CN117816056A - Method for synthesizing N, N, N ', N' -tetramethyl-di-propylene triamine by pipelining and production device used by same - Google Patents
Method for synthesizing N, N, N ', N' -tetramethyl-di-propylene triamine by pipelining and production device used by same Download PDFInfo
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- CN117816056A CN117816056A CN202311860766.2A CN202311860766A CN117816056A CN 117816056 A CN117816056 A CN 117816056A CN 202311860766 A CN202311860766 A CN 202311860766A CN 117816056 A CN117816056 A CN 117816056A
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 43
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000007259 addition reaction Methods 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229940085605 saccharin sodium Drugs 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 239000006179 pH buffering agent Substances 0.000 claims description 2
- 229940081974 saccharin Drugs 0.000 claims description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019204 saccharin Nutrition 0.000 claims description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 23
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 19
- 230000006872 improvement Effects 0.000 description 8
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 4
- 229910001260 Pt alloy Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- BXYVQNNEFZOBOZ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n',n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCNCCCN(C)C BXYVQNNEFZOBOZ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JPJMSWSYYHNPLD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCNCCN(C)C JPJMSWSYYHNPLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of chemical industry, in particular to a production device and a device for synthesizing N, N, N ', N' -tetramethyl-propylene triamine. The device of the invention comprises a mixer, a pipelining reactor and the like; the pipelining reactor is a pipelining reactor internally coated with a Ni-Pt catalyst coating. The invention also provides a method for synthesizing N, N, N ', N' -tetramethyl-propylene triamine by utilizing the device, which comprises the following steps: the acrylonitrile and dimethylamine complete the addition reaction in the mixer, the reaction liquid obtained by the addition reaction directly flows into the pipelining reactor, part of the hydrogen passes through the mixer and then enters the pipelining reactor, and the rest of the hydrogen directly enters the pipelining reactor for continuous hydrogenation reaction. The invention adopts a single pipelining reactor to realize continuous addition and hydrogenation processes, avoids the use of repeated pipelining reactors, and has the characteristics of simple device, high production efficiency and high product yield.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a production device and a device for synthesizing N, N, N ', N' -tetramethyl-propylene triamine.
Background
N, N, N ', N' -tetramethyl-bisacryltriamine, abbreviated bis-DMAPA, molecular formula C 10 H 25 N 3 Colorless to yellow, ammoniacal liquid. Is easily dissolved in organic solvents such as alcohol, ether, acetone, etc. Bis-DMAPA is active in chemical property, has tertiary amino and secondary amino, has certain nucleophilicity, is easy to react with electrophilic compounds, is mainly used for preparing cationic surfactants and amphoteric surfactants, is used as a rigid foam low-odor catalyst in molding soft foam and polyether polyurethane, can be used as an epoxy resin curing agent and an accelerator, and has a structure shown in a scheme 1:
at present, the industrial production route mainly takes DMAPN or DMAPA single raw material or a mixture of the DMAPN and the DMAPA as a starting raw material, and the synthesis is carried out in a kettle type or a fixed bed under the condition of high temperature and high pressure. For example, the basf patent US2003013873A1 reports the use of Pt, ni, co multimetal catalyst supported on A1 with DMAPA as feedstock in a fixed bed tubular reactor 2 O 3 On a carrier, reaction temperatureThe temperature is 120-160 ℃, the hydrogen pressure is 1-3 MPa, and the yield of bis-DMAPA is only 52%.
In the above-mentioned document reports that in the method for synthesizing bis-DMAPA, in the existing reaction apparatus such as a reaction kettle or a fixed bed reactor, the reaction apparatus is complicated, and the reaction conditions are severe, the product selectivity is to be further improved; in the process for synthesizing bis-DMAPA from dimethylaminopropylamine, most of the U.S. patents adopt noble metal catalysts, but the problems of high noble metal load, high production cost, complex reaction process, low reaction yield and the like exist.
