CN106633028A - Method for continuously producing amine-terminated polyether - Google Patents
Method for continuously producing amine-terminated polyether Download PDFInfo
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- CN106633028A CN106633028A CN201611224667.5A CN201611224667A CN106633028A CN 106633028 A CN106633028 A CN 106633028A CN 201611224667 A CN201611224667 A CN 201611224667A CN 106633028 A CN106633028 A CN 106633028A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
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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
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
Abstract
The invention discloses a method for continuously producing an amine-terminated polyether. The method comprises the steps of adopting a hydroxyl-terminated polyether as a polyether material, wherein the molecular weight of polyether is low molecular weight 200-2,000, the polyether polyol contains 1-3 hydroxy; mixing a polyether polyol material with liquid ammonia, wherein the volume velocity of the polyether polyol material is 0.01-0.1h<-1> and the volume velocity of the liquid ammonia is 0.05-3.0h<-1>; and carrying out heating in a preheating furnace until the reaction temperature is 180-260 DEG C, controlling the reaction pressure to be 0.05-2.5MPa and carrying out continuous production under the action of a catalyst to obtain the amine-terminated polyether. The problem that the quality of the produced small-molecular amine-terminated polyether product cannot reach the requirements is solved, the method has relatively high conversion rate and primary amine selectivity; the reaction conversion rate is greater than or equal to 95.0%; and the primary amine selectivity is greater than or equal to 95.0%.
Description
Technical field
The invention belongs to chemosynthesis technical field, specifically related to low molecular weight hydroxy-terminated polyethers low-voltage hydrogenation preparation end ammonia
Base polyethers and its catalyst method.
Background technology
Ending amino polyether is the polyalkylene oxide hydrocarbon compound that a class is blocked by primary amino radical or primary amino radical, according to molecular weight, official
Quantity can be rolled into a ball can be divided into various series of products.Because the Amino End Group of its strand contains active hydrogen, can be with various reactive groups
Effect, it is widely used as the curing agent of the synthesis material of polyurethane (polyureas) material and epoxy resin, additionally, can also be in engine
It is used as anti-muddy, antisolvent precipitation additive in fuel oil.Middle low-molecular-weight ending amino polyether can replace amine curing agent to apply
Epoxy resin field.Ending amino polyether unique properties, are almost related to all of epoxy application, such as coating, Embedding Material, build
Build material, composite and adhesive etc..Amine system curing agent accounts for prominent position in all curing agent, and consumption maximum, kind are most
It is many, the 80% of curing agent total amount is accounted for, it is the epoxy curing agent answered emphasis from now on and greatly develop.And China's epoxy resin
The problem of curing agent industry be product yield it is little, far from the market demand is met, producing needs particularly thorny, high-grade and many solidifyings
Agent needs import；Another market application of middle low-molecular-weight ending amino polyether is as SPUA, Spray Polyurea Elastomer
Technology is a kind of new " omnipotent " application techniques, is described as greatest of the late 20th century coating, application techniques field
Existing, it has hydrophobicity extremely strong, insensitive to ambient humidity, it might even be possible to spray film forming on water (or ice), is extremely disliking
Under bad environmental condition can normal construction, show it is particularly pertinent：Traditional anti-corrosion and protection idea are broken completely, have been that material is protected
Shield industry sets up a higher standard：Its not only fine and close, continuous, seamless, completely isolation moisture in air and oxygen
Penetrate into, anti-corrosion and barrier propterty are unrivaled, and with wear-resisting, waterproof, shock resistance, antifatigue, ageing-resistant, high temperature resistant, resistance to
The several functions such as nuclear radiation, therefore application is quite varied.
Amine terminated polyether product because property is active, excellent performance, so using widely, its synthesising process research
Also receive much concern always.Nineteen fifty-seven, Simons DM propose first the synthetic method of amine terminated polyether, Texaco companies of the U.S.
Then take the lead in completing the industrialized production of polyetheramine.Hereafter, people have carried out more deeply wide to amine terminated polyether synthetic method
General research.At present, the conventional synthetic method of amine terminated polyether mainly includes：Study on Catalytic Amination of Alcohols method, leaving group method, aminobutene
Acid esters method and Hydrolyze method etc., using end hydroxy polyether face hydrogen ammoniation process prepare amine terminated polyether have production process be easy to continuously,
The advantages such as side reaction is few, efficiency high, the three wastes are few, process is green, productivity effect is high, are increasingly becoming the main flow skill for producing the product
Art.
