CN112159323A - Synthesis method of pentamethyldiethylenetriamine - Google Patents
Synthesis method of pentamethyldiethylenetriamine Download PDFInfo
- Publication number
- CN112159323A CN112159323A CN202011188433.6A CN202011188433A CN112159323A CN 112159323 A CN112159323 A CN 112159323A CN 202011188433 A CN202011188433 A CN 202011188433A CN 112159323 A CN112159323 A CN 112159323A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dimethylamine
- pentamethyldiethylenetriamine
- methyldiethanolamine
- active component
- 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.)
- Pending
Links
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract 2
- 239000011949 solid catalyst Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000243 solution Substances 0.000 abstract description 18
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005913 hydroamination reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QWKQSQDBKIRFCZ-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;formaldehyde Chemical compound O=C.NCCNCCN QWKQSQDBKIRFCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- 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
- C07C213/08—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 not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application discloses a method for synthesizing pentamethyl diethylenetriamine, wherein under the conditions of set temperature, hydrogen pressure and dimethylamine pressure, N-methyldiethanolamine solution of dimethylamine is introduced into a fixed bed, the solution passes through a catalyst bed layer to obtain reaction solution containing pentamethyl diethylenetriamine, and the pentamethyl diethylenetriamine is obtained through separation and purification. The invention uses dimethylamine and N-methyldiethanolamine as raw materials, and has low cost and good economic benefit; the process avoids using a formaldehyde aqueous solution, reduces the production amount of process wastewater, and saves a large amount of energy consumption.
Description
Technical Field
The application relates to the field of chemical synthesis, in particular to a continuous synthesis method of pentamethyl diethylenetriamine.
Background
In the urethane reaction and the gel reaction, the pentamethyldiethylenetriamine catalyst is a high-activity tertiary amine catalyst, and the alkaline characteristic can more effectively catalyze the reaction between water and isocyanate due to the unique space shielding effect of amino nitrogen, so that the pentamethyldiethylenetriamine catalyst is used as a foaming catalyst for hard foam and soft foam. Therefore, the synthesis of pentamethyldiethylenetriamine is a great concern for scientists.
The synthesis routes of pentamethyldiethylenetriamine reported in the literature at present mainly comprise the following routes:
chinese patent CN 93110707 reports a method for preparing pentamethyl diethylenetriamine from formaldehyde, formic acid and diethylenetriamine as raw materials. The synthetic process route has the defects of long reaction time of the process route, complicated post-treatment operation and the like
U.S. Pat. No. 4, 5105013,893,78 discloses a process for synthesizing diethylenetriamine by dropwise adding formaldehyde solution in the presence of nickel-based catalyst and hydrogen gas. The route reported in the patent has the defects of long formaldehyde dripping time and low product yield, and a large amount of wastewater is generated by dripping formaldehyde aqueous solution.
Chinese patent CN 101659618A discloses a synthetic route for preparing pentamethyl diethylenetriamine by hydrogenation reaction of formaldehyde and diethylenetriamine under the action of palladium or platinum supported catalyst. The catalyst in the route uses noble metal, the cost is high, and the use of formaldehyde aqueous solution causes a large amount of process wastewater.
Disclosure of Invention
In order to make up for the defects of the prior art, the application provides an economic, green, continuous and efficient synthesis method of pentamethyldiethylenetriamine.
A synthetic method of pentamethyldiethylenetriamine comprises the following steps: n-methyldiethanolamine and dimethylamine are used as raw materials and react under the action of a catalyst to form the catalyst.
The process synthesis route is as follows:
namely: the N-methyldiethanolamine and dimethylamine are subjected to hydroamination to generate an intermediate 2- (dimethylaminoethylmethylamino) ethanol, and then the intermediate and one molecule of dimethylamine are subjected to hydroamination to generate the target product pentamethyldiethylenetriamine.
The invention uses dimethylamine and N-methyldiethanolamine as raw materials, and has low cost and good economic benefit; the production process adopts continuous production, and the production efficiency is high; meanwhile, compared with the diethylenetriamine formaldehyde production process, the process avoids using a formaldehyde aqueous solution, greatly reduces the production amount of process wastewater, and has simple product separation and low energy consumption.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Alternatively, the reaction is carried out in a fixed bed. Simple process and is suitable for industrial continuous production.
