CN111100285B - Method for preparing polyetheramine - Google Patents
Method for preparing polyetheramine Download PDFInfo
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- CN111100285B CN111100285B CN201811262149.1A CN201811262149A CN111100285B CN 111100285 B CN111100285 B CN 111100285B CN 201811262149 A CN201811262149 A CN 201811262149A CN 111100285 B CN111100285 B CN 111100285B
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 229920000570 polyether Polymers 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 64
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 49
- 239000003729 cation exchange resin Substances 0.000 claims description 29
- 238000005192 partition Methods 0.000 claims description 29
- 239000011964 heteropoly acid Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- 239000006004 Quartz sand Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005576 amination reaction Methods 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- 238000004176 ammonification Methods 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 14
- 238000005507 spraying Methods 0.000 description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 238000001035 drying Methods 0.000 description 21
- 238000001291 vacuum drying Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 15
- 239000003456 ion exchange resin Substances 0.000 description 14
- 229920003303 ion-exchange polymer Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 polyoxypropylene Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbamic acid group Chemical group C(N)(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000768 polyamine Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing polyether amine adopts a fixed bed tubular reactor, the middle part is a catalyst bed layer, the upper part is provided with a clapboard along the axial direction, the lower end of the clapboard extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts, the two sides of the clapboard are an upper feeding section and a discharging section, and a lower feeding section is arranged below a catalyst filling layer; polyether, liquid ammonia and hydrogen enter from a raw material inlet of an upper feeding section as feeding I, liquid ammonia and hydrogen enter from a raw material inlet of a lower feeding section as feeding II, the feeding I is subjected to ammoniation reaction on a catalyst bed layer, the reacted material is mixed with the feeding II from bottom to top for further reaction, and a product is discharged from a discharge port of a discharge section. The reaction mode of the method ensures that the materials react more fully, improves the conversion rate of the ammoniation reaction, feeds at the upper end pass through the catalyst bed layer repeatedly, the reaction is more fully, and the conversion rate of polyether is improved.
Description
Technical Field
The invention relates to a method for preparing polyether amine, in particular to a method for preparing polyether amine by taking polyether polyol and liquid ammonia as raw materials.
Background
The polyether amine is also called amine terminated polyether, and is a polyoxyalkylene compound with a polyether skeleton as a molecular main chain and a terminated end by an amino group. These amine-terminated polyethers mostly use polyethers (polyethylene glycol, polyoxypropylene ether, etc.) as reaction raw materials, and the terminal hydroxyl groups of polyether polyols are converted into corresponding amine groups or amino groups (the terminal groups are usually primary amino groups, secondary amino groups or polyamine groups containing active hydrogen) by different treatment methods. Due to the reactivity of the terminal amino group or the amine group at the tail end of the polyether framework, the polyether framework can react with various reactive groups, such as epoxy groups, isocyanate groups and the like; in addition, due to the existence of ether bond in polyether chain, the polyether is easy to be dissolved in various organic matters, thus greatly widening the application range of the amino-terminated polyether in the industrial field. The amino-terminated polyether is widely applied to the fields of synthetic raw materials of polyurethane (polyurea), curing agents of epoxy resin, new-generation gasoline detergents and the like due to the excellent performance of the amino-terminated polyether.
The synthesis method of the amino-terminated polyether mainly comprises a catalytic amination method, a leaving group method, a hydrolysis method and an amino phenoxy method. The method for synthesizing the amino-terminated polyether by the leaving group method has the hidden troubles that raw materials are not easy to purchase and the environment is easy to pollute, particularly, the post-treatment of the product needs a large amount of acid generated by the neutralization reaction of alkali, a large amount of inorganic salt is generated in the production process, and the separation is difficult. In the hydrolysis process, although the viscosity of the product can be controlled by optimizing the synthesis and hydrolysis conditions of the prepolymer, a small amount of chain extension reaction occurs in the reaction process, and a carbamic acid group exists in the synthesis process, so that the viscosity of the product is higher than that of the original polyether polyol. The amino-terminated polyether prepared by the amino phenoxy method has a simple process route, but in the reaction process of polyether polyol and a compound with an unsaturated group, more side reactions are generated, so the requirements on reaction conditions are strict, and the actual operation is difficult.
The synthesis of the amine-terminated polyether by the catalytic amination starts with the terminal hydroxyl group of polyether polyol, and replaces the terminal hydroxyl group with an amino group by aminolysis reaction in the presence of a catalyst. Compared with the process route, the direct synthesis of the amino-terminated polyether by the catalytic amination method has the advantages of simple and convenient steps, cleanness, environmental protection, high product purity, less side reaction and the like. Is the main technical method for synthesizing the polyether amine at present.