Experimental study shows that the technical difficulty that end hydroxy polyether faces hydrogen ammonification is close with the size of its molecular weight with industrial practice
Cut is closed, and with the continuous decline of its molecular weight, its reaction difficulty gradually increases.Therefore at present middle low-molecular-weight end amido gathers
Typically using in the case where hydrogen state is faced, low-molecular-weight ending amino polyether in being prepared using continuous catalysis ammoniation process, is to be in a leading position to ether
The ending amino polyether production technology of level, but its working condition and its harshness.Catalyst is generally Ni-Cu-Cr-M types, its activity
General relatively low, according to foreign literature, the working condition of ending amino polyether (particularly its molecular weight is 200～300) exists
Temperature 200-260 DEG C, pressure 3.5-20MPa, therefore, but the method for this reduction amination needs higher pressure and temperature,
Reaction temperature is typically required at 200 DEG C or so, 3.5～34.5MPa of reaction pressure, the requirement to production equipment is very high.
In recent years, the country occurs in that the method for producing amine terminated polyether using fixed bed reactors, but because of its presence catalysis
Activity is relatively low, thus its reaction pressure is generally 4.0MPa or more, and polyethers liquid air speed is extremely low, and catalyst is generally Ni-
Cu-Cr-M types, generally 0.01h-1, the less stable of low molecular weight hydroxy-terminated polyethers in adding, thus actual yield compared with
It is low.Therefore further reduce reaction pressure, realize that low-molecular-weight is the task of top priority in efficiently production.The present invention provides one kind to be used for
Low-molecular-weight ending amino polyether catalyst preparation technology in low pressure fixed bed production.
The content of the invention
Present invention aims to the defect and deficiency of prior art presence, there is provided in a kind of low pressure fixed bed production
Low-molecular-weight ending amino polyether technology, further to reduce the difficulty of the production, simplifies the production procedure of the product, improves
The efficiency of low-molecular-weight ending amino polyether in the technique productions；Its core technology is to provide a kind of effective catalyst, and a kind of
The method that the high fixed bed process of high conversion rate, primary amine selectivity prepares amine terminated polyether.
Technical scheme：A kind of method of continuous manufacturing side primary amine groups polyethers provided by the present invention, be with end hydroxy polyether
Polyethers raw material, pfpe molecule amount is low-molecular-weight 200～2000,1～3 hydroxyl is contained in PPG, by PPG
Raw material mixes with liquefied ammonia, PPG raw material volume 0.01～1.0h of air speed-1, liquefied ammonia 0.05～3.0h of volume space velocity-1,
180～260 DEG C of reaction temperature is warming up in preheating furnace, reaction pressure is controlled in 0.05～2.5MPa, in the presence of catalyst,
Continuous production, obtains amine terminated polyether.
In above-mentioned production process, described catalyst is loaded catalyst, and its main component is Ni-Cu-Cr-M-N, its
Middle M is co-catalyst, is made up of two or more auxiliary agent；N is carrier.The addition of the co-catalyst (M) is catalysis
The 0.5～5.0% of agent weight；The addition of the carrier (N) is the 10～50% of catalyst weight.
Described auxiliary agent can be metal promoters, pore structure modifying agent；Described metal promoters are rare earth unit
Element or noble metal；Described pore structure modifying agent is mixed for one or more in citric acid, oxalic acid.
For the present invention, catalyst is particularly important, when described catalyst main component is following several schemes, instead
Answer best results：Ni-Cu-Cr-Al2O3、Ni-Cu-Cr-La-SiO2、Ni-Cu-Cr-Pd-Al2O3、Ni-Cu-Cr-La-Al2O3。
Present invention also offers the preparation method of described catalyst：Sent out at a certain temperature with alkali using metallic compound
Raw coprecipitation reaction, wherein metallic compound can be one or two in sulfate, nitrate, chloride, alkali be sodium carbonate,
One or two in saleratus, potassium carbonate, NaOH, then in turn through aging, washing, suction filtration, drying, mixing,
Roasting, mixing, compressing tablet are obtained required catalyst.
