CN107880260B - Continuous preparation device and preparation method of small molecular weight amino-terminated polyether - Google Patents
Continuous preparation device and preparation method of small molecular weight amino-terminated polyether Download PDFInfo
- Publication number
- CN107880260B CN107880260B CN201711392065.5A CN201711392065A CN107880260B CN 107880260 B CN107880260 B CN 107880260B CN 201711392065 A CN201711392065 A CN 201711392065A CN 107880260 B CN107880260 B CN 107880260B
- Authority
- CN
- China
- Prior art keywords
- fixed bed
- bed reactor
- liquid
- tower
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 109
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 148
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000001035 drying Methods 0.000 claims abstract description 52
- 229920005862 polyol Polymers 0.000 claims abstract description 46
- 150000003077 polyols Chemical class 0.000 claims abstract description 46
- 238000001704 evaporation Methods 0.000 claims abstract description 41
- 230000008020 evaporation Effects 0.000 claims abstract description 41
- 230000009615 deamination Effects 0.000 claims abstract description 39
- 238000006481 deamination reaction Methods 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 238000003860 storage Methods 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000004176 ammonification Methods 0.000 claims abstract description 26
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 230000018044 dehydration Effects 0.000 claims description 23
- 238000006297 dehydration reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 19
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 18
- 238000004064 recycling Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 4
- 208000012839 conversion disease Diseases 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 63
- 230000004913 activation Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910000510 noble metal Chemical group 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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)
Landscapes
- 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 continuous preparation device and a preparation method of small molecular weight amino-terminated polyether. A continuous preparation device of small molecular weight amino-terminated polyether comprises a hydrogen storage device, a liquid ammonia storage tank, a polyether polyol storage tank, a mixing preheater, a fixed bed reactor I, a fixed bed reactor II, a primary gas-liquid separator, a middle section drying tower, a secondary gas-liquid separator, a circulating hydrogen compressor, a flash evaporation deamination tower, a pressurizing liquefying device, a dehydrating tower, a wastewater tank and a product storage tank; the preparation is carried out by using polyether polyol with small molecular weight and H 2 And liquid NH 3 The method is characterized in that the method adopts two fixed bed reactors in series under the action of a catalyst to produce a 'two-step' hydro-ammonification reaction to prepare the small molecular weight amino-terminated polyether. The invention has continuous operation process, stable and controllable product quality and mild reaction conditions; realization of H 2 Liquid NH 3 Is more environment-friendly and economical; the reaction conversion rate is more than or equal to 99.0%, and the primary amine selectivity is more than or equal to 98.5%.
Description
Technical Field
The invention relates to a continuous preparation device and a preparation method of small molecular weight amino-terminated polyether, and belongs to the field of preparation of amino-terminated polyether.
Background
Amine-terminated polyether (Amine-Terminated Polyether, ATPE), also known as polyetheramine, is a polyoxyalkylene compound whose molecular backbone is a polyether backbone, but whose ends are terminated by amino groups. The amino group can be classified into primary amino group and secondary amino group terminated polyether according to the number of H atoms replaced in the amino group. At present, most of domestic amino-terminated polyether products are produced by an intermittent method, the types of the products are incomplete, the quality is unstable, and the productivity can not meet the market demand at all.
The synthesis of the amino polyether at the end of foreign companies at present mainly comprises continuous gas, liquid and solid three-phase fixed bed hydro-ammonification reaction. The fixed bed continuous synthesis method is the method which is the most feasible for synthesizing amino-terminated polyether at present, has the most stable product quality and is more environment-friendly, and more enterprises in China are carrying out related researches.
Patent CN103626988 discloses a metal Ni/Cu/M/Al 2 O 3 As a catalyst, a method of continuously synthesizing small molecular weight amino-terminated polyether by adopting a fixed bed is adopted, and M is one or more mixed auxiliary agents of Cr, fe and Zn. The method for preparing amino-terminated polyether by hydro-ammonification reaction of the polyether polyol with small molecular weight at 180-220 ℃ and 14-25 MPa. The selectivity of primary amine products is 97.5%, the reaction conversion rate can only reach 85.1%, the products can not reach the indexes of similar products in the market, the reaction temperature and the reaction pressure are high, and the operation safety is poor.
Patent CN102585211 discloses a method for continuously synthesizing amino-terminated polyether at 180-260 ℃ and 10-14 MPa by using a macroporous nickel-based catalyst. The method comprises the following three successive stages: a pretreatment stage, a reaction stage and a post-treatment stage. The catalyst contains 75-80% of Ni, 15-20% of Cu, 1-5% of Cr and 0.5-2% of Co by mass percent. The amine-terminated polyether product synthesized by the method has the primary amine selectivity of 97-99 percent and the reaction conversion rate of 95-99 percent, and only refers to unreacted NH although the ideal reaction conversion rate and primary amine product selectivity are obtained 3 And H 2 But cannot realize the recycling, the probability of environmental pollution is increased, and the safety of process operation is reduced. And the reaction pressure of 10-14 MPa is difficult to realize industrial amplification and production.
Patent CN106633028 utilizes a fixed bed to continuously synthesize amine-terminated polyether at 180-260 ℃ and 1-20 MPa with an ammonia-alcohol molar ratio of 1-15, has simple and convenient process operation and realizes NH 3 And H 2 The pollution is reduced, and the production efficiency is improved. However, the reaction conversion rate of the amino-terminated polyether prepared by the method is only about 92%, the primary amine selectivity is only 91-95%, only the small molecular weight amino-terminated polyether with the molecules of 230 and 400 is synthesized, and other low molecular weight amino-terminated polyether products are not involved.