One optional specific process is: and (2) introducing an N-methyldiethanolamine solution of dimethylamine into the fixed bed under the conditions of set temperature, hydrogen pressure and dimethylamine pressure, allowing the solution to pass through a catalyst bed layer to obtain a reaction solution containing pentamethyldiethylenetriamine, and separating and purifying to obtain the pentamethyldiethylenetriamine.
Optionally, the reaction temperature is 80-200 ℃, and further, the temperature is 150-; the hydrogen pressure is 0.5-4MPa, further, the pressure is 1-2 MPa; the dimethylamine pressure is 0.1-0.5MPa, and further, the pressure is 0.2-0.3 MPa; the WHSV of the solution passing through the catalyst bed layer is 0.05-7 h-1Further, the WHSV is 3-5 h-1。
Optionally, the catalyst is a supported solid catalyst, and comprises a carrier, an active component and an auxiliary active component; the active component is one or more of Ni, Cu and Co; the catalyst promoter component is one or more of Zn, Fe, La, Cr, Mn and Ce; the carrier is one or a mixture of more of alumina, molecular sieve, silica gel and kaolin. The catalyst has long service life and low cost, and is suitable for industrial production.
Optionally, in the supported solid catalyst, in percentage by weight, the content of the active component ranges from 10 to 50%, the content of the cocatalyst ranges from 5 to 30%, and the balance is the carrier.
Furthermore, the content range of the active component is 20-30%, the content range of the cocatalyst is 10-20%, and the balance is the carrier.
Further, the active component is Cu, and the content is 30%; the auxiliary active component is Zn or Cr, and the content is 10%.
Optionally, the supported solid catalyst is prepared by the following method: the metal salt of the active component and the auxiliary active component and the carrier are prepared into a load type oxide by an impregnation method or a coprecipitation-kneading extrusion method, and then the load type oxide is reduced in a hydrogen atmosphere to obtain the reducing solid catalyst.
Optionally, in the coprecipitation-kneading extrusion method, the temperature of the water bath for coprecipitation is controlled to be 50-90 ℃, and the pH value is adjusted to be 7.0-8.0; stirring for 30-90 min at 50-90 ℃; filtering, washing to neutrality and detecting NO3 -Until the end; drying the filter cake at 110-130 ℃ for 12-24 hours; and crushing the filter cake, uniformly mixing the crushed filter cake with carrier powder, stirring, grinding, extruding into strips by using a strip extruder, drying for 12-24 hours at 110-130 ℃ in a drying oven, and slowly raising the temperature to 350-650 ℃ in a muffle furnace by a program for roasting for 3-6 hours.
Optionally, in the impregnation method, the carrier is impregnated with the aqueous solution of the metal salts of the active component and the auxiliary active component for several times, the carrier is filtered after being impregnated for 6 to 18 hours for the first time, the carrier carrying the metal nitrate is dried for 12 to 24 hours at 110 to 130 ℃, and then is roasted for 3 to 6 hours at 300 to 400 ℃; and (3) soaking the carrier for 6-18 hours for the second time after cooling, filtering, drying at 110-130 ℃ for 12-24 hours, and roasting at 350-650 ℃ for 3-6 hours.
Optionally, finally, reducing for 4 hours at 240 ℃ under the hydrogen pressure of 1-2MPa to obtain the reducing supported catalyst.
Optionally, the molar ratio of dimethylamine to N-methyldiethanolamine is 2: 1-10: 1; further, the molar ratio of dimethylamine to N-methyldiethanolamine is 4: 1-6: 1; further, the molar ratio of dimethylamine to N-methyldiethanolamine is 4: 1.
Optionally, the catalyst is filled in a single-tube fixed bed reactor, and the diameter and the length of the single-tube fixed bed reactor are respectively 15mm and 1 m; the filling height of the catalyst is 0.2-0.5 m.
Compared with the prior art, the application has at least one of the following beneficial effects:
(1) the dimethylamine and the N-methyldiethanolamine are used as raw materials, so that the cost is low, and the economic benefit is good;
(2) the production by utilizing the fixed bed has simple process and is suitable for industrial continuous production;
(3) the catalyst prepared by the method has long service life and low cost, and is suitable for industrial production;
(4) the process avoids using a formaldehyde aqueous solution, reduces the production amount of process wastewater, and saves a large amount of energy consumption.
Drawings
FIG. 1 is a 1H-NMR spectrum of pentamethyldiethylenetriamine prepared in example 1.
