Bundespatent EP0081701A, by the polyether-tribasic alcohol ammonolysis of molecular weight 6000 is poly- with general radium Buddhist nun Raney nickel
Ether tertiary amine, its conversion ratio is only 80%.
United States Patent (USP) US5003107, from the mixture of ambrose alloy molybdenum, wherein nickel content 70~75%, copper content 20~
25%, molybdenum content 1~5%, in the PolyTHF polyethers ammonifying process of molecular weight 1000 and 2000, conversion ratio 91~
96%, primary amine content accounts for an amine content 92~97%, 160~190 DEG C of temperature, 14.0~17.0MPa of pressure.
The content of the invention
It is an object of the invention to provide a kind of method for preparing polyetheramine, high-conversion rate, high primary amine selectivity are characterized in.
To achieve these goals, the present invention provides a kind of synthetic method of polyetheramine, comprises the following steps：Polyether polyols
Alcohol is passed through the first fixed bed device and the second fixed bed device for being loaded with Ni-Cu-Cr catalyst, heating pressurization successively with ammonia
Reaction, obtains the product polyetheramine.
Further, heating-up temperature is 170~230 DEG C, 2.0~10.0MPa of pressure in first fixed bed device；The
170~230 DEG C of heating-up temperature in two fixed bed devices, 2.0~10.0MPa of pressure.
Further, heating-up temperature is 160~220 DEG C, 4.0~7.0MPa of pressure in first fixed bed device；
180~210 DEG C of heating-up temperature in second fixed bed device, 4.0~7.0MPa of pressure.
Further, the ammonia addition is 2-15 times, preferably 4-8 times of mole of hydroxyl in the polyetheramine.
Using above-mentioned technical proposal, reacted using segmented device, it is possible to increase polynary alcohol conversion, and improve primary
Amine selectivity, increases volume space velocity, increases production capacity, reduces energy consumption.
Further, the reaction solution obtained in first fixed bed device enters back into second and consolidated after water removal phase
Fixed bed device.By water removal phase, the moisture in reaction system is removed so that reaction is easier to carry out to positive direction.
Further, the volume space velocity of the relatively described Ni-Cu-Cr catalyst of the PPG is 0.1~2:1.
Further, the volume space velocity of the relatively described Ni-Cu-Cr catalyst of the PPG is 0.4~1:1.
Further, the amount of the catalyst loaded in first fixed bed device is more than or equal to second fixed bed
The amount of the catalyst loaded in device.
Further, in the Ni-Cu-Cr catalyst, by mass percentage, nickel content 20~70% (preferably 40~
60%), copper content 1~15% (preferably 3~8%), chromium content 0.1~3% (preferably 0.5~2%), remaining is Al2O3、SiO2、
TiO2And ZrO2In one or more.
Further, the preparation method of the Ni-Cu-Cr catalyst is：The corresponding salt of Ni, Cu, Cr is weighed on demand, successively
By precipitation, aging, drying, roasting, sheeting operation formation catalyst, powder is milled into, is packed into reduction apparatus and is urged
Agent is activated, and the activation of catalyst is used：180~350 DEG C of reduction temperature, 8~14h of the recovery time, GHSV=800~
1200h-1。
Embodiment
It is an object of the invention to provide a kind of method for preparing polyetheramine, high-conversion rate, high primary amine selectivity are characterized in.
A kind of polyalcohol ammonification is prepared first into the Ni-Cu-Cr catalyst of polyetheramine, and coprecipitation prepares catalyst, in mass ratio example
A certain amount of Ni, Cu, Cr correspondence salt is weighed, catalyst is formed by the operation such as precipitation, aging, drying, roasting, tabletting, mills and urge
Agent, is packed into reduction apparatus and carries out catalyst reduction.Catalyst optimum condition of the present invention：180~350 DEG C of reduction temperature,
8~14h of recovery time, GHSV=800~1200h-1.In following examples, the polyalcohol used is that molecular weight is less than 200
Low molecular polylol.
Still reaction used catalyst, is reduced in reduction apparatus, is then transferred under nitrogen protection in autoclave, fixed
In bed and segmentation reaction, used catalyst is directly first reduced in a device, then directly charging reaction again.
Below by specific embodiment, the present invention will be further described：
Embodiment 1
Ni (40%)-Cu (5%)-Cr (1%)/Al2O3 (54%) catalyst is prepared, example in mass ratio weighs a certain amount of
Ni, Cu, Cr correspondence salt, form catalyst, catalyst of milling is packed into by the operation such as precipitation, aging, drying, roasting, tabletting
Catalyst reduction is carried out in reduction apparatus.Activation procedure, 180~350 DEG C of reduction temperature, 8~14h of recovery time, GHSV=800
~1200h-1。
Under nitrogen protection, it is transferred in 500ml autoclaves, polyalcohol 250g, catalyst 10g, temperature：180 DEG C, pressure：
5.0MPa, ammonia/OH (mol)=7, reaction time 10h.
Embodiment 2
Temperature：200 DEG C, pressure：6.0MPa, ammonia/OH (mol)=9, other conditions are same as Example 1；
Embodiment 3
Temperature：220 DEG C, pressure：7.0MPa, ammonia/OH (mol)=11, other conditions are same as Example 1；
Embodiment 4
Catalyst preparation and catalyst reduction program be the same as Example 1 are identical, take 10ml catalyst, load fixed bed reactors
In, reducing catalyst, polyalcohol and the direct feed pump of liquid ammonia are fed, temperature：180 DEG C, pressure：5.0MPa, ammonia/OH
(mol)=8, volume space velocity 0.4h-1, the total amine value of sampling analysis, primary amine value calculates polynary alcohol conversion and primary amine selectivity.
