CN107880260A - A kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether - Google Patents
A kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether Download PDFInfo
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- CN107880260A CN107880260A CN201711392065.5A CN201711392065A CN107880260A CN 107880260 A CN107880260 A CN 107880260A CN 201711392065 A CN201711392065 A CN 201711392065A CN 107880260 A CN107880260 A CN 107880260A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 69
- 150000001412 amines Chemical class 0.000 title claims abstract description 60
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 150
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 44
- 230000009615 deamination Effects 0.000 claims abstract description 38
- 238000006481 deamination reaction Methods 0.000 claims abstract description 38
- 238000001704 evaporation Methods 0.000 claims abstract description 38
- 230000008020 evaporation Effects 0.000 claims abstract description 38
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003860 storage Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 88
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- -1 small molecule amine Chemical class 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000003141 primary amines Chemical class 0.000 abstract 1
- 229920001451 polypropylene glycol Polymers 0.000 description 32
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 22
- 229910052804 chromium Inorganic materials 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Chemical group 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
-
- 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)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether.A kind of continuous preparation device of small-molecular-weight amine terminated polyether, including hydrogen-storing device, liquid ammonia storage tank, PPG storage tank, mixing preheater, fixed bed reactors I, fixed bed reactors II, one-level gas-liquid separator, stage casing drying tower, two level gas-liquid separator, circulating hydrogen compressor, flash evaporation deamination tower, pressurized liquefied device, dehydrating tower, wastewater disposal basin and product storage tank；With small-molecular-weight PPG, H during preparation2With liquid NH3For raw material, respectively under catalyst action, by the way of two fixed bed reactors are connected, generation " two steps " faces hydrogen aminating reaction and prepares small-molecular-weight amine terminated polyether.Operating process of the present invention is continuous, and product quality is stably and controllable, and reaction condition is gentle；Realize H2And liquid NH3Circulating and recovering, more environmental protection and economy；Reaction conversion ratio >=99.0%, primary amine selectivity >=98.5%.
Description
Technical field
The present invention relates to a kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether, belong to Amino End Group and gather
The preparation field of ether.
Background technology
Amine terminated polyether (Amine-Terminated Polyether, ATPE), also known as polyetheramine, are a kind of polyoxyalkylenes
Hydrocarbon compound, its molecular backbone are polyether skeleton, and end is by amino-terminated.Being substituted according to H atom in amino
Number, can be divided into primary amine groups, secondary amine amine terminated polyether again.At present, the production of domestic amine terminated polyether product is mostly batch process, production
Kind class is not complete, quality is unstable, and production capacity can not also meet the market demand at all.
And the fixed bed that the synthesis of offshore company's amine terminated polyether at present is mainly the gas, liquid, solid three-phase of serialization faces hydrogen
Aminating reaction.Fixed bed continuous synthesis are that current synthesis amine terminated polyether is the most feasible, and product quality is most stable and more
A kind of method of environmental protection, domestic increasing enterprise also carry out correlative study.
Patent CN103626988 is disclosed with W metal/Cu/M/Al2O3For catalyst, continuously synthesized using fixed bed small
The method of molecular weight amine terminated polyether, one or more of mixed aids in M Cr, Fe and Zn.Small-molecular-weight polyethers is more
First alcohol carries out facing the method that hydrogen aminating reaction prepares amine terminated polyether under 180~220 DEG C, 14~25MPa.Primary amine product selects
Property 97.5%, but reaction conversion ratio can only achieve 85.1%, and product fails to reach market like product index, and reaction temperature and
Pressure is higher, and processing safety is poor.
Patent CN102585211 is disclosed with large hole nickel-based catalyst, is continuously closed under 180~260 DEG C, 10~14MPa
Into the method for preparing amine terminated polyether.The method includes following three continuous stages：Pretreatment stage, the stage of reaction and rear place
The reason stage.Its catalyst Ni containing mass fraction 75~80%, 15~20% Cu, 1~5% Cr's and 0.5~2%
Co.The amine terminated polyether product primary amine selectivity 97~99% of this method synthesis, reaction conversion ratio 95%~99%, although achieving
Ideal reaction conversion ratio and primary amine product selectivity, but only it is referred to not reacted NH3And H2Recovery, but not
Its recycled can be realized, adds the probability of environmental pollution, reduces the security of technological operation.And 10~14MPa's is anti-
It is difficult to carry out industrialization amplification and production to answer pressure.
Patent CN106633028 using fixed bed at 180~260 DEG C, 1~20MPa, the condition of ammonia alcohol mol ratio 1~15
Lower continuous synthesis amine terminated polyether, process operation is easy, and realizes NH3And H2Recycle, reduce pollution, improve
Production efficiency.But using the method prepare amine terminated polyether reaction conversion ratio only 92% or so, primary amine selection rate also only have 91~
95%, and the small-molecular-weight amine terminated polyether that molecule is 230 and 400 has only been synthesized, the amine terminated polyether production of other low molecule amounts
Product without reference to.