FIG. 2 is an IR spectrum of pentamethyldiethylenetriamine prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Example 1
(1) Preparation of the reducing catalyst (coprecipitation-kneading extrusion method):
76g of Cu (NO)3)2·3H2O，27g Cr(NO3)2·6H2O and 12g Zn (NO)3)2·6H2Mechanically stirring an aqueous solution of O and 35g of sodium carbonate until the precipitation is complete; keeping the temperature of the water bath at 75 ℃, and adjusting the pH value to 7.5; after keeping the temperature and continuing stirring for 60 minutes, filtering and washing to be neutral, and detecting NO3 -Until the end; drying the filter cake for 12 hours at 120 ℃; the filter cake is crushed and then evenly mixed with 40g of gamma-alumina powder, stirred and ground, extruded into strips by a strip extruder, dried for 12 hours at 120 ℃ in a drying oven, and then slowly heated to 500 ℃ by a program in a muffle furnace and roasted for 4 hours to prepare the oxidizing solid catalyst. Reducing for 4h at 240 ℃ under the hydrogen pressure of 1MPa to obtain the reducing load catalyst Cu-Cr-Zn/Al2O3. The content of active components in the obtained reducing supported catalyst is 30%, the content of auxiliary active components is 10%, and the balance is a carrier.
(2) Synthesis of pentamethyldiethylenetriamine:
15 g of the reduced solid catalyst prepared in step (1) was packed in a single-tube fixed-bed reactor having a diameter of 15mm and a length of 1.0m, and the packing height of the catalyst layer was about 0.3 m. Raising the temperature to 200 ℃, introducing dimethylamine gas at the system pressure of 0.2MPa, and introducing hydrogen gas at the system pressure of 2.2MPa to ensure that the hydrogen partial pressure is 2 MPa. Then the N-methyldiethanolamine and the dimethylamine are pumped into a catalytic amination reactor from the upper end through a preheater by a pump, the molar ratio is controlled to be 1:4 (N-methyldiethanolamine: dimethylamine), and the WHSV is 5h-1And the reaction product flows out from the lower end of the fixed bed reactor, and the effluent is cooled and subjected to gas-liquid separation to obtain a product mixed solution. Through gas chromatographic analysis, the conversion rate of N-methyldiethanolamine is 95%, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol is 10.7%, and the selectivity of pentamethyldiethylenetriamine is 88.3%.
Preparation of pentamethyldiethylenetriamine1H-NMR is shown in FIG. 1; the infrared spectrum is shown in FIG. 2.
Example 2
(1) Preparation of the reductive catalyst (impregnation method)
76g of Cu (NO)3)2·3H2O，27g Cr(NO3)2·6H2O and 12g Zn (NO)3)2·6H2Soaking the water solution of O twice with 40g of formed gamma-alumina; the first dipping is carried out for 12 hours, then the filtration is carried out, and the carrier loaded with the metal nitrate is dried for 12 hours at the temperature of 120 ℃; after cooling, the support is dipped for the second time for 12 hours, filtered and dried at 120 ℃ for 12 hours, and then calcined at 500 ℃ for 4 hours. Finally, reducing for 4h at 240 ℃ under the hydrogen pressure of 1MPa to obtain the reducing supported catalyst.
The content of active components in the obtained reducing supported catalyst is 30%, the content of auxiliary active components is 10%, and the balance is a carrier.
(2) Synthesis of pentamethyldiethylenetriamine:
the catalyst activity test is the same as that in example 1, the conversion rate of N-methyldiethanolamine is 96%, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol is 15.2%, and the selectivity of pentamethyldiethylenetriamine is 83.4% after the reaction solution is analyzed by gas chromatography.
Comparative example 1
The preparation process is exactly the same as in example 1, except that the catalyst is Cu/Al2O3The reaction solution is analyzed by gas chromatography, the conversion rate of N-methyldiethanolamine is 60%, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol is 35.2%, the selectivity of pentamethyldiethylenetriamine is 63.4%, the reaction solution is blue, and the active components of the catalyst are lost.
From the comparison between the results of comparative example 1 and example 1, it can be seen that both N-methyldiethanolamine and dimethylamine, which are raw materials in the present application, react under the action of a conventional catalyst or a catalyst preferred in the present application to synthesize pentamethyldiethylenetriamine; when a supported solid catalyst comprising a carrier, an active component and a co-active ingredient is used, the conversion is better.