CN1546550A discloses a method for preparing polyetheramine, which adopts Raney nickel catalyst, the reaction is carried out in a high-pressure kettle, the reaction temperature is 180-280 ℃, and the reaction pressure is 11-21 MPa. CN101982482 discloses a method for preparing polyetheramine, which adopts amorphous alloy as a catalyst, and the reaction is carried out in a high-pressure kettle, the reaction temperature is 200 ℃, and the reaction pressure is 3.0-7.0 MPa. These methods have problems that the reaction is not continuous and the reaction conditions are severe. CN201310442410.7 discloses a device and a method for continuously synthesizing polyether amine, wherein the device is provided with 1-3 fixed bed reactors, the reaction temperature is 150-300 ℃, and the reaction pressure is 1-20 MPa. CN104119239A discloses a process method for continuously producing small molecular weight polyether amine, which adopts 2-6 fixed bed reactors connected in series, wherein the reactors are filled with different catalysts to improve the reaction conversion rate. CN105542146A discloses a continuous production process of polyether amine, which adopts a tubular reactor and a reaction junctionRectifying twice after finishing to obtain polyether amine product, wherein the catalyst is metal supported catalyst, and the carrier is gamma-Al 2 O 3 . Although the method is a continuous reaction, the process flow is complex, the reaction conditions are harsh, and the gamma-Al is adopted 2 O 3 The carrier catalyst is easy to have Al ion migration under the action of liquid ammonia, which causes the reduction of the service life of the catalyst.
Disclosure of Invention
The invention provides a method for preparing polyether amine, aiming at the problems of complex flow, harsh reaction conditions, low raw material conversion rate and low product selectivity in the method for preparing polyether amine by taking polyether polyol and liquid ammonia as raw materials in the prior art. The method takes polyether and liquid ammonia as raw materials, a fixed bed tubular reactor with a partition plate in the middle is adopted as the reactor, an ammoniation reaction is carried out under the action of a supported heteropolyacid catalyst, and the feeding mode adopts an upper feeding mode and a lower feeding mode simultaneously. The method can effectively improve the conversion rate of polyether, and has the advantages of simple process, high efficiency, mild conditions, stable catalyst activity and long-period operation.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for preparing polyether amine adopts a fixed bed tubular reactor, wherein a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is arranged on the upper portion of the fixed bed tubular reactor along the axial direction, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; polyether, liquid ammonia and hydrogen enter the reactor from a raw material inlet of an upper feeding section as feeding I, liquid ammonia and hydrogen enter the reactor from a raw material inlet of a lower feeding section as feeding II, the feeding I is subjected to an ammoniation reaction on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feeding II from bottom to top for further reaction, and a reaction product is discharged from a discharge port of a discharge section.
In the method, the length of the partition plate is 1/2-2/3 of the length of the reactor, and the top of the partition plate and two side edges of the partition plate are hermetically connected with the wall of the reactor.
In the method, the molar ratio of liquid ammonia to polyether in the feed I is 50:1 to 150:1, preferably 100:1 to 120:1, the polyether liquid hourly space velocity is 0.05-0.5 h -1 Preferably 0.1 to 0.2h -1 The molar ratio of the hydrogen to the polyether is 100 to 150:1, preferably 50 to 80:1.
in the method, the liquid hourly space velocity of the liquid ammonia in the feed material II on the catalyst is 0.05-0.2 h -1 Preferably 0.1 to 0.15h -1 The molar ratio of hydrogen to polyether is 300 to 100:1.
in the process of the present invention, the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
In the method, quartz sand is filled at two ends of a reactor, and a mixture of the catalyst and the quartz sand is filled in a catalyst bed section, wherein the granularity range of the quartz sand is 1.0-1.2 mm, and the catalyst accounts for 50-70 v% of the total filling amount.
In the method of the present invention, the reaction conditions of the amination reaction are as follows: the reaction temperature is 160-190 ℃, preferably 170-180 ℃; the reaction pressure is 3 to 9MPa, preferably 4 to 6MPa.
In the method, the catalyst used in the ammoniation reaction is a supported heteropolyacid catalyst. Wherein, the carrier is cation exchange resin, the exchange capacity is 4.4-5.3 mol/kg, the mass content of water is 49-53%, the wet apparent density is 0.75-0.95 g/mL, the wet true density is 1.1-1.3 g/mL, and the granularity range is 0.5-1.0 mm; the active component heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, arsenic tungstic acid, germanium tungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid.