Patent CN106633208 discloses a method for preparing amino-terminated polyether by continuous catalytic synthesis by taking Ni-Cu-Cr-M-N as a catalyst.M is rare earth metal or noble metal promoter, N is carrier, and specific surface area of catalyst is 150M 2 The volume of pores is more than 0.3 ml/g. The amine-terminated polyether product synthesized by the method has the primary amine selectivity of more than 95 percent and the reaction conversion rate of more than 95 percent, but cannot realize H in the reaction process 2 And liquid NH 3 The primary amine content in the product is lower than that of related products in China, and the product quality is poor.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a continuous preparation device and a preparation method of small molecular weight amino-terminated polyether.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a continuous preparation device of small molecular weight amino-terminated polyether comprises a hydrogen storage device, a liquid ammonia storage tank, a polyether polyol storage tank, a mixing preheater, a fixed bed reactor I, a fixed bed reactor II, a primary gas-liquid separator, a middle section drying tower, a secondary gas-liquid separator, a circulating hydrogen compressor, a flash evaporation deamination tower, a pressurizing liquefying device, a dehydrating tower, a wastewater tank and a product storage tank;
the material outlet of the hydrogen storage device, the material outlet of the liquid ammonia storage tank and the material outlet of the polyether polyol storage tank are respectively communicated with the material inlet of the mixing preheater through pipelines;
the material outlet of the mixing preheater is communicated with the material inlet at the top of the fixed bed reactor I through a pipeline, and the material outlet at the bottom of the fixed bed reactor I is communicated with the material inlet of the primary gas-liquid separator through a pipeline; the liquid outlet at the bottom of the first-stage gas-liquid separator is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline, the gas outlet at the top of the first-stage gas-liquid separator is communicated with the material inlet of the middle-stage drying tower through a pipeline, and the material outlet of the middle-stage drying tower is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline;
the material outlet at the bottom of the fixed bed reactor II is communicated with the material inlet of the secondary gas-liquid separator through a pipeline; the gas outlet at the top of the secondary gas-liquid separator is communicated with the material inlet of the circulating hydrogen compressor through a pipeline, and the material outlet of the circulating hydrogen compressor is communicated with the material inlet of the hydrogen storage device through a pipeline; the liquid outlet at the bottom of the secondary gas-liquid separator is communicated with the material inlet of the flash evaporation deamination tower through a pipeline;
the gas outlet at the top of the flash evaporation deamination tower is communicated with the material inlet of the pressurizing and liquefying device through a pipeline, and the material outlet of the pressurizing and liquefying device is communicated with the material inlet of the liquid ammonia storage tank through a pipeline; the liquid outlet at the bottom of the flash evaporation deamination tower is communicated with the material inlet of the dehydration tower through a pipeline, the waste water outlet at the top of the dehydration tower is communicated with the waste water pool through a pipeline, and the product outlet at the bottom of the dehydration tower is communicated with the product storage tank through a pipeline.
Pumps, flow meters and other devices can be arranged on the connecting pipelines according to the need.
For convenient use, the middle section drying tower adopts a structure that two towers are connected in parallel, one is used for drying, and the other is used for regenerating the filler in the tower, and the two towers are used in a circulating switching way.
In order to ensure the drying efficiency, the filler in the middle section drying tower is selected from one or a mixture of more of silica gel, activated carbon or activated alumina.
A continuous preparation method of small molecular weight amino-terminated polyether comprises the following steps of:
1) Respectively filling the fixed bed reactor I and the fixed bed reactor II with an equal volume of supported nickel catalyst and a Raney nickel catalyst for hydro-ammoniation reaction;
2) Raw material liquid NH 3 Polyether polyol of small molecular weight and H 2 Entering a mixing preheater for full mixing and preheating, and then entering a fixed bed reactor I, and carrying out a first-step hydro-ammoniation reaction under the action of a supported nickel catalyst;
3) The reaction liquid flowing out of the bottom of the fixed bed reactor I is subjected to high-temperature gas-liquid separation through a first-stage gas-liquid separator, the obtained gas is dried through a middle-stage drying tower, and then enters a fixed bed reactor II together with the liquid material flowing out of the bottom of the first-stage gas-liquid separator, and a second-step hydro-ammonification reaction occurs under the action of a Raney nickel catalyst;
4) Fixed bed reactor IISeparating the liquid from the bottom by a secondary gas-liquid separator at normal temperature to obtain H 2 Compressing by a circulating hydrogen compressor and circularly applying;
5) Removing unreacted ammonia from the discharged liquid at the bottom of the secondary gas-liquid separator through a flash evaporation deamination tower, pressurizing, liquefying and recycling the ammonia obtained by flash evaporation;
6) And dehydrating the feed liquid flowing out from the bottom of the flash evaporation deamination tower through a dehydration tower to obtain a micromolecular amino-terminated polyether product.
Step 2) raw material liquid NH 3 Polyether polyol of small molecular weight and H 2 Respectively pumping the mixture into a mixing preheater by a feed pump, H 2 Before entering the mixing preheater, a hydrogen mass flow meter was used for metering.
The invention is further improved and optimized based on the patent CN 104231256: firstly, the defect that the original continuous method for preparing amino-terminated polyether has harsh process conditions, high reaction temperature (190-240 ℃) and high reaction pressure (6-13 MPa) and is not easy to industrially popularize is overcome, and the application provides a method for continuously preparing small molecular weight amino-terminated polyether, wherein the reaction temperature and the reaction pressure are lower; secondly, the invention adopts the two-step process technology of combining the supported catalyst with the Raney catalyst and connecting two fixed bed reactors in series, thereby not only reducing the catalyst cost of the final product, but also effectively improving the feeding airspeed of the raw material micromolecular polyether polyol, and simultaneously obviously reducing H 2 The use amount of the catalyst is greatly improved, the expected economic benefit is obviously increased, and the catalyst has better industrialized popularization prospect.