Patent CN106633208 is disclosed using Ni-Cu-Cr-M-N as the synthetically prepared amine terminated polyether of catalyst continuous catalysis
Method.M is rare earth metal or precious metal catalytic agent, and N is carrier, specific surface area of catalyst 150m2/ more than g, pore volume
More than 0.3ml/g.The amine terminated polyether product primary amine selectivity that the method synthesizes be more than 95%, reaction conversion ratio also greater than
95%, but fail to realize the H in course of reaction2With liquid NH3Recycled, and the more domestic Related product of primary amine content in product
Relatively low, product quality is poor.
The content of the invention
In order to solve drawbacks described above present in prior art, the present invention provides a kind of company of small-molecular-weight amine terminated polyether
Continuous preparation facilities and preparation method.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
A kind of continuous preparation device of small-molecular-weight amine terminated polyether, including hydrogen-storing device, liquid ammonia storage tank, PPG
Storage tank, mixing preheater, fixed bed reactors I, fixed bed reactors II, one-level gas-liquid separator, stage casing drying tower, two level gas
Liquid/gas separator, circulating hydrogen compressor, flash evaporation deamination tower, pressurized liquefied device, dehydrating tower, wastewater disposal basin and product storage tank；
The material outlet of the material outlet of hydrogen-storing device, the material outlet of liquid ammonia storage tank and PPG storage tank is respectively
Connected by pipeline with mixing the material inlet of preheater；
The material outlet for mixing preheater is connected by pipeline with the material inlet at the top of fixed bed reactors I, fixed bed
The material outlet of the bottom of reactor I is connected by pipeline with the material inlet of one-level gas-liquid separator；One-level gas-liquid separator bottom
The liquid outlet in portion is connected by pipeline with the material inlet at the top of fixed bed reactors II, the gas at the top of one-level gas-liquid separator
Body outlet is connected by pipeline with the material inlet of stage casing drying tower, and the material outlet of stage casing drying tower passes through pipeline and fixed bed
The material inlet connection at the top of reactor II；
The material outlet of the bottom of fixed bed reactors II is connected by pipeline with the material inlet of two level gas-liquid separator；Two
Gas vent at the top of level gas-liquid separator is connected by pipeline with the material inlet of circulating hydrogen compressor, circulating hydrogen compressor
Material outlet is connected by pipeline with the material inlet of hydrogen-storing device；The liquid outlet of two level gas-liquid separator bottom passes through pipeline
Connected with the material inlet of flash evaporation deamination tower；
The gas vent of flash evaporation deamination top of tower is connected by pipeline with the material inlet of pressurized liquefied device, pressurized liquefied
The material outlet of device is connected by pipeline with the material inlet of liquid ammonia storage tank；The liquid outlet of flash evaporation deamination tower bottom passes through pipe
Road connects with the material inlet of dehydrating tower, and the wastewater outlet at the top of dehydrating tower, by pipeline connection, is dehydrated tower bottom with wastewater disposal basin
Products export and product storage tank pass through pipeline connection.
The equipment such as pump, flowmeter can be set on above-mentioned each connecting line as needed.
In order to facilitate use, stage casing drying tower uses the structure of parallel two towers, and one is used for drying, and another is used in tower
The regeneration of filler, cyclic switching use.
In order to ensure drying efficiency, one of inner-tower filling material in silica gel, activated carbon or activated alumina is dried in stage casing
Kind or a variety of mixtures.
A kind of continuous preparation method of small-molecular-weight amine terminated polyether, including following steps connected in order：
1) loaded respectively in fixed bed reactors I and fixed bed reactors II isometric load-type nickel series catalysts and
Thunder Buddhist nun's type nickel catalyst is used to face hydrogen aminating reaction；
2) material liquid NH3, small-molecular-weight PPG and H2Enter admittedly after being sufficiently mixed preheating into mixing preheater
Fixed bed reactor I, the generation first step faces hydrogen aminating reaction under the effect of load-type nickel series catalysts；
3) reaction solution of the bottom of fixed bed reactors I outflow carries out high temperature gas-liquid separation, gained through one-level gas-liquid separator
Liquid material of the gas with the outflow of one-level gas-liquid separator bottom after the drying of stage casing drying tower enters fixed bed reactors II in the lump,
Second step occurs again in the presence of thunder Buddhist nun's type nickel catalyst and faces hydrogen aminating reaction；
4) bottom of fixed bed reactors II outflow feed liquid carries out normal temperature gas-liquid separation through two level gas-liquid separator, isolates
H2Applied mechanically through circulating hydrogen compressor compression Posterior circle；
5) two level gas-liquid separator bottom institute's out-feed liquid removes unreacted ammonia through flash evaporation deamination tower, and will flash distillation gained ammonia
It is pressurized liquefied and recycle；
6) small molecule amine terminated polyether product is obtained after dehydrating tower is dehydrated by the feed liquid that flash evaporation deamination tower bottom flows out.
Material liquid NH in step 2)3, small-molecular-weight PPG and H2Need to squeeze into mixing preheater through feed pump respectively
In, H2Before mixing preheater is entered, measured with hydrogen quality flowmeter.