Catalyst obtained by said method, with high-specific surface area and big pore volume.Specific surface area is 150m2/ more than g,
Pore volume is more than 0.30ml/g.
Further description said method：Using coprecipitation, metal-nitrate solutions concentration is 0.5～2mol/L, is sunk
Shallow lake agent is Na2CO3, concentration is 0.5～2mol/L, and precipitation temperature is 40～80 DEG C, 60～80 DEG C of aging temperature, ageing time 0.5
～2h, carries out successively suction filtration, washing, selects carrier Al2O3、SiO2, 10～20h is dried after suction filtration, through grinding material granulation, 300
Catalyst after roasting is finally carried out compressing tablet, in H by～450 DEG C of high-temperature roastings, 2～4h of roasting time2-N2Under gaseous mixture environment
Carry out reduction activation.
Further, nickel source can be nitrate, sulfate, acetate, citrate etc., and its addition is catalyst weight
The 20～80% of amount；Copper source can be nitrate, sulfate, acetate, citrate etc., and its addition is the 5 of catalyst weight
～30%；Chromium source can for nitrate, sulfate, acetate, citrate etc., its addition for catalyst weight 0.01～
0.10%；
Further, described metal mold promoter source can be nitrate or chloride etc., and its addition is
0.001～1.000%.
Beneficial effect：Compared with prior art, the present invention has following features：Compared to the system of the methods such as other autoclaves
Standby terminal primary amine base polyethers, fixed bed process equipment is simple, successive reaction is easily operated, reaction pressure is low, and product quality is also relatively intermittently
Method is more stable, with low viscosity, color be shallow, low volatility.This law not only solves production small molecule end primary amino radical polyether product
Quality can not reach the problem of requirement, with higher conversion ratio and primary amine selectivity, reaction conversion ratio >=95.0%；And
Primary amine selectivity >=95.0%.
Specific embodiment：
Embodiment 1：
Coprecipitation prepares Ni-Cu-Cr-La-Al2O3Catalyst：By nickel, copper, chromium, the nitrate of lanthanum and sodium carbonate one
Determine to be co-precipitated at temperature and catalyst is obtained.Adopt addition tenor (reduction-state) for：Nickel 50%, copper 30%, lanthanum 1.00%, gold
Genus nitrobacter solution concentration is 0.5mol/L, precipitating reagent Na2CO3For 0.5mol/L, there is coprecipitation reaction under the conditions of 40 DEG C,
Aging 30min under the conditions of 60 DEG C, carries out successively suction filtration, washing, selects carrier Al2O3Measure as 14%, 10h is dried after suction filtration, pass through
Material granulation is ground, in 350 DEG C of high-temperature roasting 2h, finally the catalyst after roasting 1% weight in catalyst Precursors thing is added into
The auxiliary agents such as oxalic acid carry out mixed pressuring plate, obtain column shape catalyst 1, and the specific surface area of catalyst is 168.58m2/ g, pore volume is
0.30ml/g。
Embodiment 2：
Coprecipitation prepares Ni-Cu-Cr-Pd-Al2O3Catalyst：Nickel, copper, chromium, the nitrate of palladium and saleratus are existed
It is co-precipitated under uniform temperature and catalyst is obtained, for Ni-Cu-Cr-Pd-Al2O3The preparation of catalyst.Using addition tenor
(reduction-state) is：Nickel 80%, copper 5%, palladium 0.005%, metal-nitrate solutions concentration is 1mol/L, precipitating reagent K2CO3For
1mol/L, precipitation temperature is 60 DEG C, the aging 30min under the conditions of 70 DEG C, and suction filtration, washing are carried out successively, selects carrier S iO2Amount
For 10%, 10h is dried after suction filtration, through grinding material granulation, in 300 DEG C of high-temperature roasting 2h, finally in catalyst after baking plus
Entering the citric acid of parent thing 5.0% carries out compressing tablet, obtains cylindrical catalyst 2, and the specific surface area of catalyst is 157.64m2/ g, pore volume
For 0.35ml/g.