Example 3
The preparation process is completely the same as that in example 1, except that the reaction temperature is 150 ℃, the reaction solution is analyzed by gas chromatography, the conversion rate of N-methyldiethanolamine is 85 percent, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol is 23.5 percent, and the selectivity of pentamethyldiethylenetriamine is 75.3 percent
Example 4
The preparation process is completely the same as that in example 1, except that the dimethylamine pressure and the partial pressure of dimethylamine are 0.5Mpa, and the conversion rate of N-methyldiethanolamine, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol and the selectivity of pentamethyldiethylenetriamine are 97%, respectively, through gas chromatography analysis of the reaction solution, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol and 90.2% respectively.
Example 5
The preparation process was identical to that of example 1, except for the feed rate, WHSV of 3h-1The reaction solution was analyzed by gas chromatography, and the conversion of N-methyldiethanolamine was 100%, the selectivity of 2- (dimethylaminoethylmethylamino) ethanol was 3.6%, and the selectivity of pentamethyldiethylenetriamine was 95.0%.
Example 6
The preparation process is the same as that in example 1 except that the active component of the catalyst is Ni-Cr-Zn/Al2O3The reaction solution was analyzed by gas chromatography, and the conversion of N-methyldiethanolamine was 93%, the selectivity for 2- (dimethylaminoethylmethylamino) ethanol was 13.6%, and the selectivity for pentamethyldiethylenetriamine was 85.5%.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A synthetic method of pentamethyldiethylenetriamine is characterized by comprising the following steps: n-methyldiethanolamine and dimethylamine are used as raw materials and react under the action of a catalyst to form the catalyst.
2. The synthesis process according to claim 1, characterized in that the reaction is carried out in a fixed bed.
3. The synthesis method according to claim 2, characterized in that under the conditions of set reaction temperature, hydrogen pressure and dimethylamine pressure, N-methyldiethanolamine solution of dimethylamine is introduced into a fixed bed filled with catalyst, and after the solution passes through a catalyst bed layer, reaction solution containing pentamethyldiethylenetriamine is obtained, and the pentamethyldiethylenetriamine is obtained through separation and purification.
4. The synthesis method according to claim 3, characterized in that the reaction temperature is 80-200 ℃; the hydrogen pressure is 0.5-4 MPa; the pressure of dimethylamine is 0.1-0.5 MPa; the WHSV of the solution passing through the catalyst bed layer is 0.05-7 h-1。
5. The synthesis method according to claim 1, wherein the catalyst is a supported solid catalyst comprising a carrier, an active component and a co-active ingredient; the active component is one or more of Ni, Cu and Co; the catalyst promoter component is one or more of Zn, Fe, La, Cr, Mn and Ce; the carrier is one or a mixture of more of alumina, molecular sieve, silica gel and kaolin.
6. The synthesis method according to claim 5, wherein the supported solid catalyst comprises, by weight, 10-50% of active component, 5-30% of cocatalyst and the balance of carrier.
7. The synthesis method according to claim 5, wherein the supported solid catalyst is prepared by the following method: the metal salts of the active component and the auxiliary active component and the carrier are prepared into a load type oxide by an impregnation method or a coprecipitation kneading extrusion strip method, and then the load type oxide is reduced in a hydrogen atmosphere to obtain the reducing solid catalyst.
8. The synthesis method according to claim 1, wherein the molar ratio of dimethylamine to N-methyldiethanolamine is 2: 1-10: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011188433.6A CN112159323A (en) | 2020-10-30 | 2020-10-30 | Synthesis method of pentamethyldiethylenetriamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011188433.6A CN112159323A (en) | 2020-10-30 | 2020-10-30 | Synthesis method of pentamethyldiethylenetriamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112159323A true CN112159323A (en) | 2021-01-01 |
Family
ID=73865235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011188433.6A Pending CN112159323A (en) | 2020-10-30 | 2020-10-30 | Synthesis method of pentamethyldiethylenetriamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112159323A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385109A (en) * | 2021-06-24 | 2021-09-14 | 江苏万盛大伟化学有限公司 | Device and method for coproducing pentamethyl diethylenetriamine and trimethyl hydroxyethyl ethylenediamine |
| CN114605268A (en) * | 2022-03-22 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3422610A1 (en) * | 1984-06-19 | 1985-12-19 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AMINES |
| US4795834A (en) * | 1987-03-02 | 1989-01-03 | Stepan Company | Catalytic alkylation of primary and secondary amino groups in linear polyamines |
| EP0510493A2 (en) * | 1991-04-22 | 1992-10-28 | Kao Corporation | Process for producing N-alkyl-N-methylamine or N-alkenyl-N-methylamine |
| JPH0987235A (en) * | 1995-09-22 | 1997-03-31 | Kao Corp | Production of n,n-dimethyl-n-alkylamine or-alkenylamine |
| JP2001151734A (en) * | 1999-11-26 | 2001-06-05 | Kao Corp | Method for producing tertiary amine |
| CN1869001A (en) * | 2006-06-27 | 2006-11-29 | 浙江大学 | Production method of N-ethyl iso penlyl amine and its device |
| DE102005047464A1 (en) * | 2005-09-30 | 2007-04-05 | Basf Ag | Preparation of ethylene amine, useful as solvent and stabilizer for synthesizing e.g. synthetic resins, comprises reacting a monoethanol amine with ammonia in the presence of a transition metal heterogeneous catalyst |
| CN101012172A (en) * | 2006-01-30 | 2007-08-08 | 花王株式会社 | Method of preparing tertiary amine |
| CN101659618A (en) * | 2009-09-15 | 2010-03-03 | 烟台万华聚氨酯股份有限公司 | Preparation method of pentamethyldiethylenetriamine |
| CN104557562A (en) * | 2015-01-28 | 2015-04-29 | 无锡市杨市化工有限公司 | Method for producing N,N,N',N'- tetramethylethylenediamine by virtue of direct catalytic amination of dimethylethanolamine |
| CN106513002A (en) * | 2016-11-03 | 2017-03-22 | 中南大学 | Catalyst used for catalyzing synthesis of aliphatic tertiary amine from primary amine or secondary amine and fatty alcohol as well as preparation and application of catalyst |
| CN109574855A (en) * | 2018-11-27 | 2019-04-05 | 万华化学集团股份有限公司 | Serialization prepares the method for pentamethyl-diethylenetriamine and the catalyst system for this method |
| CN109761819A (en) * | 2019-01-23 | 2019-05-17 | 浙江新化化工股份有限公司 | A kind of N, N-dimethyl propylamine continuous preparation method |
| CN109908900A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of loaded catalyst and the preparation method and application thereof |
| CN110511153A (en) * | 2019-04-15 | 2019-11-29 | 绍兴兴欣新材料股份有限公司 | A kind of preparation method of bis- (2- dimethyl amido ethyl) ethers |
| CN111116386A (en) * | 2019-12-19 | 2020-05-08 | 山东国邦药业有限公司 | Synthetic method of hydroxyethyl ethylenediamine |
-
2020
- 2020-10-30 CN CN202011188433.6A patent/CN112159323A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3422610A1 (en) * | 1984-06-19 | 1985-12-19 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AMINES |
| US4795834A (en) * | 1987-03-02 | 1989-01-03 | Stepan Company | Catalytic alkylation of primary and secondary amino groups in linear polyamines |
| EP0510493A2 (en) * | 1991-04-22 | 1992-10-28 | Kao Corporation | Process for producing N-alkyl-N-methylamine or N-alkenyl-N-methylamine |
| US5296631A (en) * | 1991-04-22 | 1994-03-22 | Kao Corporation | Process for producing N-alkyl-N-methylamine or N-alkenyl-N-methylamine |
| JPH0987235A (en) * | 1995-09-22 | 1997-03-31 | Kao Corp | Production of n,n-dimethyl-n-alkylamine or-alkenylamine |
| JP2001151734A (en) * | 1999-11-26 | 2001-06-05 | Kao Corp | Method for producing tertiary amine |
| DE102005047464A1 (en) * | 2005-09-30 | 2007-04-05 | Basf Ag | Preparation of ethylene amine, useful as solvent and stabilizer for synthesizing e.g. synthetic resins, comprises reacting a monoethanol amine with ammonia in the presence of a transition metal heterogeneous catalyst |
| CN101012172A (en) * | 2006-01-30 | 2007-08-08 | 花王株式会社 | Method of preparing tertiary amine |
| CN1869001A (en) * | 2006-06-27 | 2006-11-29 | 浙江大学 | Production method of N-ethyl iso penlyl amine and its device |
| CN101659618A (en) * | 2009-09-15 | 2010-03-03 | 烟台万华聚氨酯股份有限公司 | Preparation method of pentamethyldiethylenetriamine |
| CN104557562A (en) * | 2015-01-28 | 2015-04-29 | 无锡市杨市化工有限公司 | Method for producing N,N,N',N'- tetramethylethylenediamine by virtue of direct catalytic amination of dimethylethanolamine |
| CN106513002A (en) * | 2016-11-03 | 2017-03-22 | 中南大学 | Catalyst used for catalyzing synthesis of aliphatic tertiary amine from primary amine or secondary amine and fatty alcohol as well as preparation and application of catalyst |
| CN109908900A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of loaded catalyst and the preparation method and application thereof |
| CN109574855A (en) * | 2018-11-27 | 2019-04-05 | 万华化学集团股份有限公司 | Serialization prepares the method for pentamethyl-diethylenetriamine and the catalyst system for this method |
| CN109761819A (en) * | 2019-01-23 | 2019-05-17 | 浙江新化化工股份有限公司 | A kind of N, N-dimethyl propylamine continuous preparation method |
| CN110511153A (en) * | 2019-04-15 | 2019-11-29 | 绍兴兴欣新材料股份有限公司 | A kind of preparation method of bis- (2- dimethyl amido ethyl) ethers |
| CN111116386A (en) * | 2019-12-19 | 2020-05-08 | 山东国邦药业有限公司 | Synthetic method of hydroxyethyl ethylenediamine |
Non-Patent Citations (2)
| Title |
|---|
| 李秋小等: "脂肪醇催化胺化制叔胺工艺技术现状及前景", 《日用化学工业》 * |
| 钱霞等: "脂肪醇固定床胺化理论与实践", 《日用化学工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385109A (en) * | 2021-06-24 | 2021-09-14 | 江苏万盛大伟化学有限公司 | Device and method for coproducing pentamethyl diethylenetriamine and trimethyl hydroxyethyl ethylenediamine |
| CN114605268A (en) * | 2022-03-22 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
| CN114605268B (en) * | 2022-03-22 | 2023-02-28 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2154630C2 (en) | Method of preparing aliphatic alpha, omega-aminotriles | |
| US6977237B2 (en) | Catalyst and process for the preparation of hydrocarbons | |
| US6680280B1 (en) | Hydrogenating catalyst containing nickel and method for producing the same | |
| EP1409447B1 (en) | A process for the manufacture of diethylenetriamine and higher polyethylenepolyamines | |
| CN112159323A (en) | Synthesis method of pentamethyldiethylenetriamine | |
| US7468342B2 (en) | Catalysts and process for producing aromatic amines | |
| CN102698761A (en) | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application | |
| CN108889313B (en) | Supported nickel catalyst and preparation method and application thereof | |
| CN103316676A (en) | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof | |
| US20110105313A1 (en) | Use of sulphur-containing supports for catalytic reforming | |
| CN1239468C (en) | Method for the racemization of optically active amines | |
| CN108014821B (en) | Catalyst for synthesizing polyether amine and preparation method and application thereof | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| EP0566197A1 (en) | Process for preparing primary amines and catalyst system suitable therefor | |
| CN105061176A (en) | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone | |
| CN117623327A (en) | Ni modified micropore-mesoporous molecular sieve and preparation method and application thereof | |
| CN115970707A (en) | Preparation method and application method of hydrogenation catalyst | |
| KR20120103323A (en) | Catalyst for manufacturing alkylamine from reductive amination | |
| CN115779912A (en) | Catalyst for synthesizing 2, 2-bipyridine by one-step method and preparation method and application thereof | |
| CN112604709B (en) | Hydrogenation catalyst for sulfur-containing waste gas treatment and application thereof | |
| CN114797947A (en) | Efficient dehydrogenation catalyst and application thereof in preparation of pyridine by dehydrogenation of piperidine raw materials | |
| CN117085684A (en) | Catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, preparation and application thereof | |
| CN113731442B (en) | Catalyst for dimethyl maleate hydrogenation reaction and preparation method and application thereof | |
| CN112457158B (en) | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof | |
| CN112569943B (en) | Nickel-based benzene hydrogenation catalyst and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210101 |