Embodiment 5
Temperature：190 DEG C, pressure：6.0MPa, ammonia/OH (mol)=9, other conditions are same as Example 4；
Embodiment 6
Temperature：200 DEG C, pressure：7.0MPa, ammonia/OH (mol)=10, other conditions are same as Example 4；
Embodiment 7
Air speed 0.3h-1, other conditions are same as Example 6；
Embodiment 8
Segmented device, catalyst preparation and catalyst reduction program be the same as Example 1 are identical, and two sections of fixed beds are loaded respectively
5ml catalyst, reducing catalyst, polyalcohol and the direct feed pump charging of liquid ammonia.
One section of reaction temperature：200 DEG C, pressure：7.0MPa, ammonia/OH (mol)=4, volume space velocity 0.4h-1, by one section of production
Product do water removal and remove ammonia treatment, enter back into second-stage reaction.
Second-stage reaction temperature：200 DEG C, pressure：6.0MPa, ammonia/OH (mol)=6, volume space velocity 0.4h-1, sampling analysis
Total amine value, primary amine value calculates polynary alcohol conversion and primary amine selectivity.
Embodiment 9
Second-stage reaction temperature：210 DEG C, volume space velocity 0.4h-1, other conditions and embodiment 8 are identical；
Embodiment 10
Second-stage reaction temperature：210 DEG C, volume space velocity 0.6h-1, other conditions and embodiment 8 are identical；
Embodiment 11
Second-stage reaction temperature：210 DEG C, volume space velocity 0.8h-1, other conditions and embodiment 8 are identical；
Embodiment 12
Second-stage reaction temperature：210 DEG C, ammonia/OH (mol)=5, volume space velocity 0.6h-1, other conditions and the phase of embodiment 8
Together；
Embodiment 13
Second-stage reaction temperature：210 DEG C, ammonia/OH (mol)=7, volume space velocity 0.6h-1, other conditions and the phase of embodiment 8
Together；
Embodiment 14
Second-stage reaction temperature：210 DEG C, ammonia/OH (mol)=8, volume space velocity 0.6h-1, other conditions and the phase of embodiment 8
Together；
After above-described embodiment reaction terminates, the separately sampled total amine value of analysis, primary amine value calculate polynary alcohol conversion and primary
Amine selectivity, concrete outcome see the table below：
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
1. a kind of synthetic method of polyetheramine, comprises the following steps：PPG is passed through and is loaded with Ni-Cu- successively with ammonia
The first fixed bed device and the second fixed bed device of Cr catalyst, heat compressive reaction, obtain the product polyetheramine.
2. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：In first fixed bed device
Heating-up temperature is 170~230 DEG C, 2.0~10.0MPa of pressure；170~230 DEG C of heating-up temperature, pressure in second fixed bed device
2.0~10.0MPa.
3. a kind of synthetic method of polyetheramine according to claim 2, it is characterised in that：In first fixed bed device
Heating-up temperature is 160~220 DEG C, 4.0~7.0MPa of pressure；180~210 DEG C of heating-up temperature, pressure in second fixed bed device
4.0~7.0MPa.
4. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：The ammonia addition is described
2-15 times of the mole of hydroxyl, preferably 4-8 times in polyetheramine.
5. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：In first fixed bed device
Obtained reaction solution enters back into the second fixed bed device after water removal phase.
6. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：The PPG is with respect to institute
The volume space velocity for stating Ni-Cu-Cr catalyst is 0.1~2:1.
7. a kind of synthetic method of polyetheramine according to claim 6, it is characterised in that：The PPG is with respect to institute
The volume space velocity for stating Ni-Cu-Cr catalyst is 0.4~1:1.
8. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：In first fixed bed device
The amount of the catalyst of loading is more than or equal to the amount of the catalyst loaded in second fixed bed device.
9. a kind of synthetic method of polyetheramine according to claim 1, it is characterised in that：The Ni-Cu-Cr catalyst
In, by mass percentage, nickel content 20~70% (preferably 40~60%), copper content 1~15% (preferably 3~8%), chromium contains
0.1~3% (preferably 0.5~2%) is measured, remaining is Al2O3、SiO2、TiO2And ZrO2In one or more.
10. a kind of synthetic method of polyetheramine according to claim 9, it is characterised in that：The Ni-Cu-Cr catalyst
Preparation method be：The corresponding salt of Ni, Cu, Cr is weighed on demand, sequentially passes through precipitation, aging, drying, roasting, sheeting operation shape
Into catalyst, powder is milled into, is packed into reduction apparatus and carries out activation of catalyst, the activation of catalyst is used：Reduction temperature
180~350 DEG C of degree, 8~14h of recovery time, GHSV=800~1200h-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569441A (en) * | 2018-12-14 | 2019-04-05 | 南京红宝丽聚氨酯有限公司 | A kind of method of reactor and serialization preparation small molecule polyetheramine |
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| CN109569441A (en) * | 2018-12-14 | 2019-04-05 | 南京红宝丽聚氨酯有限公司 | A kind of method of reactor and serialization preparation small molecule polyetheramine |
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