In the method, the preparation method of the supported heteropolyacid catalyst comprises the following steps:
(1) Washing the cation exchange resin with deionized water;
(2) Vacuum drying the washed cation exchange resin;
(3) Then the obtained cation exchange resin is treated by aqueous solution of heteropoly acid with certain concentration, and the supported heteropoly acid catalyst is obtained after drying and roasting.
In the method, the washing in the step (1) is carried out for 3 to 5 times, and each time lasts for 5 to 10 minutes; the drying temperature in the step (2) is 70-90 ℃, and the drying time is 4-8 h; in the step (3), the mass percent concentration of the heteropoly acid aqueous solution is 10-50%; the treatment process of the heteropoly acid aqueous solution comprises the following steps: a. filling cation exchange resin into a fine steel wire mesh bag, wherein the thickness of the steel wire mesh bag is 1-5 mm, preferably 2-3 mm, and the steel wire mesh bag is flatly paved in an ultrasonic vibrator; b. under the condition that the ultrasonic vibration frequency is 50-60 kHz, spraying cation exchange resin on a gas-liquid mixture of 30-50% heteropoly acid aqueous solution and nitrogen through an atomizing nozzle, wherein the spraying distance is 0-2 cm, preferably 0.5-1 cm, the spraying pressure is 0.02-0.2 MPa, preferably 0.05-0.1 MPa, and the spraying time is 1-4 h, preferably 2-3 h; c. then drying and roasting the cation exchange resin for later use; d. repeating the operation process of the step b by using 10-20% heteropoly acid aqueous solution, and then drying and roasting the cation exchange resin to obtain a supported heteropoly acid catalyst; wherein the drying temperature is 70-90 ℃, and the drying time is 6-8 h; the roasting temperature is 180-220 ℃, and the roasting time is 8-12 h.
In the method, the prepared polyether amine main chain is of a polyether structure, the active functional group at the tail end is an amino group, and the amino-terminated polyether has double functional groups and has the average molecular weight of 230.
Compared with the prior art, the invention has the following advantages:
(1) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the materials are fed in an upper and lower simultaneous feeding mode, the reaction materials fed in the upper mode enter the reactor and pass through a catalyst bed layer under a certain airspeed condition, part of the reactants firstly react to a certain degree and move downwards, the reaction materials fed in the lower mode enter the reactor under a certain airspeed condition, are mixed with the materials moving downwards and then pass through the catalyst bed layer and move upwards, the reaction is further carried out after the materials are mixed, and the conversion rate of the ammoniation reaction is improved.
(2) The upper feeding and the lower feeding have an airspeed difference (the upper feeding airspeed is greater than the lower feeding airspeed), so that the feeding at the upper end of the reactor passes through the catalyst bed layer in a reciprocating manner, the reaction is more sufficient, and the conversion rate of polyether is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding material is mixed with liquid ammonia and hydrogen, and the catalyst is continuously boiled in a gap formed by the quartz sand under the driving action of the hydrogen with certain air flow and air speed, so that the contact probability and the mass transfer efficiency of reaction materials and the active center of the catalyst are increased, and the reaction efficiency and the conversion rate are improved.
(4) The axial baffle is added in the reactor, so that the moving path of the feeding material at the inlet I is limited, the process that the feeding material at the inlet I is partially reacted firstly and then is further reacted with the feeding material at the inlet II is realized, the reaction is more sufficient, and the conversion rate is higher.
(5) Under the condition of ultrasonic wave, nitrogen and heteropoly acid solution are used for spraying and treating the catalyst twice, so that tiny impurities in the pore canal of the catalyst are blown out, and meanwhile, active components are more uniformly and firmly loaded in the pore canal, so that the catalyst has better activity and stability.
Drawings
FIG. 1 is a schematic diagram of a process for preparing polyetheramines according to the invention.
Wherein: 1-an upper feeding section; 2-a lower feeding section; 3-discharging section; 4-a separator; 5-catalyst bed layer.