Supported nickel catalysts and methods for preparing Raney nickel catalysts are well known to those skilled in the art and are not described in detail.
Preferably, the molecular weight of the small molecular weight raw material polyether polyol is 200-900, and the functionality is 2-3.
In order to improve the reaction selectivity and the primary amine conversion rate, the reaction temperature in the fixed bed reactor I is 140-180 ℃, and the reaction pressure is 1.5-2.0 Mpa; the reaction temperature in the fixed bed reactor II is 180-200 ℃ and the reaction pressure is 0.2-1.0 Mpa; the temperature in the mixing preheater is 50-100 ℃; the temperature in the primary gas-liquid separator is 110-160 ℃, and the temperature in the secondary gas-liquid separator is 5-25 ℃; the temperature in the flash evaporation deamination tower is 10-50 ℃ and the pressure is 0-0.5 Mpa; the temperature in the dehydration tower is 50-90 ℃, and the pressure is-0.093 to-0.075 MPa.
In order to improve the drying efficiency and further improve the quality of products, the filler in the middle section drying tower is selected from one or a mixture of more of silica gel, active carbon or active alumina, and the temperature in the tower is 80-130 ℃; the middle section drying tower adopts two groups of parallel connection, one is used for drying, and the other is used for regenerating the filler in the tower, and the two groups of drying towers are used in a circulating switching way.
Preferably, in step 2), the liquid NH 3 Molar ratio of the hydroxyl (-OH) to the hydroxyl (-OH) in the small molecular weight polyether polyol molecule is 5-15:1, H 2 The molar ratio of the hydroxyl (-OH) in the molecule of the polyether polyol with small molecular weight is 0.1-1:1.
In order to ensure the quality of the product obtained, it is preferred that in step 2), the NH liquid is 3 The space velocity of the feed is 1.0 to 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Polyether polyol feeding volume space velocity is 1.0-10.0 h -1 ；H 2 The flow rate is 5-20L/h.
In order to improve the reaction efficiency, preferably, the supported nickel catalyst in the fixed bed reactor I contains 90-95% of metal Ni, 1-8% of metal Cr and 0.2-4% of metal Fe by mass percent; the particle size of Raney nickel catalyst in the fixed bed reactor II is 20-60 meshes, and the activity is 1-5 ml H 2 And g, wet packing the Raney nickel catalyst, and drying for use.
The volume of the fixed bed reactor is 5 ml-50L, the volume of the fixed bed reactor I and the volume of the fixed bed reactor II are 350ml, the volume ratio of the catalyst filling volume in the fixed bed reactor I and the fixed bed reactor II to the volume of the fixed bed reactor is 0.1-0.5:1, and the volume ratio of the catalyst filling volume in the fixed bed reactor I and the fixed bed reactor II is 0.2-0.4:1 is preferable in view of raw material consumption and catalyst filling amount.
The method has the advantages that the continuous reaction conversion rate of the small molecular weight amino-terminated polyether is more than 99.0%, and the primary amine selectivity is more than 98.5%.
The technology not mentioned in the present invention refers to the prior art.
The beneficial effects are that:
compared with the prior art, the invention has the following advantages:
1. the reaction condition is milder, the temperature and the pressure are reduced to a great extent, and the industrial popularization and the application are easy;
2. the raw material feeding airspeed of the equipment is effectively improved, and the productivity and economic benefit are remarkably improved;
3. reduce H 2 The use amount of the catalyst improves the atom economy of the reaction process;
4. realize liquid NH 3 And H 2 The recycling is environment-friendly and saves;
5. under the control condition of the invention, the invention is suitable for preparing amino-terminated polyether by taking polyether polyol with the molecular weight of 230-900 as a raw material, the reaction conversion rate is more than or equal to 99.0%, the primary amine selectivity is more than or equal to 98.5%, and the popularization value is high.
Drawings
FIG. 1 is a schematic structural diagram of a continuous preparation apparatus for small molecular weight amino-terminated polyethers according to the present invention;
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
As shown in FIG. 1, the continuous preparation device of the small molecular weight amino-terminated polyether for preparation in each example comprises a hydrogen storage device, a liquid ammonia storage tank, a polyether polyol storage tank, a mixing preheater, a fixed bed reactor I, a fixed bed reactor II, a primary gas-liquid separator, a middle drying tower, a secondary gas-liquid separator, a circulating hydrogen compressor, a flash evaporation deamination tower, a pressurizing liquefying device, a dehydrating tower, a wastewater tank and a product storage tank;
the material outlet of the hydrogen storage device, the material outlet of the liquid ammonia storage tank and the material outlet of the polyether polyol storage tank are respectively communicated with the material inlet of the mixing preheater through pipelines;
the material outlet of the mixing preheater is communicated with the material inlet at the top of the fixed bed reactor I through a pipeline, and the material outlet at the bottom of the fixed bed reactor I is communicated with the material inlet of the primary gas-liquid separator through a pipeline; the liquid outlet at the bottom of the first-stage gas-liquid separator is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline, the gas outlet at the top of the first-stage gas-liquid separator is communicated with the material inlet of the middle-stage drying tower through a pipeline, and the material outlet of the middle-stage drying tower is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline;
the material outlet at the bottom of the fixed bed reactor II is communicated with the material inlet of the secondary gas-liquid separator through a pipeline; the gas outlet at the top of the secondary gas-liquid separator is communicated with the material inlet of the circulating hydrogen compressor through a pipeline, and the material outlet of the circulating hydrogen compressor is communicated with the material inlet of the hydrogen storage device through a pipeline; the liquid outlet at the bottom of the secondary gas-liquid separator is communicated with the material inlet of the flash evaporation deamination tower through a pipeline;
the gas outlet at the top of the flash evaporation deamination tower is communicated with the material inlet of the pressurizing and liquefying device through a pipeline, and the material outlet of the pressurizing and liquefying device is communicated with the material inlet of the liquid ammonia storage tank through a pipeline; the liquid outlet at the bottom of the flash evaporation deamination tower is communicated with the material inlet of the dehydration tower through a pipeline, the waste water outlet at the top of the dehydration tower is communicated with the waste water pool through a pipeline, and the product outlet at the bottom of the dehydration tower is communicated with the product storage tank through a pipeline.