The present invention has carried out further improvement and optimization on the basis of patent CN104231256：First, overcome
Original continuity method prepares amine terminated polyether process conditions harshness, and reaction temperature is high (190~240 DEG C), reaction pressure height (6~
13MPa), the shortcomings that being not easy to carry out industrialization promotion, this application provides a kind of reaction temperature and pressure are lower, milder
The continuous method for preparing small-molecular-weight amine terminated polyether；Secondly, the present invention is shared using support type with thunder Buddhist nun's type catalyst, and will
" two-step method " technique of two fixed bed reactors series connection, the catalyst cost of final products is not only reduced, also effectively lifting
The Feed space velocities of raw material small molecule PPG, while significantly reduce H2Usage amount, so as to substantially increase equipment
Production capacity, it is contemplated that economic benefit be significantly increased, there is more preferable industrialization promotion prospect.
Load-type nickel series catalysts and Lei Ni type nickel catalyst preparation methods are known to the skilled person, not in detail
Narration.
It is preferred that the molecular weight of small-molecular-weight raw material PPG is 200~900, degree of functionality is 2~3.
In order to improve reaction selectivity and primary amine conversion ratio, the interior reaction temperature of fixed bed reactors I is 140~180 DEG C, instead
It is 1.5~2.0Mpa to answer pressure；The interior reaction temperature of fixed bed reactors II be 180~200 DEG C, reaction pressure be 0.2~
1.0Mpa；It is 50~100 DEG C to mix temperature in preheater；Temperature is 110~160 DEG C in one-level gas-liquid separator, two level gas-liquid
Temperature is 5~25 DEG C in separator；Temperature is 10~50 DEG C in flash evaporation deamination tower, and pressure is 0~0.5Mpa；Temperature in dehydrating tower
For 50~90 DEG C, pressure is -0.093~-0.075MPa.
In order to improve drying efficiency, and then improve the quality of product, stage casing dry inner-tower filling material be selected from silica gel, activated carbon or
One or more mixtures in person's activated alumina, temperature is 80~130 DEG C in tower；Stage casing drying tower uses two groups simultaneously
Connection, one is used for drying, and another is used for the regeneration of inner-tower filling material, and cyclic switching uses.
It is preferred that in step 2), liquid NH3With the mol ratio 5~15 of hydroxyl (- OH) in small-molecular-weight PPG molecule:
1,H2Mol ratio with hydroxyl (- OH) in small-molecular-weight PPG molecule is 0.1~1:1.
In order to ensure the quality of products obtained therefrom, it is preferable that in step 2), liquid NH3Feed space velocities are 1.0~5.0h-1；Polyethers is more
First alcohol feed volume air speed is 1.0~10.0h-1；H2Flow velocity is 5~20L/h.
In order to improve reaction efficiency, it is preferable that in fixed bed reactors I load-type nickel series catalysts containing mass percent 90~
95% W metal, 1~8% metal Cr, 0.2~4% metal Fe；The Nei Leini type nickel catalysts of fixed bed reactors II
Granularity be 20~60 mesh, activity is 1~5ml H2/ min ﹒ g, thunder Buddhist nun's type nickel catalyst wet method dress post, use after drying.
The optional volume 5ml~50L of fixed bed reactors of the present invention, it is contemplated that raw materials consumption and Catalyst packing
Amount, it is preferable that the volume of fixed bed reactors I and fixed bed reactors II is 350ml, and fixed bed reactors I and fixed bed are anti-
It is 0.1~0.5 to answer the admission space of catalyst and fixed bed reactors volumetric ratio in device II:1, more preferably 0.2~
0.4:1。
Above method small-molecular-weight amine terminated polyether successive reaction conversion ratio is more than 99.0%, and primary amine selectivity is more than
98.5%.
The NM technology of the present invention is with reference to prior art.
Beneficial effect：
Compared with prior art, the invention has the advantages that:
1. reaction condition milder, temperature, pressure are significantly reduced, and are easy to industrialization promotion and application；
2. effectively improving the feedstock air speed of equipment, production capacity and economic benefit have been obviously improved；
3. reduce H2Usage amount, improve the Atom economy of course of reaction；
4. realize liquid NH3And H2Circulating and recovering, not only environmental protection but also saving；
5. under the control condition of the present invention, the present invention is applied to by 230~900 PPG of molecular weight be former
Material prepares amine terminated polyether, reaction conversion ratio >=99.0%, primary amine selectivity >=98.5%, promotional value height.