Detailed Description
The preparation process of the supported heteropolyacid catalyst of the present invention is specifically described below: 1. 50-100 g of strong acid cation exchange resin is washed by deionized water for 3-5 times, each time for 5-10 minutes, the washing temperature is 50-60 ℃, and then the strong acid cation exchange resin is dried in a vacuum drying oven for 4-6 hours under the condition of 80-90 ℃. 2. Filling the dried strong-acid cation exchange resin into a steel wire mesh bag, flatly spreading the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, and spraying heteropoly acid aqueous solution with a certain concentration and nitrogen gas by using an atomizing nozzle to impregnate the resin under the ultrasonic vibration condition, wherein the spraying distance is 1-2 cm, the spraying pressure is 0.05-0.1 MPa, and the spraying time is 1-2 h. 3. And then after washing the resin, drying the resin according to the condition of the step one, and roasting the resin for 6 to 8 hours at the temperature of between 200 and 220 ℃ for later use. 4. And (3) treating the resin to be used with heteropoly acid aqueous solutions with different concentrations according to the method of the step two, and drying and roasting the washed resin according to the conditions of the step three to obtain the supported heteropoly acid catalyst.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass% unless otherwise specified. The ultrasonic vibrator used in the preparation of the supported heteropolyacid catalyst is KQ-550B, and the atomizing nozzle is JLN-G type high-pressure fine atomizing nozzle, and is purchased from Jining Jun atomizing equipment Co. Ion exchange resin catalysts were purchased from special resins, inc. of Mingzhu, dendong.
The preparation of polyetheramines according to the invention is carried out as shown in the process scheme of FIG. 1: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a partition plate, wherein a catalyst bed layer 5 is arranged in the middle of the fixed bed continuous reactor, a partition plate 4 is arranged on the upper portion of the fixed bed continuous reactor along the axial direction, the length of the partition plate is 1/2 of the length of the reactor, the lower end of the partition plate 4 extends into the catalyst bed layer 5 and does not completely penetrate through the catalyst bed layer 5, the reactor is divided into three parts by the partition plate 4 and the catalyst bed layer 5, an upper feeding section 1 and a discharging section 3 are arranged on two sides of the partition plate, and a lower feeding section 2 is arranged below the catalyst bed layer 5; liquid ammonia, polyether and hydrogen get into the reactor as feeding I from the raw materials entry of last feeding section 1, the liquid ammonia is squeezed into by the lining tile metal diaphragm pump, polyether is squeezed into by lining tile micro-metering pump, liquid ammonia and hydrogen are squeezed into the reactor as feeding II from the raw materials entry of lower feeding section 2 by the lining tile metal diaphragm pump, feeding I reacts at catalyst bed 5 at the reactor middle part, the material after the reaction mixes with feeding II from bottom to top, further react, the reaction product is discharged from the discharge gate of ejection of compact section 3.
Example 1
(1) Preparation of modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 3 times, each time is 5 minutes, and the styrene strong acid cation exchange resin is placed in a vacuum drying oven to be dried for 4 hours at the temperature of 80 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 2mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 58kHz, and spraying and soaking 30% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 1cm, and the spraying pressure is 0.05MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 20% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 170 ℃, the reaction pressure is 5MPa, and the upper feeding total volume airspeed is 0.5h -1 The molar ratio of the amino ether is 100:1, the molar ratio of hydrogen to polyether is 60; the volume space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.3 h -1 The molar ratio of hydrogen to polyether was 200 and the reaction results are shown in Table 1.
Example 2
(1) Preparation of modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 58kHz, and spraying and soaking 35% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.06MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 220 ℃ for 8 hours; d: and then treating the resin with 15% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 180 ℃, the reaction pressure is 5MPa, and the feeding is totalVolume space velocity of 0.6h -1 The molar ratio of amino ether is 120:1, the molar ratio of hydrogen to polyether is 70; the volume space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.3 h -1 The molar ratio of hydrogen to polyether was 250 and the reaction results are shown in Table 1.
Example 3
(1) Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 3 times, each time is 5 minutes, and the styrene strong acid cation exchange resin is placed in a vacuum drying oven to be dried for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 60kHz, and spraying and soaking 40% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.05MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 220 ℃ for 8 hours; d: and then treating the resin with 20% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 180 ℃, the reaction pressure is 5MPa, and the upper feeding total volume space velocity is 0.7h -1 The molar ratio of the amino ether is 150:1, the molar ratio of hydrogen to polyether is 60; the volume space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.3 h -1 The molar ratio of hydrogen to polyether was 200 and the reaction results are shown in Table 1.
Example 4
(1) Preparation of modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 3 times, each time is 5 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 80 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 59kHz, and spraying and soaking 45 mass percent of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.05MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 220 ℃ for 8 hours; d: and then treating the resin with 15% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 180 ℃, the reaction pressure is 6MPa, and the upper feeding total volume airspeed is 0.4h -1 The molar ratio of the amino ether is 100:1, the molar ratio of hydrogen to polyether is 80; the volume space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.2h -1 The molar ratio of hydrogen to polyether was 250 and the reaction results are shown in Table 1.