The middle section drying tower adopts a structure that two towers are connected in parallel, a gas outlet at the top of the primary gas-liquid separator is respectively communicated with material inlets of the two middle section drying towers through pipelines, and a material outlet of each middle section drying tower is respectively communicated with a material inlet at the top of the fixed bed reactor II through a pipeline.
Example 1
100mL of the supported nickel catalyst (containing Ni 92%, cr 7.8%, and Fe 0.2%) and 100mL of the Raney nickel catalyst (particle size 20 mesh, activity 1mL of H) were each prepared 2 In a fixed-bed reactor I and II (catalyst volume to fixed-bed volume ratio of 0.29:1) filled with phi 25X 720mm (diameter 25mm, height 720mm, volume about 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 12L/H 2 Space velocity of volumeFor 2.0h -1 NH of (C) 3 A volume space velocity of 1.0h -1 Small molecular weight polyethers (NH) with a molecular weight of 230 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 8:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.6:1); fully mixing and preheating at 60 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammoniation reaction at 180 ℃ and 2.5 MPa; the product is subjected to gas-liquid separation at 110 ℃ through a primary gas-liquid separator, the top gas is dried at 80 ℃ through a drying tower (filled with silica gel particles in the tower), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 190 ℃ and 1.0MPa; the product is subjected to gas-liquid separation at 25 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 10 ℃ and 0MPa; the bottom material enters a dehydration tower and is dehydrated at 50 ℃ and minus 0.093MPa to obtain a small molecular weight amino-terminated polyether product D230 (D represents the functionality of polyether polyol being 2, 230 represents the molecular weight of polyether polyol and the following examples are the same).
Through detection, the amine value of the D230 product is 480mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 59.8g/eq; the reaction conversion rate is 99.3%, and the primary amine yield is 98.8%.
Example 2
35mL of the supported nickel catalyst (containing Ni 95%, cr 3%, and Fe 2%) and 35mL of the Raney nickel catalyst (particle size: 40 mesh, activity: 5mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.2:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 8L/H 2 The volume space velocity is 4.0h -1 NH of (C) 3 A volume space velocity of 2.0h -1 Small molecular weight polyethers (NH) having a molecular weight of 400 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 15:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 1:1); fully mixing and preheating at 50 ℃, then entering a fixed bed reactor I from the top, and finally, inThe first step of hydro-ammonification reaction is carried out at 140 ℃ and 1.5 MPa; the product is subjected to gas-liquid separation at 160 ℃ through a first-stage gas-liquid separator, the top gas is dried at 130 ℃ through a drying tower (mixed particles of active carbon and silica gel are filled in the tower), and then enters a fixed bed reactor II together with liquid at the bottom of the first-stage gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 200 ℃ and 0.8 MPa; the product is subjected to gas-liquid separation at 5 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 50 ℃ and 0.5MPa; the tower bottom material enters a dehydration tower to be dehydrated at 80 ℃ and minus 0.075MPa, and a small molecular weight amino-terminated polyether product D400 is obtained.
Through detection, the amine value of the D400 product is 255mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 110g/eq; the reaction conversion rate is 99.3%, and the primary amine generation rate is 98.6%.
Example 3
155mL of the supported nickel catalyst (containing Ni 90%, cr 8%, and Fe 2%) and 155mL of the Raney nickel catalyst (particle size: 30 mesh, activity: 3mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.44:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 20L/H 2 The volume space velocity is 1.0h -1 NH of (C) 3 A volume space velocity of 2.0h -1 Small molecular weight polyethers (NH) having a molecular weight of 600 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 5:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.9:1); fully mixing and preheating at 100 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammoniation reaction at 160 ℃ and 2.0MPa; the product is subjected to gas-liquid separation at 130 ℃ through a primary gas-liquid separator, the top gas is dried through a drying tower (the tower is filled with activated alumina particles), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 180 ℃ and 0.2 MPa; the product is subjected to gas-liquid separation at 15 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; secondary gas-liquid separationIntroducing the liquid at the bottom of the separator into a flash evaporation deamination tower, and flash evaporation deamination is carried out at 30 ℃ and 0.1 MPa; the bottom material enters a dehydration tower and is dehydrated at 90 ℃ and minus 0.084MPa to obtain a small molecular weight amino-terminated polyether product ED600 (E represents that the polyether polyol initiator is glycol and the following examples are the same).
Through detection, the amine value of the ED600 product is 188mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 132g/eq; the reaction conversion rate is 99.5%, and the primary amine yield is 98.7%.