Disclosure of Invention
The invention aims to provide a method for synthesizing N, N, N ', N' -tetramethyl-di-propylene triamine in a pipeline manner and a production device used by the method.
In order to solve the technical problems, the invention provides a device for synthesizing N, N, N ', N' -tetramethyl-di-propylene triamine in a pipeline way, which comprises a hydrogen storage tank, a nitrogen storage tank, a dimethylamine tank, an acrylonitrile raw material tank, a mixer, a pipeline reactor, a condenser and a crude product collection tank; the pipelining reactor is a pipelining reactor internally coated with a Ni-Pt catalyst coating.
As an improvement of the device for synthesizing N, N, N ', N' -tetramethyl-di-propylene triamine in a pipelining manner, the invention comprises the following steps:
the nitrogen storage tank is communicated with an inlet of the mixer after passing through the stop valve;
the dimethylamine tank is communicated with the inlet of the mixer after passing through a stop valve and a metering pump I;
the acrylonitrile raw material tank is communicated with an inlet of the mixer through a stop valve and a metering pump II;
the outlet of the mixer is communicated with the inlet of the pipelining reactor through a stop valve, a one-way valve I and a connecting pipe;
the hydrogen storage tank is divided into two branches after passing through a stop valve, a flowmeter and a one-way valve II, one branch is communicated with the inlet of the mixer after passing through a needle valve, and the other branch is directly communicated with the connecting pipe.
That is, the present invention is provided with a hydrogen gas inlet port at the front and rear of the mixer, the former regulates the flow rate of hydrogen gas through a needle valve, and the latter aims to remove heat generated by exothermic reaction.
As a further improvement of the apparatus for the pipelined synthesis of N, N' -tetramethyldiacryltriamine of the present invention:
the outlet of the pipelining reactor is connected with the inlet of the condenser after passing through the filter and the back pressure valve; the liquid phase outlet of the condenser is communicated with the crude product collecting tank after passing through the ball valve, and the gas phase outlet of the condenser is communicated with the gas phase outlet of the crude product collecting tank to form a gas phase total outlet.
Description: the gas phase is discharged after being collected and treated by a gas phase total outlet.
As a further improvement of the apparatus for the pipelined synthesis of N, N' -tetramethyldiacryltriamine of the present invention:
a pressure device II is arranged on the connecting pipe; a pressure device I is arranged in front of the needle valve.
As a further improvement of the apparatus for the pipelined synthesis of N, N' -tetramethyldiacryltriamine of the present invention:
a thermometer is arranged on the mixer;
a discharge valve is arranged on the condenser, and a discharge is arranged on the crude product collecting tank.
The invention also provides a method for synthesizing N, N, N ', N' -tetramethyl-propylene triamine by utilizing the device, which comprises the following steps:
the thickness of the Ni-Pt catalyst coating in the pipelining reactor is 0.5-3 mm (preferably 1-3 mm), and the mole ratio of Ni to Pt is 10-50: 1 (preferably 10 to 40:1, more preferably 10 to 30:1);
the acrylonitrile and the dimethylamine are subjected to addition reaction in a mixer, and the mass ratio of the dimethylamine to the acrylonitrile is 1.05-1: 1 (preferably 1.01-1.05:1), and controlling the temperature in the mixer to be 10-40 ℃;
the reaction liquid obtained by the addition reaction directly flows into the pipelining reactor, part of hydrogen firstly passes through the mixer and then enters the pipelining reactor, and the rest of hydrogen directly enters the pipelining reactor for continuous hydrogenation reaction; the mass flow rate ratio of the total amount of the hydrogen to the acrylonitrile is 0.05-0.3: 1 (preferably 0.05-0.15:1), the reaction temperature in the pipelining reactor is 40-80 ℃ (preferably 60-80 ℃), the reaction pressure is 1.0-3.0 Mpa (preferably 0.5-2 Mpa), and the residence time of the reaction solution obtained by the addition reaction in the pipelining reactor is 0.1-5 h (preferably 30-300 min).