Brief description of the drawings
Fig. 1 is the structural representation of the continuous preparation device of small-molecular-weight amine terminated polyether of the present invention；
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
As shown in figure 1, each example prepares the continuous preparation device of small-molecular-weight amine terminated polyether used, including hydrogen storage dress
Put, liquid ammonia storage tank, PPG storage tank, mixing preheater, fixed bed reactors I, fixed bed reactors II, one-level gas-liquid point
From device, stage casing drying tower, two level gas-liquid separator, circulating hydrogen compressor, flash evaporation deamination tower, pressurized liquefied device, dehydrating tower, useless
Pond and product storage tank；
The material outlet of the material outlet of hydrogen-storing device, the material outlet of liquid ammonia storage tank and PPG storage tank is respectively
Connected by pipeline with mixing the material inlet of preheater；
The material outlet for mixing preheater is connected by pipeline with the material inlet at the top of fixed bed reactors I, fixed bed
The material outlet of the bottom of reactor I is connected by pipeline with the material inlet of one-level gas-liquid separator；One-level gas-liquid separator bottom
The liquid outlet in portion is connected by pipeline with the material inlet at the top of fixed bed reactors II, the gas at the top of one-level gas-liquid separator
Body outlet is connected by pipeline with the material inlet of stage casing drying tower, and the material outlet of stage casing drying tower passes through pipeline and fixed bed
The material inlet connection at the top of reactor II；
The material outlet of the bottom of fixed bed reactors II is connected by pipeline with the material inlet of two level gas-liquid separator；Two
Gas vent at the top of level gas-liquid separator is connected by pipeline with the material inlet of circulating hydrogen compressor, circulating hydrogen compressor
Material outlet is connected by pipeline with the material inlet of hydrogen-storing device；The liquid outlet of two level gas-liquid separator bottom passes through pipeline
Connected with the material inlet of flash evaporation deamination tower；
The gas vent of flash evaporation deamination top of tower is connected by pipeline with the material inlet of pressurized liquefied device, pressurized liquefied
The material outlet of device is connected by pipeline with the material inlet of liquid ammonia storage tank；The liquid outlet of flash evaporation deamination tower bottom passes through pipe
Road connects with the material inlet of dehydrating tower, and the wastewater outlet at the top of dehydrating tower, by pipeline connection, is dehydrated tower bottom with wastewater disposal basin
Products export and product storage tank pass through pipeline connection.
Stage casing drying tower uses the structure of parallel two towers, and the gas vent at the top of one-level gas-liquid separator is distinguished by pipeline
Connected with the material inlet of two stage casing drying towers, the material outlet of each stage casing drying tower is anti-with fixed bed by pipeline respectively
Answer the material inlet connection at the top of device II.
Embodiment 1
Respectively by 100mL load-type nickels series catalysts (containing Ni 92%, Cr 7.8%, Fe 0.2%) and 100mL thunder Buddhist nun's types
Nickel catalyst (mesh of granularity 20, active 1ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ and (a diameter of 25mm, is highly
720mm, volume about 350ml) fixed bed reactors I and II in (catalyst volume and fixed bed volumetric ratio are 0.29:1), rise
Temperature is simultaneously passed through H2Activated and dried.After the completion of, H is pressed into mixing preheater with 12L/h flow velocitys2, volume space velocity be
2.0h-1NH3And volume space velocity is 1.0h-1, molecular weight 230, degree of functionality be 2 small-molecular-weight polyethers (NH3With polyether polyols
Hydroxyl mol ratio is 8 in alcohol molecule:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.6:1)；Filled at 60 DEG C
Divide mixing preheating, then fixed bed reactors I are entered by top, the first step, which occurs, at 180 DEG C, under 2.5MPa faces hydrogen aminating reaction；
Product is through the gas-liquid separation at 110 DEG C of one-level gas-liquid separator, and top gas is through 80 DEG C of drying tower (filling gel particle in tower)
Enter fixed bed reactors II after drying together with the liquid of one-level gas-liquid separator bottom, occurs under 190 DEG C, 1.0MPa
Two steps face hydrogen aminating reaction；Product is through the gas-liquid separation at 25 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level
Gas-liquid separator bottom liquid enters flash evaporation deamination tower, at 10 DEG C, 0MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 50
DEG C, be dehydrated under -0.093MPa, obtain small-molecular-weight amine terminated polyether product D230 (D represents functional group's degree of PPG as 2,
230 represent the molecular weight of PPG, and following examples are herewith).
After testing, D230 products amine value 480mgKOH/g, active hydrogen equivalent weight (AHEW) 59.8g/eq；Reaction conversion ratio
99.3%, primary amine production rate 98.8%.
Embodiment 2
35mL load-type nickels series catalysts (containing Ni 95%, Cr 3%, Fe 2%) and 35mL thunder Buddhist nun's type nickel system are urged respectively
Agent (mesh of granularity 40, active 5ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.2 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Carry out
Activate and dry.After the completion of, H is pressed into mixing preheater with 8L/h flow velocitys2, volume space velocity 4.0h-1NH3And volume
Air speed is 2.0h-1, molecular weight 400, degree of functionality be 2 small-molecular-weight polyethers (NH3With hydroxyl mol ratio in PPG molecule
For 15:1；H2Mol ratio with hydroxyl in PPG molecule is about 1:1)；Preheating is sufficiently mixed at 50 DEG C, then by top
Into fixed bed reactors I, the first step occurs at 140 DEG C, under 1.5MPa and faces hydrogen aminating reaction；Product is through one-level gas-liquid separator
The gas-liquid separation at 160 DEG C, top gas is after 130 DEG C of dryings of drying tower (hybrid particles of filling activated carbon and silica gel in tower)
With entering fixed bed reactors II together with the liquid of one-level gas-liquid separator bottom, second step occurs at 200 DEG C, under 0.8MPa and faces
Hydrogen aminating reaction；Product is through the gas-liquid separation at 5 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level gas-liquid point
Enter flash evaporation deamination tower from device bottom liquid, at 50 DEG C, 0.5MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 80 DEG C ,-
It is dehydrated under 0.075MPa, obtains small-molecular-weight amine terminated polyether product D400.