Example 4
100mL of the supported nickel catalyst (containing Ni 95%, cr 1%, fe 4%) and 100mL of the Raney nickel catalyst (particle size: 60 mesh, activity: 2mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.29:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 5L/H 2 The volume space velocity is 5.0h -1 NH of (C) 3 A volume space velocity of 10.0h -1 Small molecular weight polyether (NH) with molecular weight 900 and functionality 2 3 The molar ratio of the hydroxyl to the polyether polyol is 8:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.1:1); fully mixing and preheating at 90 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammonification reaction at 175 ℃ and 1.8 MPa; the product is subjected to gas-liquid separation at 120 ℃ through a first-stage gas-liquid separator, the top gas is dried at 100 ℃ through a drying tower (filled with mixed particles of silica gel and active alumina), and then enters a fixed bed reactor II together with liquid at the bottom of the first-stage gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 185 ℃ and 0.75 MPa; the product is subjected to gas-liquid separation at 20 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 45 ℃ and 0.4 MPa; the tower bottom material enters a dehydration tower to be dehydrated at 85 ℃ and minus 0.090MPa, and a small molecular weight amino-terminated polyether product ED900 is obtained.
Through detection, the amine value of the ED900 product is 100mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 252g/eq; the conversion rate of the ammonification reaction is 99.6%, and the primary amine generation rate is 98.6%.
Example 5
100mL of the supported nickel catalyst (containing Ni 95%, cr 1%, fe 4%) and 100mL of the Raney nickel catalyst (particle size: 40 mesh, activity: 3mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.29:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was pressed into the mixing preheater at a flow rate of 9.1L/H 2 The volume space velocity is 3.5h -1 NH of (C) 3 A volume space velocity of 3.0h -1 Low molecular weight polyethers (NH) having a molecular weight of 440 and a functionality of 3 3 The molar ratio of the hydroxyl to the polyether polyol is 6:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.2:1); fully mixing and preheating at 80 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammonification reaction at 165 ℃ and 2.5 MPa; the product is subjected to gas-liquid separation at 135 ℃ through a primary gas-liquid separator, the top gas is dried at 120 ℃ through a drying tower (the tower is filled with active carbon particles), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammoniation reaction is carried out at 195 ℃ and 0.85 MPa; the product is subjected to gas-liquid separation at 20 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 35 ℃ and 0.3 MPa; the tower bottom material enters a dehydration tower to be dehydrated at the temperature of 85 ℃ and the pressure of minus 0.089MPa, and a small molecular weight amino-terminated polyether product T403 is obtained. (T represents a polyether polyol having a functionality of 3, as in the examples below).
Through detection, the amine value of the T403 product is 345mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 82g/eq; the conversion rate of the ammonification reaction is 99.7%, and the primary amine generation rate is 98.6%.
Example 6
100mL of the supported nickel catalyst (containing Ni 95%, cr 4.8%, and Fe 0.2%) and 100mL of the Raney nickel catalyst (particle size: 50 mesh, activity: 2mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume and fixed-bed capacity) of phi 25X 720mm (diameter 25mm, height 720mm, volume about 350 ml)The product ratio is 0.29:1), heating and introducing H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 20L/H 2 The volume space velocity is 3.8h -1 NH of (C) 3 A volume space velocity of 1.5h -1 Small molecular weight polyethers (NH) with a molecular weight of 230 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 10:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.7:1); fully mixing and preheating at 65 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammoniation reaction at 190 ℃ and 2.4 MPa; the product is subjected to gas-liquid separation at 150 ℃ through a primary gas-liquid separator, the top gas is dried at 115 ℃ through a drying tower (filled with silica gel particles in the tower), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 190 ℃ and 0.5MPa; the product is subjected to gas-liquid separation at 25 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 15 ℃ and 0.4 MPa; the tower bottom material enters a dehydration tower to be dehydrated at 60 ℃ and minus 0.088MPa, and a small molecular weight amino-terminated polyether product D230 is obtained.
Through detection, the amine value of the D230 product is 482mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 60.0g/eq; the conversion rate of the ammonification reaction is 99.4%, and the primary amine generation rate is 98.5%.
Example 7
70mL of the supported nickel catalyst (containing Ni 94%, cr 5.6%, and Fe 0.4%) and 70mL of the Raney nickel catalyst (particle size: 40 mesh, activity: 3mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.2:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 12L/H 2 The volume space velocity is 2.2h -1 NH of (C) 3 A volume space velocity of 1.5h -1 Small molecular weight polyethers (NH) having a molecular weight of 400 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 10:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 1:1); at 95℃ fullyMixing and preheating, and then entering a fixed bed reactor I from the top, wherein the first-step hydro-ammoniation reaction is carried out at 180 ℃ and 1.7 MPa; the product is subjected to gas-liquid separation at 155 ℃ through a primary gas-liquid separator, the top gas is dried at 120 ℃ through a drying tower (the tower is filled with active alumina and active carbon mixed particles), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and the second-step hydro-ammonification reaction is carried out at 190 ℃ and 0.7 MPa; the product is subjected to gas-liquid separation at 15 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 40 ℃ and 0.2 MPa; the tower bottom material enters a dehydration tower to be dehydrated at 80 ℃ and minus 0.089MPa, and a small molecular weight amino-terminated polyether product D400 is obtained.
Through detection, the amine value of the D400 product is 243.5mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 115g/eq; the conversion rate of the ammonification reaction is 99.7%, and the primary amine generation rate is 98.9%.