Namely, hydrogen is respectively introduced into the pipeline reactor before and after the mixer to carry out continuous hydrogenation reaction. The temperature in the mixer is regulated by the flow of hydrogen into the mixer.
As an improvement of the method of the invention:
plating solution is coated on the inner wall of the pipelining reactor in an electroplating mode, so that a Ni-Pt catalyst coating is formed;
the electroplating solution used for electroplating consists of main salt, pH buffering agent, additive, complexing agent and water,
the main salt consists of metal salts of Ni and Pt, and the molar ratio of the Ni to the Pt is 10-50: 1 (preferably 10 to 40:1, more preferably 10 to 30:1).
As a further improvement of the process of the invention:
ni and Pt may exist as simple metal ions or complex ions,
the Ni source is at least any one (any one or more) of sulfate, sulfamate, chloride and citrate of Ni;
the Pt source is at least any one (any one or more) of sulfate, sulfamate, chloride, and citrate of Pt;
nickel sulfate, copper sulfate, and the like are preferable;
the pH buffer is at least any one (any one or more) of boric acid (preferred), phosphoric acid, acetic acid, oxalic acid, and salts thereof;
the complexing agent is trisodium citrate;
the additive is at least any one (any one or more) of saccharin, saccharin sodium and sodium dodecyl sulfate.
As a further improvement of the process of the invention:
the electrolyte is prepared by adding each component into water, and stirring by ultrasonic or magnetic force to obtain uniform solution. The current density used in the electroplating is 1-5A/dm 2 (preferably 3-4A-dm 2 ) The electroplating temperature is 50-80 ℃, and the electroplating time is 10-60 min (preferably 20-60 min).
As a further improvement of the process of the invention: in the electroplating solution, nickel sulfate is 90+/-5 g/L, trisodium citrate is 80+/-5 g/L, boric acid is 15+/-1 g/L, sodium dodecyl sulfate is 0.12+/-0.02 g/L, saccharin sodium is 0.2+/-0.02 g/L, and the molar ratio of Ni to Pt is 10-30: 1.
according to the invention, acrylonitrile and dimethylamine are used as raw materials, an addition reaction is carried out in a mixer to obtain dimethylaminopropionitrile, and then hydrogenation reaction is carried out in a pipeline reactor coated with a Ni-Pt catalyst coating to obtain the bis-DMAPA product.
The synthesis equation of the N, N, N ', N' -tetramethyl-dipropylene triamine is as follows:
the reaction is first completed in a mixer with michael addition to form dimethylaminopropionitrile:
in a tubular reactor, the dimethylaminopropionitrile is continuously hydrogenated to tetramethyl-dipropylenetriamine:
in the present invention: the conversion rate of acrylonitrile is above 99.5%, and the yield of the product is above 99.0%; the reaction liquid obtained by the pipelining reactor is distilled and purified under reduced pressure, and the purity of the product is more than 99.5 percent.
The invention relates to a method for preparing N, N, N ', N' -tetramethyl-dipropylenetriamine (bis-DMAPA) by continuous amination and hydrogenation of acrylonitrile in a pipeline reactor. And finally, carrying out reduced pressure distillation on the effluent reaction liquid to obtain a pure product.
Compared with the prior art, the invention has the following technical advantages:
(1) The temperature of the pipelining reactor can be accurately controlled, the pipelining reactor has the characteristics of large heat release and quick heat release aiming at the first-step acrylonitrile addition reaction, the concentration of a reactant is diluted by introducing hydrogen in advance, the heat released in the first step is recovered for the second-step hydrogenation reaction, the safety of the reaction process is improved, an additional pipelining reaction device is not required to be built for carrying out the addition reaction, and the investment of equipment cost is reduced.
Description: in the mixer, hydrogen did not participate in the reaction.
(2) The production device with the mixer connected with the pipeline reactor in series is adopted, the acrylonitrile and the amine are directly fed into the pipeline reactor after the addition reaction in the first step, the reaction intermediate is not required to be stored and pretreated, the reaction operation is simple, the continuous process can be realized, and the production efficiency is improved;
(3) The Ni-Pt catalyst coating is adopted, so that the contact area of the catalyst and the reaction liquid is increased, the catalyst can be reused, and the conversion rate of reactants and the selectivity of products are obviously improved;
(4) The method has the advantages of simple post-treatment of the product due to higher selectivity and conversion rate, high-purity product can be obtained through simple reduced pressure distillation, and the operation procedure is simplified.
In conclusion, the invention adopts a single pipelining reactor to realize continuous addition and hydrogenation processes, avoids the use of repeated pipelining reactors, and has the characteristics of simple device, high production efficiency and high product yield. And the Ni-Pt catalyst coating is adopted, so that the contact area of the reaction liquid and the catalyst is increased, the reaction efficiency and the product selectivity are improved, the catalyst can be recycled, and the catalyst has good industrial application prospect.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic structural view of a fixed bed apparatus
FIG. 2 is a nuclear magnetic pattern of the product N, N, N ', N' -tetramethyldiethylenetriamine.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
device example 1, a production device for the pipelined synthesis of N, N' -tetramethyldipropylenetriamine:
comprises a hydrogen storage tank 1, a nitrogen storage tank 2, a dimethylamine tank 3, an acrylonitrile raw material tank 4, a mixer 5, a pipelining reactor 6, a condenser 7 and a crude product collection tank 8; the pipelining reactor 6 is a pipelining reactor internally coated with a Ni-Pt catalyst; the mixer 5 is provided with a thermometer.
The nitrogen storage tank 2 is communicated with the inlet of the mixer 5 after passing through the stop valve 12;
the dimethylamine tank 3 is communicated with the inlet of the mixer 5 after sequentially passing through a stop valve 13, a metering pump I and a stop valve 14;
the acrylonitrile raw material tank 4 is communicated with the inlet of the mixer 5 after sequentially passing through a stop valve 15, a metering pump II and a stop valve 16;
the outlet of the mixer 5 is communicated with the inlet of the pipelining reactor 6 through a stop valve 17, a one-way valve I and a connecting pipe 10; a press ii is provided on the connection pipe 10. The pressure vessel II shows the pressure before entering the pipelining reactor 6. The check valve I prevents the liquid in the piping reactor 6 from flowing back.
The hydrogen storage tank 1 sequentially passes through a stop valve 11, a flowmeter and a one-way valve II and then is divided into two branches, one branch is communicated with the inlet of the mixer 5 after passing through a needle valve 21, and a pressure device I is arranged in front of the needle valve 21; the other branch is directly communicated with the connecting pipe 10; that is, the hydrogen gas is introduced into the mixer 5 before and after, the flow rate of the hydrogen gas is regulated by the needle valve 21, and the heat generated by the exothermic reaction is removed. The check valve II is used for preventing the liquid in the mixer from flowing backwards. The pressure vessel i shows the pressure of the hydrogen before it enters the needle 21 on the branch.
The outlet of the pipelining reactor 6 is connected with the inlet of the condenser 7 after passing through the filter and the back pressure valve in sequence; the liquid phase outlet of the condenser 7 is communicated with the crude product collecting tank 8 after passing through the ball valve 20, the gas phase outlet of the condenser 7 is communicated with the gas phase outlet of the crude product collecting tank 8 to form a gas phase total outlet, and the gas phase is emptied after being collected and treated by the gas phase total outlet. The condenser 7 is provided with a discharge valve 18, and the discharge valve 18 is used for discharging unstable reaction liquid in the early stage of reaction, namely, the discharge valve 18 is only opened in the early stage of reaction and the cleaning pipeline. The crude product collecting tank 8 is provided with a discharge valve 19. The discharge valve 19 is opened at the time of product detection and discharge.
In the invention, a mixer 5 and a pipelining reactor 6 are connected in series, the addition reaction of acrylonitrile and dimethylamine is completed in the mixer 5, the reaction liquid after the addition reaction directly flows into the pipelining reactor 6, and hydrogen is respectively introduced into the pipelining reactor for continuous hydrogenation reaction before and after the mixer 5.
Example 1-1: a method for continuously preparing N, N, N ', N' -tetramethyl-dipropylene triamine (bis-DMAPA) by hydrogenation after acrylonitrile and dimethylamine are added in a pipeline reactor, which comprises the following steps of:
(1) Filling electroplating liquid into the pipelining reactor 6 until the pipelining reactor 6 is filled with the electroplating liquid; at 3.0A/dm 2 Is electroplated at 50 c for 20min, so that a Ni-Pt alloy film of about 1mm thickness is formed on the inner wall of the piping reactor 6, i.e., the piping reactor 6 having the Ni-Pt catalyst coating layer (Ni-Pt catalyst-coated layer) built therein is obtained. The piping reactor 6 with the Ni-Pt catalyst coating inside was prepared as a corresponding production apparatus according to apparatus example 1;
the plating solution is a solution composed of 90g/L nickel sulfate, 9g/L chloroplatinic acid, 80g/L trisodium citrate, 15g/L boric acid, 0.12g/L sodium dodecyl sulfate, 0.2g/L saccharin sodium and water; at this time, ni to Pt molar ratio = 25:1, a step of;
the reaction occurring after the electroplating solution is electrified is as follows: ni (Ni) 2+ +Pt 2+ +4e - Ni-Pt, thus producing a Ni-Pt alloy film (the alloy film contains gold as a componentGeneric Ni and Pt).
(2) Firstly, the stop valve 12 and the stop valve 17 are opened, and the pipeline is purged by nitrogen, so that air in the pipeline system (discharged from a gas phase main outlet) is discharged; and then the shut-off valve 12 is closed.
Opening the stop valve 11, the needle valve 21 and the stop valves 13-16, wherein the mass ratio of the acrylonitrile to the dimethylamine is 1:1.05 was injected into the mixer 5 through the metering pump II and the metering pump I, respectively, the flow rates of acrylonitrile and dimethylamine were 10g/min and 10.5g/min, respectively, the pressure in the piping reactor 6 was regulated by the back pressure valve, and the temperature of the mixer 5 was regulated by regulating the opening of the needle valve 21 to maintain 20℃for addition reaction, to prepare dimethylaminopropionitrile.
The hydrogen is divided into 2 paths, one path directly enters the pipelining reactor 6, and the other path enters the pipelining reactor 6 after being preheated in the mixer 5. The total amount of hydrogen is controlled by a flow meter.
Description: the acrylonitrile and dimethylamine completed the addition reaction in the mixer 5, which was exothermic, and therefore, the opening degree of the needle valve 21 was adjusted to adjust the flow rate of hydrogen gas into the mixer 5, thereby removing the heat of reaction, i.e., the temperature in the mixer 5 was adjusted so that the temperature of the mixer 5 was maintained at 20 ℃. The temperature in the mixer 5 is displayed by a thermometer provided on the mixer 5. The hydrogen after heat exchange enters the pipelining reactor 6 through a pipeline 10 to provide heat for pipelining hydrogenation.
In the mixer 5, hydrogen does not participate in the reaction.
(3) The addition reaction liquid (dimethylaminopropionitrile) discharged from the outlet of the mixer 5 directly flows into the pipelining reactor 6 (with the inner diameter of 10mm and the pipe length of 25 m) after passing through the one-way valve I, meanwhile, two paths of hydrogen are simultaneously introduced into the pipelining reactor 6 for hydrogenation reaction, the hydrogen pumping speed is 0.24L/min (0.5 g/min), the reaction temperature of the pipelining reactor 6 is 60 ℃, the reaction residence time of the addition reaction liquid in the pipelining reactor 6 is 100min, and the reaction pressure is regulated to be stable at 2MPa through the back pressure valve after the pipelining reactor 6.
The mass flow rate ratio of the hydrogen to the acrylonitrile is 0.05:1.
(4) The hydrogenation reaction liquid discharged from the outlet of the pipelining reactor 6 is condensed by a condenser 7 to obtain gas-liquid two phases; the liquid phase thus obtained flows into the crude product collection tank 8, is finally discharged from the discharge valve 19, and is purified by distillation under reduced pressure to obtain bis-DMAPA as a product. The method comprises the following steps: firstly rectifying under normal pressure, collecting fraction of 132-134 ℃ as DMAPA, then distilling under reduced pressure, and collecting fraction of 128-131 ℃ under the pressure of 0.03bar as bis-DMAPA.
The gas (dimethylamine, hydrogen, etc.) discharged from the condenser 7 and the gas (hydrogen, etc.) discharged from the gas phase outlet of the raw product collection tank 8 are discharged after being combined at the gas phase total outlet, and then are discharged after being subjected to conventional acid treatment.
A small amount of liquid was taken through the discharge valve 19 for gas chromatography.
The conversion of acrylonitrile was 99.8% and the yield of bis-DMAPA was 98.0%. The purity of the bis-DMAPA product obtained after reduced pressure distillation and purification is more than or equal to 99.5 percent.
5) After the reaction is finished, closing the flowmeter, the metering pump I and the metering pump II; firstly, a stop valve 12 is opened, a purging pipeline is opened, and the purging product is discharged from a discharge valve 18 of the condenser 7; and then closing the shut-off valve 12; the shutoff valves 11, 13 to 17 and the needle valve 21 are closed again.
Examples 1-2 to 1-5
The thickness of the Ni-Pt alloy film (Ni-Pt catalyst coating) on the inner wall of the piping reactor 6 was changed by changing the current density, the plating time, and the temperature with respect to example 1-1, and the remainder was equivalent to example 1-1; thus, corresponding examples 1-2 to 1-5 were obtained, and comparative examples 1-1 and 1-2 were obtained. The acrylonitrile conversion and the product yield of the raw material were examined to obtain the following data (Table 1).
TABLE 1 influence of Ni-Pt alloy film thickness of the piping reactor on acrylonitrile selectivity and bis-DMAPA yield
Examples 2-1 to 2-7
The concentration of nickel sulfate was unchanged (still 90 g/L) relative to example 1-1, and the molar ratio of Ni to Pt of the plating solution used for the plating in the piping reactor was changed by changing the concentration of chloroplatinic acid, the remainder being equivalent to example 1-1. Thus, corresponding examples 2-1 to 2-7 were obtained. The acrylonitrile conversion and the product yield of the raw material were examined to obtain the following data (Table 2).
TABLE 2 influence of the Ni to Pt molar ratio of the plating solution on the acrylonitrile selectivity and bis-DMAPA yield
Examples 3-1 to 3-6
The remainder was identical to example 1-1 by varying the reaction temperature of mixer 5 and/or the piped reactor 6 relative to example 1-1. Reactant conversion and product yield were measured to yield the following data (table 3).
TABLE 3 influence of the reaction temperature on the acrylonitrile conversion and the yield of bis-DMAPA
Examples 4-1 to 4-4
The pipe length of the piping reactor 6 was changed with respect to example 1-1, and the reaction residence time of the addition reaction liquid in the piping reactor 6 was changed correspondingly, and the remainder was identical to example 1-1. The reactant conversion and product yield were measured to give the following data (table 4).
TABLE 4 influence of the reaction residence time on the acrylonitrile conversion and the yield of bis-DMAPA
Examples 5-1 to 5-3
The pressure of the reaction in the piping reactor 6 was changed by adjusting the back pressure valve after the piping reactor 6 with respect to example 1-1, and the rest was equivalent to example 1-1. Reactant conversion and product yield were measured to yield the following data (table 5).
TABLE 5 influence of the reaction pressure on the acrylonitrile conversion and the yield of bis-DMAPA
Examples 6-1 to 6-2
The flow rates of dimethylamine and acrylonitrile were changed with respect to example 1-1, and the tube lengths of the piping reactor 6 were adjusted accordingly, thereby ensuring that the reaction residence time of the addition reaction solution in the piping reactor 6 remained unchanged, and the remainder was identical to example 1-1. Thus, corresponding examples 6-1 to 6-2 were obtained. The product yield was checked to give the following data (Table 7).
TABLE 7 influence of the ratio of the material flow on the acrylonitrile conversion and the yield of bis-DMAPA
Examples 7-1 to 7-2
The flow rate of acrylonitrile was kept constant with respect to example 1-1, the flow rate of hydrogen was changed to change the mass flow rate ratio of hydrogen to acrylonitrile, and the tube length of the piping reactor 6 was adjusted accordingly to ensure that the reaction residence time of the addition reaction solution in the piping reactor 6 was kept constant, and the remainder was identical to example 1-1. Thus, corresponding examples 7-1 to 7-2 were obtained. The product yield was checked to give the following data (Table 8).
TABLE 8 influence of the mass flow of Hydrogen to acrylonitrile on the conversion of acrylonitrile and the yield of bis-DMAPA
Comparative example 1
In comparative example 1-1, the needle valve 21 was closed and hydrogen was not introduced into the mixer 5, that is, the reaction temperature in the mixer 5 was rapidly increased to 80℃or higher by the addition reaction of dimethylamine and acrylonitrile in the mixer 5, thereby increasing side reactions (by-product of the self-polymerization of acrylonitrile) and finally the conversion of acrylonitrile was 99%, but the yield of bis-DMAPA was reduced to 50%.
Comparative example 2 the concentration of nickel sulfate was unchanged relative to example 1-1, and the molar ratio of Ni to Pt of the plating solution used for the plating in the piping reactor was changed to 1:1 by changing the concentration of chloroplatinic acid, and the remainder was the same as example 1-1.
The acrylonitrile conversion (%) was 99%, and the bis-DMAPA yield (%) was 66%.
This comparative example 2 illustrates: too much Pt increases the selectivity of tertiary amine, but rather decreases the selectivity of secondary amine.
Comparative example 3 the temperature of the mixer 5 was adjusted to 50 c by adjusting the opening of the needle valve 21, and the rest was identical to example 1-1. The acrylonitrile conversion (%) was 98%, and the bis-DMAPA yield (%) was about 70%.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (10)
1. A device for synthesizing N, N' -tetramethyl-di-propylene triamine in a pipelining manner, which is characterized in that:
the device comprises a hydrogen storage tank (1), a nitrogen storage tank (2), a dimethylamine tank (3), an acrylonitrile raw material tank (4), a mixer (5), a pipelining reactor (6), a condenser (7) and a crude product collecting tank (8); the pipelining reactor (6) is a pipelining reactor internally coated with a Ni-Pt catalyst coating.
2. The apparatus for the pipelined synthesis of N, N' -tetramethyldipropylenetriamine of claim 1, wherein:
the nitrogen storage tank (2) is communicated with an inlet of the mixer (5) after passing through a stop valve;
the dimethylamine tank (3) is communicated with the inlet of the mixer (5) through a stop valve and a metering pump I;
the acrylonitrile raw material tank (4) is communicated with an inlet of the mixer (5) through a stop valve and a metering pump II;
the outlet of the mixer (5) is communicated with the inlet of the pipelining reactor (6) through a stop valve, a one-way valve I and a connecting pipe (10);
the hydrogen storage tank (1) is divided into two branches after passing through a stop valve, a flowmeter and a one-way valve II, one branch is communicated with the inlet of the mixer (5) after passing through a needle valve (21), and the other branch is directly communicated with the connecting pipe (10).
3. The apparatus for the pipelined synthesis of N, N' -tetramethyldipropylenetriamine of claim 2, wherein:
the outlet of the pipelining reactor (6) is connected with the inlet of the condenser (7) after passing through the filter and the back pressure valve; the liquid phase outlet of the condenser (7) is communicated with the crude product collecting tank (8) through a ball valve (20), and the gas phase outlet of the condenser (7) is communicated with the gas phase outlet of the crude product collecting tank (8) to form a gas phase total outlet.
4. A device for the pipelined synthesis of N, N' -tetramethyldipropylenetriamine according to claim 3, characterized in that:
a press II is arranged on the connecting pipe (10); a presser I is arranged in front of the needle valve (21).
5. The apparatus for the pipelined synthesis of N, N' -tetramethyldipropylenetriamine of claim 4, wherein:
a thermometer is arranged on the mixer (5);
a discharge valve (18) is arranged on the condenser (7), and a discharge valve (19) is arranged on the crude product collecting tank (8).
6. A method for the pipelined synthesis of N, N' -tetramethylbisallyl triamine using the apparatus of any one of claims 1 to 5, characterized by:
the thickness of the Ni-Pt catalyst coating in the pipelining reactor (6) is 0.5-3 mm, and the mole ratio of Ni to Pt is 10-50: 1, a step of;
the acrylonitrile and the dimethylamine are subjected to addition reaction in a mixer (5), and the mass ratio of the dimethylamine to the acrylonitrile is 1.05-1: 1, controlling the temperature in the mixer (5) to be 10-40 ℃;
the reaction liquid obtained by the addition reaction directly flows into a pipelining reactor (6), part of hydrogen firstly passes through a mixer (5) and then enters the pipelining reactor (6), and the rest of hydrogen directly enters the pipelining reactor (6) for continuous hydrogenation reaction; the mass flow rate ratio of the total amount of the hydrogen to the acrylonitrile is 0.05-0.3: 1, the reaction temperature in the pipelining reactor (6) is 40-80 ℃, the reaction pressure is 1.0-3.0 Mpa, and the residence time of the reaction solution obtained by the addition reaction in the pipelining reactor (6) is 0.1-5 h.
7. The method according to claim 6, wherein:
plating solution is coated on the inner wall of the pipelining reactor (6) in an electroplating mode, so that a Ni-Pt catalyst coating is formed;
the electroplating solution used for electroplating consists of main salt, pH buffering agent, additive, complexing agent and water,
the main salt consists of metal salts of Ni and Pt, and the molar ratio of the Ni to the Pt is 10-50: 1.
8. the method according to claim 7, wherein:
the Ni source is at least any one of sulfate, sulfamate, chloride and citrate of Ni;
the Pt source is at least any one of sulfate, sulfamate, chloride and citrate of Pt;
the pH buffer is at least any one of boric acid, disodium hydrogen phosphate, acetic acid, oxalic acid and salts thereof;
the complexing agent is trisodium citrate;
the additive is at least one of saccharin, saccharin sodium and sodium dodecyl sulfate.
9. A method according to any one of claims 6 to 8, characterized in that:
the current density used in the electroplating is 1-5A/dm 2 The electroplating temperature is 50-80 ℃, and the electroplating time is 10-60 min.
10. The method according to any one of claims 6 to 9, characterized in that:
in the electroplating solution, nickel sulfate is 90+/-5 g/L, trisodium citrate is 80+/-5 g/L, boric acid is 15+/-1 g/L, sodium dodecyl sulfate is 0.12+/-0.02 g/L, saccharin sodium is 0.2+/-0.02 g/L, and the molar ratio of Ni to Pt is 10-30: 1.
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