Example 5
(1) Preparation of modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 3 times, each time for 5 minutes, and dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 59kHz, and spraying and soaking 50% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.06MPa; c: drying the washed ion exchange resin in a vacuum drying oven at 90 ℃ for 6 hours, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 15% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 190 ℃, the reaction pressure is 6MPa, and the upper feeding total volume space velocity is 0.4h -1 The molar ratio of the amino ether is 100:1, the molar ratio of hydrogen to polyether is 70; the volume space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.2h -1 The molar ratio of hydrogen to polyether was 300 and the reaction results are shown in Table 1.
Example 6
(1) Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 56kHz, and spraying and soaking 35% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.07MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 220 ℃ for 8 hours; d: and then treating the resin with 10% phosphotungstic acid aqueous solution according to the method b, washing, drying for 6 hours in a vacuum drying oven at the temperature of 80 ℃, and roasting the dried ion exchange resin for 8 hours at the temperature of 210 ℃ to obtain the supported heteropolyacid catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 190 ℃, the reaction pressure is 6MPa, and the upper feeding total volume space velocity is 0.5h -1 The molar ratio of the amino ether is 150:1, the molar ratio of hydrogen to polyether is 80; the volume space velocity of liquid ammonia to the catalyst in the lower feeding is 0.2h -1 The molar ratio of hydrogen to polyether was 250 and the reaction results are shown in Table 1.
Example 7
The catalyst used in the reaction was a DNW II type resin catalyst, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Comparative example 1
During the reaction, only the feeding mode is adopted, other conditions are the same as example 4, and the reaction results are shown in table 1.
Comparative example 2
In the reaction process, the fixed bed reactor has no partition plate in the middle, the other conditions are the same as example 4, and the reaction results are shown in Table 1.
Comparative example 3
During the reaction, only liquid ammonia was fed as the lower feed, and hydrogen was not fed, and the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Comparative example 4
The preparation process of the used catalyst has no ultrasonic vibration and mixed spraying process of the modification liquid and nitrogen, only the catalyst is modified by adopting a conventional supersaturated impregnation method, other conditions are the same as those of the example 4, and the reaction results are shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (11)
1. A method for preparing polyetheramine adopts a fixed bed tubular reactor, and is characterized in that a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, quartz sand is filled at two ends of the reactor, a catalyst filling mode that a catalyst and quartz sand mixture is filled in a catalyst bed layer is adopted, a partition plate is axially arranged at the upper part of the fixed bed tubular reactor, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; polyether, liquid ammonia and hydrogen enter the reactor as feeding I from the raw material inlet of the upper feeding section, liquid ammonia and hydrogen enter the reactor as feeding II from the raw material inlet of the lower feeding section, feeding I is subjected to ammoniation reaction on a catalyst bed layer in the middle of the reactor, the reacted materials are mixed with feeding II from bottom to top for further reaction, and reaction products are discharged from a discharge port of the discharge section.
2. The method of claim 1, wherein the length of the partition is 1/2-2/3 of the length of the reactor, and the top of the partition and the two sides of the partition are hermetically connected with the reactor wall.
3. The process according to claim 1, characterized in that the molar ratio of liquid ammonia and polyether in said feed I is 50:1 to 150:1.
4. the process of claim 1, wherein the liquid hourly space velocity of the polyether in feed I is from 0.05 to 0.5h -1 。
5. The process according to claim 4, wherein the molar ratio of hydrogen to polyether in the feed I is from 100 to 50:1.
6. the process of claim 1, wherein the liquid hourly space velocity of liquid ammonia in feed II on the catalyst is in the range of from 0.05 to 0.2h -1 。
7. The process of any one of claims 1 to 6, wherein the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
8. The process according to claim 6, wherein the molar ratio of hydrogen to polyether in feed II is from 300 to 100:1.
9. the method as claimed in claim 1, wherein the quartz sand has a particle size ranging from 1.0 to 1.2mm, and the catalyst accounts for 50 to 70v% of the total loading of the catalyst bed.
10. The method according to claim 1, wherein the amination reaction is carried out under the following reaction conditions: the reaction temperature is 160-190 ℃, and the reaction pressure is 3-9 Mpa.
11. The method as claimed in claim 1, wherein the catalyst used in the ammonification reaction is a supported heteropolyacid catalyst, wherein the carrier is cation exchange resin, the exchange capacity is 4.4-5.3 mol/kg, the mass content of water is 49-53%, the wet apparent density is 0.75-0.95 g/mL, the wet true density is 1.1-1.3 g/mL, and the particle size range is 0.5-1.0 mm; the active component heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, arsenic tungstic acid, germanium tungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid.
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