Example 8
100mL of the supported nickel catalyst (containing Ni 90%, cr 8%, fe 2%) and 100mL of the Raney nickel catalyst (particle size: 30 mesh, activity: 5mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.29:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 18L/H 2 The volume space velocity is 5.0h -1 NH of (C) 3 A volume space velocity of 6.0h -1 Small molecular weight polyethers (NH) having a molecular weight of 600 and a functionality of 2 3 The molar ratio of the hydroxyl to the polyether polyol is 9:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.4:1); fully mixing and preheating at 90 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammonification reaction at 165 ℃ and 1.5 MPa; the product is subjected to gas-liquid separation at 155 ℃ through a primary gas-liquid separator, the top gas is dried through a drying tower (the tower is filled with mixed particles of activated alumina and silica gel), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 190 ℃ and 0.8 MPa; product is subjected to secondary gas-liquidThe separator performs gas-liquid separation at 25 ℃ to separate H 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 25 ℃ and 0.1 MPa; the tower bottom material enters a dehydration tower to be dehydrated at 85 ℃ and minus 0.090MPa, and a small molecular weight amino-terminated polyether product ED600 is obtained.
Through detection, the amine value of the ED600 product is 170mgKOH/g, and the Active Hydrogen Equivalent Weight (AHEW) is 130g/eq; the conversion rate of the ammonification reaction is 99.6%, and the primary amine generation rate is 99.0%.
Example 9
120mL of the supported nickel catalyst (containing Ni 90%, cr 7%, and Fe 3%) and 120mL of the Raney nickel catalyst (particle size: 20 mesh, activity: 5mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.34:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was injected into the mixing preheater at a flow rate of 18L/H 2 The volume space velocity is 4.0h -1 NH of (C) 3 A volume space velocity of 8.0h -1 Small molecular weight polyether (NH) with molecular weight 900 and functionality 2 3 The molar ratio of the hydroxyl to the polyether polyol is 8:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.38:1); fully mixing and preheating at 100 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammoniation reaction at 180 ℃ and 2.5 MPa; the product is subjected to gas-liquid separation at 125 ℃ through a primary gas-liquid separator, the top gas is dried at 110 ℃ through a drying tower (filled with silica gel particles in the tower), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and a second-step hydro-ammonification reaction is carried out at 190 ℃ and 1.0MPa; the product is subjected to gas-liquid separation at 45 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 25 ℃ and 0MPa; the tower bottom material enters a dehydration tower to be dehydrated at 80 ℃ and minus 0.079MPa, and a small molecular weight amino-terminated polyether product ED900 is obtained.
Through detection, the amine value of the ED900 product is 110mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 250g/eq; the conversion rate of the ammonification reaction is 99.4%, and the primary amine generation rate is 98.7%.
Example 10
175mL of the supported nickel catalyst (containing Ni 95%, cr 1% and Fe 4%) and 175mL of the Raney nickel catalyst (particle size: 30 mesh, activity: 1mL of H) were each prepared 2 Per min.g) are packed in fixed-bed reactors I and II (catalyst volume to fixed-bed volume ratio 0.5:1) of phi 25X 720mm (diameter 25mm, height 720mm, volume 350 ml), warmed and fed with H 2 Activation and drying are performed. After completion, H was pressed into the mixing preheater at a flow rate of 13.5L/H 2 The volume space velocity is 4.6h -1 NH of (C) 3 A volume space velocity of 3.0h -1 Low molecular weight polyethers (NH) having a molecular weight of 440 and a functionality of 3 3 The molar ratio of the hydroxyl to the polyether polyol is 8:1; h 2 Molar ratio to hydroxyl groups in the polyether polyol molecule is about 0.2:1); fully mixing and preheating at 85 ℃, then entering a fixed bed reactor I from the top, and carrying out a first-step hydro-ammonification reaction at 185 ℃ and 2.0MPa; the product is subjected to gas-liquid separation at 130 ℃ through a primary gas-liquid separator, the top gas is dried at 130 ℃ through a drying tower (the tower is filled with active carbon and active alumina mixed particles), and then enters a fixed bed reactor II together with the liquid at the bottom of the primary gas-liquid separator, and the second-step hydro-ammonification reaction is carried out at 200 ℃ and 1.0MPa; the product is subjected to gas-liquid separation at 25 ℃ by a secondary gas-liquid separator, and the separated H is 2 Recycling; the liquid at the bottom of the secondary gas-liquid separator enters a flash evaporation deamination tower, and flash evaporation deamination is carried out at 45 ℃ and 0MPa; the tower bottom material enters a dehydration tower to be dehydrated at the temperature of 85 ℃ and the pressure of minus 0.075MPa, and a small molecular weight amino-terminated polyether product T403 is obtained.
Through detection, the amine value of the T403 product is 355mgKOH/g, and the Active Hydrogen Equivalent (AHEW) is 81g/eq; the conversion rate of the ammonification reaction is 99.4%, and the primary amine generation rate is 99.0%.