Embodiment 3：
Coprecipitation prepares Ni-Cu-Cr-La-SiO2/Catalyst：By the chloride of the elements such as nickel and potassium carbonate in a constant temperature
The lower co-precipitation of degree is obtained catalyst.Adopt addition tenor (reduction-state) for：Nickel 20%, copper 20%, lanthanum 10%, metal nitrate
Concentration of salt solution is 2mol/L, precipitating reagent Na2CO3For 2mol/L, there is coprecipitation reaction under the conditions of 80 DEG C, under the conditions of 80 DEG C
Aging 30min, carries out successively suction filtration, washing, and selection carrier is Al2O3And SiO2Mixture amount (respectively accounts for 50% (weight), it adds
Enter amount for 50%, 10h is dried after suction filtration, through grinding material granulation, in 400 DEG C of high-temperature roasting 2h, last catalyst after baking
(respectively account for 50% (weight) carries out compressing tablet to the middle citric acid of addition parent thing 3.0%, obtains cylindrical catalyst 3, should with oxalic acid mixture
Specific surface area of catalyst is 165.31m2/ g, pore volume is 0.32ml/g.
Embodiment 4 (Reference Example 1)
Coprecipitation prepares Ni-Cu-Cr-Al2O3Catalyst：By nickel, copper, chromium, the nitrate of lanthanum and sodium carbonate in a constant temperature
The lower co-precipitation of degree is obtained catalyst.Adopt addition tenor (reduction-state) for：Nickel 50%, copper 30%, metal-nitrate solutions
Concentration is 0.5mol/L, precipitating reagent Na2CO3For 0.5mol/L, there is coprecipitation reaction under the conditions of 40 DEG C, it is old under the conditions of 60 DEG C
Change 30min, suction filtration, washing are carried out successively, select carrier Al2O3Measure as 14%, 10h is dried after suction filtration, through grinding material granulation, in
350 DEG C of high-temperature roasting 2h, finally add catalyst Precursors thing to carry out mixed pressuring plate the catalyst after roasting, obtain column shape and urge
Agent 4, the specific surface area of catalyst is 105.24m2/ g, pore volume is 0.15ml/g.
Embodiment 5：
Fixed bed prepares end primary amino radical polyethers：Catalyst 1 is crushed to 20～40 mesh, tightly packed 20ml samples weighings,
Ask for its heap density, calculate 4.0ml catalyst weights, accurately weigh 4.0ml20～40 mesh catalyst, be seated in Φ 8 ×
In 500mm fixed bed reactors, catalyst reduction is carried out after leak test, use 5%H2-N2It is persistently overheating in 250 DEG C of reductase 12 h, 420
DEG C reductase 12 h, contains Ni-Cu-Cr-La-Al after being activated2O3The fixed bed reactors of catalyst.Rise in reaction preheating furnace
To 180 DEG C of reaction temperature, control valve mass flowmenter makes to keep certain pressure (1.0MPa) in reactor temperature, by polyether polyols
Alcohol (molecular weight 200) mixes in proportion with hydrogen, liquefied ammonia.Mixed material enters tubular reactor, Aethoxy Sklerol raw material volume air speed
0.1h-1, liquefied ammonia volume space velocity 3h-1, mixture is fully contacted in reacting furnace with catalyst, occurs in the presence of catalyst
Catalytic ammoniation reacts.Material after reaction enters to be equipped with filter gas-liquid separator from discharging opening carries out gas-liquid separation,
Polyethers amine product can be obtained in products pot.After testing, terminal hydroxy group conversion ratio 95.2%, primary amine selectivity 95.8%.
Embodiment 6：
Catalyst 2 is crushed to 20～40 mesh, tightly packed 20ml samples weighings ask for its heap density, calculate 4.0ml and urge
Agent weight, accurately weighs 4.0ml20～40 mesh catalyst, in being seated in Φ 8 × 500mm fixed bed reactors, leak test
After carry out catalyst reduction, use 5%H2-N2In 250 DEG C of reductase 12 h, persistently overheating, 400 DEG C of reductase 12 h, contain after being activated
Ni-Cu-Cr-Pd-Al2O3The fixed bed reactors of catalyst.220 DEG C of reaction temperature is warming up in reaction preheating furnace, valve is controlled
Door mass flowmenter makes to keep certain pressure (0.05MPa) in reactor, by PPG (molecular weight 400) and hydrogen air-liquid
Ammonia mixes in proportion.Mixed material enters tubular reactor, Aethoxy Sklerol raw material volume air speed 1.0h-1, liquefied ammonia volume space velocity 3h-1,
Mixture is fully contacted in reacting furnace with catalyst, and catalytic ammoniation reaction occurs in the presence of catalyst.After reaction
Material is entered equipped with gas-liquid separation is carried out in filter gas-liquid separator from discharging opening, and polyetheramine can be obtained in products pot
Product.After testing, terminal hydroxy group conversion ratio 96.2%, primary amine selectivity 96.8%.
Embodiment 7：
Catalyst 3 is crushed to 20～40 mesh, tightly packed 20ml samples weighings ask for its heap density, calculate 4.0ml and urge
Agent weight, accurately weighs 4.0ml20～40 mesh catalyst, in being seated in Φ 8 × 500mm fixed bed reactors, leak test
After carry out catalyst reduction, use 5%H2-N2In 250 DEG C of reductase 12 h, persistently overheating, 415 DEG C of reductase 12 h, contain after being activated
Ni-Cu-Cr-La-SiO2The fixed bed reactors of catalyst.260 DEG C of reaction temperature is warming up in reaction preheating furnace, valve is controlled
Door mass flowmenter makes to keep certain pressure (2.5MPa) in reactor, by PPG (molecular weight 2000) and hydrogen air-liquid
Ammonia mixes in proportion.Mixed material enters tubular reactor, Aethoxy Sklerol raw material volume air speed 2.0h-1, liquefied ammonia volume space velocity 0.5h-1, mixture is fully contacted in reacting furnace with catalyst, and catalytic ammoniation reaction occurs in the presence of catalyst.After reaction
Material enter equipped with gas-liquid separation is carried out in filter gas-liquid separator from discharging opening, polyethers can be obtained in products pot
Amine product.After testing, terminal hydroxy group conversion ratio 99.2%, primary amine selectivity 98.8%.
Embodiment 8：
Fixed bed prepares end primary amino radical polyethers：Catalyst 4 is crushed to 20～40 mesh, tightly packed 20ml samples weighings,
Ask for its heap density, calculate 4.0ml catalyst weights, accurately weigh 4.0ml20～40 mesh catalyst, be seated in Φ 8 ×
In 500mm fixed bed reactors, catalyst reduction is carried out after leak test, use 5%H2-N2It is persistently overheating in 250 DEG C of reductase 12 h, 410
DEG C reductase 12 h, contains Ni-Cu-Cr-Al after being activated2O3The fixed bed reactors of catalyst.It is warming up in reaction preheating furnace
180 DEG C of reaction temperature, control valve mass flowmenter makes to keep certain pressure (3.0MPa) in reactor, by PPG
(molecular weight 200) mixes in proportion with hydrogen, liquefied ammonia.Mixed material enters tubular reactor, Aethoxy Sklerol raw material volume air speed
0.1h-1, liquefied ammonia volume space velocity 3h-1, mixture is fully contacted in reacting furnace with catalyst, occurs in the presence of catalyst
Catalytic ammoniation reacts.Material after reaction enters to be equipped with filter gas-liquid separator from discharging opening carries out gas-liquid separation,
Polyethers amine product can be obtained in products pot.After testing, terminal hydroxy group conversion ratio 65.3%, primary amine selectivity 84.5%.
Claims (10)
1. a kind of method of continuous manufacturing side primary amine groups polyethers, it is characterised in that with end hydroxy polyether as polyethers raw material, polyethers point
Son amount is low-molecular-weight 200～2000, and 1～3 hydroxyl is contained in PPG, and polyether polyols raw polyol is mixed with liquefied ammonia,
PPG raw material volume 0.01～1.0h of air speed-1, liquefied ammonia 0.05～3.0h of volume space velocity-1, it is warming up in preheating furnace anti-
180～260 DEG C of temperature is answered, reaction pressure is controlled in 0.05～2.5MPa, in the presence of catalyst, continuous production is held
Amino-polyether.
2. the method for continuous manufacturing side primary amine groups polyethers according to claim 1, it is characterised in that described catalyst is
Loaded catalyst, its main component is Ni-Cu-Cr-M-N, and wherein M is co-catalyst, by two or more auxiliary agent group
Into；N is carrier.
3. hydrogenation catalyst according to claim 2, it is characterised in that the addition of the co-catalyst is catalyst weight
The 0.5～5.0% of amount；The addition of the carrier is the 10～50% of catalyst weight.
4. the method for continuous manufacturing side primary amine groups polyethers according to claim 2, it is characterised in that described auxiliary agent can be with
It is metal promoters, pore structure modifying agent；Described metal promoters are rare earth element or noble metal；Described pore structure
Modifying agent is mixed for one or more in citric acid, oxalic acid.
5. the method for continuous manufacturing side primary amine groups polyethers according to claim 2, it is characterised in that described catalyst master
Composition is wanted to be Ni-Cu-Cr-Al2O3、Ni-Cu-Cr-La-SiO2、Ni-Cu-Cr-Pd-Al2O3、Ni-Cu-Cr-La-Al2O3。
6. the method for continuous manufacturing side primary amine groups polyethers according to claim 2, it is characterised in that described catalyst is adopted
There is coprecipitation reaction at a certain temperature with metallic compound and alkali, wherein metallic compound can be sulfate, nitrate, chlorine
One or two in compound, alkali is one or two in sodium carbonate, saleratus, potassium carbonate, NaOH, then successively
The catalyst needed for aging, washing, suction filtration, drying, mixing, roasting, mixing, compressing tablet are obtained.
7. the method for continuous manufacturing side primary amine groups polyethers according to claim 6, it is characterised in that described catalyst
Specific surface area is 150m2/ more than g, pore volume is more than 0.30ml/g.
8. the method for continuous manufacturing side primary amine groups polyethers according to claim 6, it is characterised in that adopt coprecipitation, gold
Genus nitrobacter solution concentration is 0.5～2mol/L, and precipitating reagent is Na2CO3, concentration be 0.5～2mol/L, precipitation temperature be 40～
80 DEG C, 60～80 DEG C of aging temperature, 0.5～2h of ageing time carries out successively suction filtration, washing, selects carrier Al2O3、SiO2, take out
10～20h is dried after filter, through grinding material granulation, in 300～450 DEG C of high-temperature roastings, 2～4h of roasting time, finally by after roasting
Catalyst carry out compressing tablet, in H2-N2Reduction activation is carried out under gaseous mixture environment.
9. the method for continuous manufacturing side primary amine groups polyethers according to claim 8, it is characterised in that nickel source can for nitrate,
Sulfate, acetate, citrate etc., its addition is the 20～80% of catalyst weight；Copper source can be nitrate, sulfuric acid
Salt, acetate, citrate etc., its addition is the 5～30% of catalyst weight；Chromium source can be nitrate, sulfate, acetic acid
Salt, citrate etc., its addition is the 0.01～0.10% of catalyst weight.
10. preparation method according to claim 9, it is characterised in that described metal mold promoter source can be nitrate
Or chloride etc., its addition is 0.001～1.000%.
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| CN107141225A (en) * | 2017-06-22 | 2017-09-08 | 江苏飞翔化工股份有限公司 | A kind of polyetheramine synthetic method |
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|---|---|---|---|---|
| CN104119239A (en) * | 2014-08-12 | 2014-10-29 | 无锡阿科力科技股份有限公司 | Process of producing small molecular weight polyether amine by continuous method |
| CN104419002A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Producing method of amine-terminated polyether |
| CN106040253A (en) * | 2016-06-01 | 2016-10-26 | 南京林业大学 | Preparation method and application of primaquine-terminated polyether catalyst prepared through static bed catalytic hydrogenation |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419002A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Producing method of amine-terminated polyether |
| CN104119239A (en) * | 2014-08-12 | 2014-10-29 | 无锡阿科力科技股份有限公司 | Process of producing small molecular weight polyether amine by continuous method |
| CN106040253A (en) * | 2016-06-01 | 2016-10-26 | 南京林业大学 | Preparation method and application of primaquine-terminated polyether catalyst prepared through static bed catalytic hydrogenation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141225A (en) * | 2017-06-22 | 2017-09-08 | 江苏飞翔化工股份有限公司 | A kind of polyetheramine synthetic method |
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