After testing, D400 products amine value 255mgKOH/g, active hydrogen equivalent weight (AHEW) 110g/eq；Reaction conversion ratio
99.3%, primary amine production rate 98.6%.
Embodiment 3
Respectively by 155mL load-type nickels series catalysts (containing Ni 90%, Cr 8%, Fe 2%) and 155mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 30, active 3ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.44 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Enter
Row is activated and dried.After the completion of, H is pressed into mixing preheater with 20L/h flow velocitys2, volume space velocity 1.0h-1NH3And
Volume space velocity is 2.0h-1, molecular weight 600, degree of functionality be 2 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 5:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.9:1)；Preheating is sufficiently mixed at 100 DEG C, then
Fixed bed reactors I are entered by top, the first step, which occurs, at 160 DEG C, under 2.0MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid
Separator gas-liquid separation at 130 DEG C, top gas after drying tower (tower in filling activated alumina particle) is dried with one-level
The liquid of gas-liquid separator bottom enters fixed bed reactors II together, and second step, which occurs, at 180 DEG C, under 0.2MPa faces hydrogen ammonification
Reaction；Product is through the gas-liquid separation at 15 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level gas-liquid separator bottom
Portion's liquid enters flash evaporation deamination tower, at 30 DEG C, 0.1MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 90 DEG C ,-
Be dehydrated under 0.084MPa, obtain small-molecular-weight amine terminated polyether product E D600 (E represents PPG initiator as ethylene glycol, with
Lower embodiment is herewith).
After testing, ED600 products amine value 188mgKOH/g, active hydrogen equivalent weight (AHEW) 132g/eq；Reaction conversion ratio
99.5%, primary amine production rate 98.7%.
Embodiment 4
Respectively by 100mL load-type nickels series catalysts (containing Ni 95%, Cr 1%, Fe 4%) and 100mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 60, active 2ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.29 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Enter
Row is activated and dried.After the completion of, H is pressed into mixing preheater with 5L/h flow velocitys2, volume space velocity 5.0h-1NH3And body
Product air speed is 10.0h-1, molecular weight 900, degree of functionality be 2 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 8:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.1:1)；Preheating is sufficiently mixed at 90 DEG C, then
Fixed bed reactors I are entered by top, the first step, which occurs, at 175 DEG C, under 1.8MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid
Separator gas-liquid separation at 120 DEG C, top gas is through drying tower (filling gel and activated alumina hybrid particles in tower) 100
DEG C dry after enter fixed bed reactors II together with the liquid of one-level gas-liquid separator bottom, at 185 DEG C, 0.75MPa is issued
Raw second step faces hydrogen aminating reaction；Product is through the gas-liquid separation at 20 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；
Two level gas-liquid separator bottom liquid enters flash evaporation deamination tower, at 45 DEG C, 0.4MPa flash evaporation deaminations；Materials at bottom of tower enters dehydration
Tower, it is dehydrated under 85 DEG C, -0.090MPa, obtains small-molecular-weight amine terminated polyether product E D900.
After testing, ED900 products amine value 100mgKOH/g, active hydrogen equivalent weight (AHEW) 252g/eq；Aminating reaction conversion ratio
99.6%, primary amine production rate 98.6%.
Embodiment 5
Respectively by 100mL load-type nickels series catalysts (containing Ni 95%, Cr 1%, Fe 4%) and 100mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 40, active 3ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.29 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Enter
Row is activated and dried.After the completion of, H is pressed into mixing preheater with 9.1L/h flow velocitys2, volume space velocity 3.5h-1NH3And
Volume space velocity is 3.0h-1, molecular weight 440, degree of functionality be 3 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 6:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.2:1)；Preheating is sufficiently mixed at 80 DEG C, then
Fixed bed reactors I are entered by top, the first step, which occurs, at 165 DEG C, under 2.5MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid
Separator gas-liquid separation at 135 DEG C, top gas after 120 DEG C of drying tower (tower in filling activated carbon granule) is dried with one-level
The liquid of gas-liquid separator bottom enters fixed bed reactors II together, and second step, which occurs, at 195 DEG C, under 0.85MPa faces hydrogen ammonia
Change reaction；Product is through the gas-liquid separation at 20 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level gas-liquid separator
Bottom liquid enters flash evaporation deamination tower, at 35 DEG C, 0.3MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 85 DEG C ,-
It is dehydrated under 0.089MPa, obtains small-molecular-weight amine terminated polyether product T403.(T represents the degree of functionality of PPG as 3, below
Embodiment is herewith).
After testing, T403 products amine value 345mgKOH/g, active hydrogen equivalent weight (AHEW) 82g/eq；Aminating reaction conversion ratio
99.7%, primary amine production rate 98.6%.
Embodiment 6
Respectively by 100mL load-type nickels series catalysts (containing Ni 95%, Cr 4.8%, Fe 0.2%) and 100mL thunder Buddhist nun's types
Nickel catalyst (mesh of granularity 50, active 2ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ and (a diameter of 25mm, is highly
720mm, volume about 350ml) fixed bed reactors I and II in (catalyst volume and fixed bed volumetric ratio are 0.29:1), rise
Temperature is simultaneously passed through H2Activated and dried.After the completion of, H is pressed into mixing preheater with 20L/h flow velocitys2, volume space velocity be
3.8h-1NH3And volume space velocity is 1.5h-1, molecular weight 230, degree of functionality be 2 small-molecular-weight polyethers (NH3With polyether polyols
Hydroxyl mol ratio is 10 in alcohol molecule:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.7:1)；At 65 DEG C
Preheating is sufficiently mixed, then fixed bed reactors I are entered by top, at 190 DEG C, it is anti-to face hydrogen ammonification for the generation first step under 2.4MPa
Should；Product is through the gas-liquid separation at 150 DEG C of one-level gas-liquid separator, and top gas is through drying tower (filling gel particle in tower)
Enter fixed bed reactors II after 115 DEG C of dryings together with the liquid of one-level gas-liquid separator bottom, at 190 DEG C, under 0.5MPa
Generation second step faces hydrogen aminating reaction；Product is through the gas-liquid separation at 25 DEG C of two level gas-liquid separator, the H isolated2It is recycled back to
With；Two level gas-liquid separator bottom liquid enters flash evaporation deamination tower, at 15 DEG C, 0.4MPa flash evaporation deaminations；Materials at bottom of tower enters de-
Water tower, it is dehydrated under 60 DEG C, -0.088MPa, obtains small-molecular-weight amine terminated polyether product D230.
After testing, D230 products amine value 482mgKOH/g, active hydrogen equivalent weight (AHEW) 60.0g/eq；Aminating reaction conversion ratio
99.4%, primary amine production rate 98.5%.
Embodiment 7
Respectively by 70mL load-type nickels series catalysts (containing Ni 94%, Cr 5.6%, Fe 0.4%) and 70mL thunder Buddhist nun's type nickel
Series catalysts (mesh of granularity 40, active 3ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.2 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Carry out
Activate and dry.After the completion of, H is pressed into mixing preheater with 12L/h flow velocitys2, volume space velocity 2.2h-1NH3And body
Product air speed is 1.5h-1, molecular weight 400, degree of functionality be 2 small-molecular-weight polyethers (NH3With hydroxyl mole in PPG molecule
Than for 10:1；H2Mol ratio with hydroxyl in PPG molecule is about 1:1)；Preheating is sufficiently mixed at 95 DEG C, then by pushing up
Portion enters fixed bed reactors I, and the first step, which occurs, at 180 DEG C, under 1.7MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid separation
Device gas-liquid separation at 155 DEG C, top gas is through 120 DEG C of drying tower (filling activated alumina and activated carbon hybrid particles in tower)
Enter fixed bed reactors II after drying together with the liquid of one-level gas-liquid separator bottom, occurs under 190 DEG C, 0.7MPa
Two steps face hydrogen aminating reaction；Product is through the gas-liquid separation at 15 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level
Gas-liquid separator bottom liquid enters flash evaporation deamination tower, at 40 DEG C, 0.2MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in
80 DEG C, it is dehydrated under -0.089MPa, obtains small-molecular-weight amine terminated polyether product D400.
After testing, D400 products amine value 243.5mgKOH/g, active hydrogen equivalent weight (AHEW) 115g/eq；Aminating reaction converts
Rate 99.7%, primary amine production rate 98.9%.
Embodiment 8
Respectively by 100mL load-type nickels series catalysts (containing Ni 90%, Cr 8%, Fe 2%) and 100mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 30, active 5ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.29 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Enter
Row is activated and dried.After the completion of, H is pressed into mixing preheater with 18L/h flow velocitys2, volume space velocity 5.0h-1NH3And
Volume space velocity is 6.0h-1, molecular weight 600, degree of functionality be 2 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 9:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.4:1)；Preheating is sufficiently mixed at 90 DEG C, then
Fixed bed reactors I are entered by top, the first step, which occurs, at 165 DEG C, under 1.5MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid
Separator gas-liquid separation at 155 DEG C, top gas are dry through drying tower (filling activated alumina and silica gel hybrid particles in tower)
Enter fixed bed reactors II after dry together with the liquid of one-level gas-liquid separator bottom, occur second under 190 DEG C, 0.8MPa
Step faces hydrogen aminating reaction；Product is through the gas-liquid separation at 25 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level gas
Liquid/gas separator bottom liquid enters flash evaporation deamination tower, at 25 DEG C, 0.1MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 85
DEG C, it is dehydrated under -0.090MPa, obtains small-molecular-weight amine terminated polyether product E D600.
After testing, ED600 products amine value 170mgKOH/g, active hydrogen equivalent weight (AHEW) 130g/eq；Aminating reaction conversion ratio
99.6%, primary amine production rate 99.0%.
Embodiment 9
Respectively by 120mL load-type nickels series catalysts (containing Ni 90%, Cr 7%, Fe 3%) and 120mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 20, active 5ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.34 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Enter
Row is activated and dried.After the completion of, H is pressed into mixing preheater with 18L/h flow velocitys2, volume space velocity 4.0h-1NH3And
Volume space velocity is 8.0h-1, molecular weight 900, degree of functionality be 2 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 8:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.38:1)；Preheating is sufficiently mixed at 100 DEG C,
Fixed bed reactors I are entered by top again, the first step, which occurs, at 180 DEG C, under 2.5MPa faces hydrogen aminating reaction；Product is through one-level gas
Liquid/gas separator gas-liquid separation at 125 DEG C, top gas after 110 DEG C of dryings of drying tower (filling gel particle in tower) with one-level
The liquid of gas-liquid separator bottom enters fixed bed reactors II together, and second step, which occurs, at 190 DEG C, under 1.0MPa faces hydrogen ammonification
Reaction；Product is through the gas-liquid separation at 45 DEG C of two level gas-liquid separator, the H isolated2Circulating and recovering；Two level gas-liquid separator bottom
Portion's liquid enters flash evaporation deamination tower, at 25 DEG C, 0MPa flash evaporation deaminations；Materials at bottom of tower enters dehydrating tower, in 80 DEG C, -0.079MPa
Lower dehydration, obtain small-molecular-weight amine terminated polyether product E D900.
After testing, ED900 products amine value 110mgKOH/g, active hydrogen equivalent weight (AHEW) 250g/eq；Aminating reaction conversion ratio
99.4%, primary amine production rate 98.7%.
Embodiment 10
Respectively by 175mL load-type nickels series catalysts (containing Ni 95%, Cr 1%, Fe 4%) and 175mL thunder Buddhist nun's type nickel system
Catalyst (mesh of granularity 30, active 1ml H2/ min ﹒ g) it is filled in 25 × 720mm of φ (diameter 25mm, height 720mm, volume
(catalyst volume is 0.5 with fixed bed volumetric ratio in fixed bed reactors I and II 350ml):1), heat up and be passed through H2Carry out
Activate and dry.After the completion of, H is pressed into mixing preheater with 13.5L/h flow velocitys2, volume space velocity 4.6h-1NH3And
Volume space velocity is 3.0h-1, molecular weight 440, degree of functionality be 3 small-molecular-weight polyethers (NH3Rubbed with hydroxyl in PPG molecule
You are than being 8:1；H2Mol ratio with hydroxyl in PPG molecule is about 0.2:1)；Preheating is sufficiently mixed at 85 DEG C, then
Fixed bed reactors I are entered by top, the first step, which occurs, at 185 DEG C, under 2.0MPa faces hydrogen aminating reaction；Product is through one-level gas-liquid
Separator gas-liquid separation at 130 DEG C, top gas is through drying tower (filling activated carbon and activated alumina hybrid particles in tower)
Enter fixed bed reactors II after 130 DEG C of dryings together with the liquid of one-level gas-liquid separator bottom, at 200 DEG C, under 1.0MPa
Generation second step faces hydrogen aminating reaction；Product is through the gas-liquid separation at 25 DEG C of two level gas-liquid separator, the H isolated2It is recycled back to
With；Two level gas-liquid separator bottom liquid enters flash evaporation deamination tower, at 45 DEG C, 0MPa flash evaporation deaminations；Materials at bottom of tower enters dehydration
Tower, it is dehydrated under 85 DEG C, -0.075MPa, obtains small-molecular-weight amine terminated polyether product T403.
After testing, T403 products amine value 355mgKOH/g, active hydrogen equivalent weight (AHEW) 81g/eq；Aminating reaction conversion ratio
99.4%, primary amine production rate 99.0%.
Claims (10)
- A kind of 1. continuous preparation device of small-molecular-weight amine terminated polyether, it is characterised in that including hydrogen-storing device, liquid ammonia storage tank, PPG storage tank, mixing preheater, fixed bed reactors I, fixed bed reactors II, one-level gas-liquid separator, stage casing are done Dry tower, two level gas-liquid separator, circulating hydrogen compressor, flash evaporation deamination tower, pressurized liquefied device, dehydrating tower, wastewater disposal basin and product Storage tank；The material outlet of the material outlet of hydrogen-storing device, the material outlet of liquid ammonia storage tank and PPG storage tank respectively passes through Pipeline connects with mixing the material inlet of preheater；The material outlet for mixing preheater is connected by pipeline with the material inlet at the top of fixed bed reactors I, fixed bed reaction The material outlet of the bottom of device I is connected by pipeline with the material inlet of one-level gas-liquid separator；One-level gas-liquid separator bottom Liquid outlet is connected by pipeline with the material inlet at the top of fixed bed reactors II, and the gas at the top of one-level gas-liquid separator goes out Mouth is connected by pipeline with the material inlet of stage casing drying tower, and the material outlet of stage casing drying tower passes through pipeline and fixed bed reaction The material inlet connection at the top of device II；The material outlet of the bottom of fixed bed reactors II is connected by pipeline with the material inlet of two level gas-liquid separator；Two level gas Gas vent at the top of liquid/gas separator is connected by pipeline with the material inlet of circulating hydrogen compressor, the material of circulating hydrogen compressor Outlet is connected by pipeline with the material inlet of hydrogen-storing device；The liquid outlet of two level gas-liquid separator bottom is by pipeline with dodging Steam the material inlet connection of deammoniation tower；The gas vent of flash evaporation deamination top of tower is connected by pipeline with the material inlet of pressurized liquefied device, pressurized liquefied device Material outlet connected by pipeline with the material inlet of liquid ammonia storage tank；The liquid outlet of flash evaporation deamination tower bottom by pipeline with The material inlet of dehydrating tower connects, and the wastewater outlet at the top of dehydrating tower, by pipeline connection, is dehydrated the production of tower bottom with wastewater disposal basin Product export passes through pipeline connection with product storage tank.
- 2. the continuous preparation device of small-molecular-weight amine terminated polyether as claimed in claim 1, it is characterised in that stage casing drying tower Using the structure of parallel two towers.
- 3. the continuous preparation device of small-molecular-weight amine terminated polyether as claimed in claim 1 or 2, it is characterised in that do in stage casing Dry inner-tower filling material is selected from least one of silica gel, activated carbon or activated alumina.
- 4. a kind of continuous preparation method of small-molecular-weight amine terminated polyether, it is characterised in that using described in claim 1 or 2 Prepared by the continuous preparation device of small-molecular-weight amine terminated polyether, including following steps connected in order：1) isometric load-type nickel series catalysts and Lei Ni are loaded respectively in fixed bed reactors I and fixed bed reactors II Type nickel catalyst is used to face hydrogen aminating reaction；2) material liquid NH3, small-molecular-weight PPG and H2Enter fixed bed after being sufficiently mixed preheating into mixing preheater Reactor I, the generation first step faces hydrogen aminating reaction under the effect of load-type nickel series catalysts；3) reaction solution of the bottom of fixed bed reactors I outflow carries out high temperature gas-liquid separation, gained gas through one-level gas-liquid separator Liquid material with the outflow of one-level gas-liquid separator bottom after the drying of stage casing drying tower enters fixed bed reactors II in the lump, in thunder Second step occurs again in the presence of Buddhist nun's type nickel catalyst and faces hydrogen aminating reaction；4) bottom of fixed bed reactors II outflow feed liquid carries out normal temperature gas-liquid separation, the H isolated through two level gas-liquid separator2Through Circulating hydrogen compressor compression Posterior circle is applied mechanically；5) two level gas-liquid separator bottom institute's out-feed liquid removes unreacted ammonia through flash evaporation deamination tower, and will flash distillation gained ammonia pressurization Liquefy and recycle；6) small molecule amine terminated polyether product is obtained after dehydrating tower is dehydrated by the feed liquid that flash evaporation deamination tower bottom flows out.
- 5. the continuous preparation method of small-molecular-weight amine terminated polyether according to claim 4, it is characterised in that fixed bed reactors I interior reaction temperature is 140~180 DEG C, and reaction pressure is 1.5~2.0Mpa；The interior reaction temperature of fixed bed reactors II be 180~ 200 DEG C, reaction pressure is 0.2~1.0Mpa；It is 50~100 DEG C to mix temperature in preheater；Temperature in one-level gas-liquid separator For 110~160 DEG C, temperature is 5~25 DEG C in two level gas-liquid separator；Temperature is 10~50 DEG C in flash evaporation deamination tower, pressure 0 ~0.5Mpa；Temperature is 50~90 DEG C in dehydrating tower, and pressure is -0.093~-0.075MPa.
- 6. the continuous preparation method of the amine terminated polyether according to claim 4 or 5, it is characterised in that in the drying tower of stage casing Filler is selected from least one of silica gel, activated carbon or activated alumina, and temperature is 80~130 DEG C in tower；Stage casing drying tower In parallel using two groups, one is used for drying, and another is used for the regeneration of inner-tower filling material, and cyclic switching uses.
- 7. according to claim 4 or 5 described amine terminated polyether continuous preparation method, it is characterised in that in step 2), liquid NH3With the mol ratio 5~15 of hydroxyl (- OH) in small-molecular-weight PPG molecule:1,H2With small-molecular-weight PPG point The mol ratio of hydroxyl (- OH) is 0.1~1 in son:1.
- 8. according to claim 4 or 5 described amine terminated polyether continuous preparation method, it is characterised in that in step 2), liquid NH3Feed space velocities are 1.0~5.0h-1；PPG feed volume air speed is 1.0~10.0h-1；H2Flow velocity is 5~20L/h.
- 9. according to claim 4 or 5 described amine terminated polyether continuous preparation method, it is characterised in that small-molecular-weight is former Expect the molecular weight 200~900 of PPG, degree of functionality 2~3.
- 10. the continuous preparation method of the amine terminated polyether according to claim 4 or 5, it is characterised in that fixed bed reactors W metal of the load-type nickel series catalysts containing mass percent 90~95% in I, 1~8% metal Cr, 0.2~4% metal Fe；The granularity of the Nei Leini type nickel catalysts of fixed bed reactors II is 20~60 mesh, and activity is 1~5mlH2/ min ﹒ g, thunder Buddhist nun Type nickel catalyst wet method dress post, use after drying；The volume of fixed bed reactors I and fixed bed reactors II is The admission space of catalyst is with fixed bed reactors volumetric ratio in 350ml, fixed bed reactors I and fixed bed reactors II 0.1~0.5:1.
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| CN114247385A (en) * | 2021-12-01 | 2022-03-29 | 浙江皇马科技股份有限公司 | System and method for preparing polyetheramine by catalytically aminating polyether diol |
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| CN116425643A (en) * | 2023-04-10 | 2023-07-14 | 浙江皇马科技股份有限公司 | Amination process of small molecular polyoxypropylene ether |
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