Claims (7)
1. The continuous preparation method of the small molecular weight amino-terminated polyether is characterized by comprising the steps of preparing by utilizing a continuous preparation device of the small molecular weight amino-terminated polyether, wherein the continuous preparation device comprises a hydrogen storage device, a liquid ammonia storage tank, a polyether polyol storage tank, a mixing preheater, a fixed bed reactor I, a fixed bed reactor II, a primary gas-liquid separator, a middle section drying tower, a secondary gas-liquid separator, a recycle hydrogen compressor, a flash evaporation deamination tower, a pressurizing liquefying device, a dehydrating tower, a wastewater tank and a product storage tank;
the material outlet of the hydrogen storage device, the material outlet of the liquid ammonia storage tank and the material outlet of the polyether polyol storage tank are respectively communicated with the material inlet of the mixing preheater through pipelines;
the material outlet of the mixing preheater is communicated with the material inlet at the top of the fixed bed reactor I through a pipeline, and the material outlet at the bottom of the fixed bed reactor I is communicated with the material inlet of the primary gas-liquid separator through a pipeline; the liquid outlet at the bottom of the first-stage gas-liquid separator is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline, the gas outlet at the top of the first-stage gas-liquid separator is communicated with the material inlet of the middle-stage drying tower through a pipeline, and the material outlet of the middle-stage drying tower is communicated with the material inlet at the top of the fixed bed reactor II through a pipeline;
the material outlet at the bottom of the fixed bed reactor II is communicated with the material inlet of the secondary gas-liquid separator through a pipeline; the gas outlet at the top of the secondary gas-liquid separator is communicated with the material inlet of the circulating hydrogen compressor through a pipeline, and the material outlet of the circulating hydrogen compressor is communicated with the material inlet of the hydrogen storage device through a pipeline; the liquid outlet at the bottom of the secondary gas-liquid separator is communicated with the material inlet of the flash evaporation deamination tower through a pipeline;
the gas outlet at the top of the flash evaporation deamination tower is communicated with the material inlet of the pressurizing and liquefying device through a pipeline, and the material outlet of the pressurizing and liquefying device is communicated with the material inlet of the liquid ammonia storage tank through a pipeline; the liquid outlet at the bottom of the flash evaporation deamination tower is communicated with the material inlet of the dehydration tower through a pipeline, the wastewater outlet at the top of the dehydration tower is communicated with the wastewater pool through a pipeline, and the product outlet at the bottom of the dehydration tower is communicated with the product storage tank through a pipeline;
the continuous preparation method comprises the following steps of sequentially connecting:
1) Respectively filling the fixed bed reactor I and the fixed bed reactor II with an equal volume of supported nickel catalyst and a Raney nickel catalyst for hydro-ammoniation reaction;
2) Raw material liquid NH 3 Polyether polyol of small molecular weight and H 2 Entering a mixing preheater for full mixing and preheating, and then entering a fixed bed reactor I, and carrying out a first-step hydro-ammoniation reaction under the action of a supported nickel catalyst;
3) The reaction liquid flowing out of the bottom of the fixed bed reactor I is subjected to high-temperature gas-liquid separation through a first-stage gas-liquid separator, the obtained gas is dried through a middle-stage drying tower, and then enters a fixed bed reactor II together with the liquid material flowing out of the bottom of the first-stage gas-liquid separator, and a second-step hydro-ammonification reaction occurs under the action of a Raney nickel catalyst;
4) The effluent liquid at the bottom of the fixed bed reactor II is subjected to normal temperature gas-liquid separation by a secondary gas-liquid separator, and the separated H is 2 Compressing by a circulating hydrogen compressor and circularly applying;
5) Removing unreacted ammonia from the discharged liquid at the bottom of the secondary gas-liquid separator through a flash evaporation deamination tower, pressurizing, liquefying and recycling the ammonia obtained by flash evaporation;
6) Dehydrating the feed liquid flowing out from the bottom of the flash evaporation deamination tower through a dehydration tower to obtain a micromolecular amino polyether product;
the reaction temperature in the fixed bed reactor I is 140-180 ℃ and the reaction pressure is 1.5-2.0 Mpa; the reaction temperature in the fixed bed reactor II is 180-200 ℃ and the reaction pressure is 0.2-1.0 Mpa; the temperature in the mixing preheater is 50-100 ℃; the temperature in the primary gas-liquid separator is 110-160 ℃, and the temperature in the secondary gas-liquid separator is 5-25 ℃; the temperature in the flash evaporation deamination tower is 10-50 ℃ and the pressure is 0-0.5 Mpa; the temperature in the dehydration tower is 50-90 ℃, and the pressure is-0.093 to-0.075 MPa;
in step 2), liquid NH 3 Molar ratio of the hydroxyl (-OH) to the hydroxyl (-OH) in the small molecular weight polyether polyol molecule is 5-15:1, H 2 The molar ratio of the hydroxyl (-OH) in the molecule of the polyether polyol with small molecular weight is 0.1-1:1.
2. The continuous production method of small molecular weight amine-terminated polyether according to claim 1, wherein the middle drying tower adopts a structure in which two towers are connected in parallel.
3. The continuous process for the preparation of small molecular weight amine terminated polyethers according to claim 1 or 2, wherein the packing in the intermediate drying tower is selected from at least one of silica gel, activated carbon or activated alumina.
4. The continuous preparation method of amino-terminated polyether according to claim 1, wherein the filler in the middle section drying tower is at least one selected from silica gel, activated carbon and activated alumina, and the temperature in the tower is 80-130 ℃; the middle section drying tower adopts two groups of parallel connection, one is used for drying, and the other is used for regenerating the filler in the tower, and the two groups of drying towers are used in a circulating switching way.
5. The continuous process for the preparation of amino-terminated polyethers according to claim 1, characterized in that in step 2) liquid NH 3 The space velocity of the feed is 1.0 to 5.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the Polyether polyol feeding volume space velocity is 1.0-10.0 h -1 ； H 2 The flow rate is 5-20L/h.
6. The continuous production method of amino-terminated polyether according to claim 1, wherein the molecular weight of the low molecular weight polyether polyol is 200 to 900 and the functionality is 2 to 3.
7. The continuous preparation method of amino-terminated polyether according to claim 1, wherein the supported nickel catalyst in the fixed bed reactor I comprises 90-95% by mass of metallic Ni, 1-8% by mass of metallic Cr and 0.2-4% by mass of metallic Fe; the particle size of Raney nickel catalyst in the fixed bed reactor II is 20-60 meshes, and the activity is 1-5 ml H 2 G, wet column packing of Raney nickel catalyst, and drying for use; the volumes of the fixed bed reactor I and the fixed bed reactor II are 350ml, and the ratio of the filling volume of the catalyst in the fixed bed reactor I to the filling volume of the catalyst in the fixed bed reactor II to the volume of the fixed bed reactor is 0.1-0.5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711392065.5A CN107880260B (en) | 2017-12-21 | 2017-12-21 | Continuous preparation device and preparation method of small molecular weight amino-terminated polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711392065.5A CN107880260B (en) | 2017-12-21 | 2017-12-21 | Continuous preparation device and preparation method of small molecular weight amino-terminated polyether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107880260A CN107880260A (en) | 2018-04-06 |
| CN107880260B true CN107880260B (en) | 2024-03-26 |
Family
ID=61772086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711392065.5A Active CN107880260B (en) | 2017-12-21 | 2017-12-21 | Continuous preparation device and preparation method of small molecular weight amino-terminated polyether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880260B (en) |
Families Citing this family (4)
| 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 |
| CN113603880B (en) * | 2021-09-10 | 2022-08-05 | 扬州晨化新材料股份有限公司 | System and method for continuously producing low molecular weight polyether amine |
| CN114247385B (en) * | 2021-12-01 | 2024-06-14 | 浙江皇马科技股份有限公司 | System and method for preparing polyether amine by catalyzing aminated polyether diol |
| CN115449068B (en) * | 2022-08-19 | 2023-08-25 | 南京克米斯璀新能源科技有限公司 | Method for preparing amino-terminated polyether by continuous hydro-ammonification |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012769A (en) * | 2013-01-05 | 2013-04-03 | 扬州晨化科技集团有限公司 | Continuous hydro-ammonization or amination reaction method |
| CN103524725A (en) * | 2013-09-25 | 2014-01-22 | 上海康达化工新材料股份有限公司 | Device and method for continuously synthesizing amine-terminated polyether by utilizing fixed bed |
| CN103936601A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Ammonia recovery method in ethanolamine production |
| 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 |
| CN104231256A (en) * | 2014-10-13 | 2014-12-24 | 南京红宝丽股份有限公司 | Continuous preparation method of amine-terminated polyether |
| CN105399940A (en) * | 2015-11-10 | 2016-03-16 | 万华化学集团股份有限公司 | Preparation method of polyether amine |
| CN207987081U (en) * | 2017-12-21 | 2018-10-19 | 红宝丽集团股份有限公司 | A kind of continuous preparation device of small-molecular-weight amine terminated polyether |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005049568A1 (en) * | 2005-10-17 | 2007-04-19 | Basf Ag | Process for continuous hydrogenation or hydrogenating amination |
-
2017
- 2017-12-21 CN CN201711392065.5A patent/CN107880260B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012769A (en) * | 2013-01-05 | 2013-04-03 | 扬州晨化科技集团有限公司 | Continuous hydro-ammonization or amination reaction method |
| CN103936601A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Ammonia recovery method in ethanolamine production |
| CN103524725A (en) * | 2013-09-25 | 2014-01-22 | 上海康达化工新材料股份有限公司 | Device and method for continuously synthesizing amine-terminated polyether by utilizing fixed bed |
| 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 |
| CN104231256A (en) * | 2014-10-13 | 2014-12-24 | 南京红宝丽股份有限公司 | Continuous preparation method of amine-terminated polyether |
| CN105399940A (en) * | 2015-11-10 | 2016-03-16 | 万华化学集团股份有限公司 | Preparation method of polyether amine |
| CN207987081U (en) * | 2017-12-21 | 2018-10-19 | 红宝丽集团股份有限公司 | A kind of continuous preparation device of small-molecular-weight amine terminated polyether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107880260A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107880260B (en) | Continuous preparation device and preparation method of small molecular weight amino-terminated polyether | |
| CN204211669U (en) | Commercial syngas pressure carbonylation produces dimethyl oxalate and the apparatus system of Hydrogenation ethylene glycol | |
| CN207987081U (en) | A kind of continuous preparation device of small-molecular-weight amine terminated polyether | |
| CN102585211B (en) | Continuous production method for amino end-capped polyether | |
| CN101691332B (en) | Method for preparing 4-amino diphenylamine by catalytic hydrogenation | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN102964278B (en) | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction | |
| CN103524725A (en) | Device and method for continuously synthesizing amine-terminated polyether by utilizing fixed bed | |
| CN104231256A (en) | Continuous preparation method of amine-terminated polyether | |
| CN114276533A (en) | Method and device for continuously preparing polyether amine | |
| CN105669379A (en) | Technology for preparing ethanol from acetic ether through hydrogenation | |
| CN113603880B (en) | System and method for continuously producing low molecular weight polyether amine | |
| CN102070464B (en) | Method for producing phenylene diamine by performing hydrogenation reduction on mixed dinitrobenzene with palladium catalyst | |
| CN103626988A (en) | Production method of amino-terminated polyether by using continuous method | |
| CN104419002A (en) | Producing method of amine-terminated polyether | |
| CN104045516A (en) | Method for improving glycol product quality | |
| CN115178191B (en) | Polyether amine continuous production system and method | |
| CN106832251A (en) | A kind of method of normal pressure catalyzed preparation of poly ether amines | |
| CN115449068B (en) | Method for preparing amino-terminated polyether by continuous hydro-ammonification | |
| CN108727580B (en) | Fluidized bed reaction process for preparing amino-terminated polyether | |
| CN102603539B (en) | Method and device for recycling catalyst particles in crude toluene diamine | |
| CN110172029B (en) | Method for continuously synthesizing 2-amino-2-methyl-1-propanol | |
| CN109651097B (en) | Process for producing polyformaldehyde dimethyl ether from methanol and paraformaldehyde | |
| CN109651099B (en) | Process method for synthesizing polyformaldehyde dimethyl ether from methanol and paraformaldehyde | |
| CN104130137A (en) | Preparation method of diethylene triamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |