CN1417200A - Hexanedinitrile hydrogenating process of preparing hexanediamine - Google Patents
Hexanedinitrile hydrogenating process of preparing hexanediamine Download PDFInfo
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- CN1417200A CN1417200A CN 01134263 CN01134263A CN1417200A CN 1417200 A CN1417200 A CN 1417200A CN 01134263 CN01134263 CN 01134263 CN 01134263 A CN01134263 A CN 01134263A CN 1417200 A CN1417200 A CN 1417200A
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Abstract
The hexanedinitrile hydrogenating process of preparing hexanediamine comprises the contact of ethanol solution of hexanedinitrile with hydrogen in the presence of catalyst and in the hexanedinitrile hydrogenating conditions. It is characterized by the Ni-containing amorphous alloy catalyst with only one diffuse peak within 20-80 deg range of its X-ray diffraction pattern. The catalyst consists of Ni 50-95 wt%, Al 0-30 wt%, P 0-25 wt%, Fe 0-25 wt% and one of Co, Cr and Mo 0-10 wt%.
Description
Invention field
The present invention relates to a kind of method of adipic dinitrile hydrogenation preparing hexanediamine.
Background technology
Hexanediamine is a monomer of producing nylon-66, and existing technology generally adopts Raney Ni catalyzer to be produced by adipic dinitrile hydrogenation.
USP5,900,511 disclosed methods by the adipic dinitrile hydrogenation preparing hexanediamine adopt skeletal Co catalysts and tank reactor, about 75 ℃ of temperature of reaction, the about 500psig of pressure.
USP4,064,172 disclosed method by the adipic dinitrile hydrogenation preparing hexanediamine adopts active oxidation iron catalyst and fixed-bed reactor, temperature of reaction 80-200 ℃, pressure 20-500 normal atmosphere.
In addition, the CN1251087A disclosed method adopts skeletal Co catalysts, and the CN1139392A disclosed method adopts skeletal nickel catalyst, and the two all adopts tank reactor.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts the adipic dinitrile hydrogenation preparing hexanediamine of new amorphous state alloy catalyst.
The method of adipic dinitrile hydrogenation preparing hexanediamine provided by the invention be under the hydrogenation technique condition of routine with a kind of catalyzer in the presence of will contain adiponitrile ethanolic soln contact with hydrogen, it is characterized in that said catalyzer is the amorphous alloy catalyst that contains Ni, in being 20-8080 ° of scope, 2 θ only locate to occur a diffuse maximum at 45 ± 1 °, the Ni that consists of 50-95 weight % of this catalyzer in the X-ray diffractogram of this catalyzer, the Al of 0-30 weight %, the P of 0-25 weight %, the iron of 0-25 weight %, and being selected from of 0-10 weight % by Co, Cr, a kind of metal in the group of being formed with Mo; Wherein the amount of Al, P, Fe and Co, Cr or Mo is not zero simultaneously.
The inventive method is owing to adopt amorphous alloy catalyst, and catalyst activity and selectivity height can be simplified flow process, cut down the consumption of energy.
Embodiment
Said activity of such catalysts component Ni preferably exists with amorphous form in the method for adipic dinitrile hydrogenation preparing hexanediamine provided by the invention, but might exist with the form of non-crystalline state and crystallite attitude Ni concurrent, perhaps the form with non-crystalline state, crystallite attitude and a small amount of crystalline state Ni concurrent exists.
The preferred group of said catalyzer becomes the Fe of P, 1-20 weight % of Al, 0-20 weight % of Ni, 5-20 weight % of 65-90 weight % and Cr or the Mo of 0-10 weight % in the method for adipic dinitrile hydrogenation preparing hexanediamine provided by the invention.
The concentration of said adiponitrile ethanolic soln is 5-95 weight % in the method for adipic dinitrile hydrogenation preparing hexanediamine provided by the invention, and more preferably 10-40 weight % most preferably is 20-35 weight %.
Said hydrogenation technique condition adopts conventional hydrogenation technique condition in the method for adipic dinitrile hydrogenation preparing hexanediamine provided by the invention, the present invention has no particular limits it, but general processing condition are temperature is 40-120 ℃, pressure is the 0.1-4.0 MPa, and the volume ratio of hydrogen and adiponitrile ethanolic soln is 10-200.Preferred processing condition are that temperature is 50-90 ℃, and pressure is the 0.3-3.0 MPa, and the volume ratio of hydrogen and adiponitrile ethanolic soln is 50-150.
Method provided by the invention can be carried out in the tank reactor at intermittence, also can carry out in magnetically stabilized bed reactor.
Method catalyst system therefor provided by the invention can prepare by following steps:
(1) mother alloy preparation
Adopt liquisol quenching method of the prior art to prepare mother alloy, soon one or more in nickel, aluminium and iron, cobalt, tungsten, chromium, molybdenum and the phosphorus etc. join in a kind of high-temperature resistant container (as silica tube or crucible) by certain proportioning, be heated to fusion more than 1300 ℃, make its alloying, be sprayed onto alloy liquid on the metal running roller that has refrigerating unit of one high speed rotating from the nozzle under this container with indifferent gas then, make its fast cooling and throw away along the running roller tangent line, form the flakey band, band is standby as mother alloy after grinding;
(2) mother alloy thermal treatment (this step is optional step)
The mother alloy of (1) gained is heat-treated in the inert gas environment that is selected from hydrogen, argon gas or nitrogen, and heat treated condition is temperature 300-900 ℃, and preferred temperature is 600-700 ℃; Heat treatment time is 0.5-4 hour.The preferred time is 2-3 hour;
(3) activation
The mother alloy of (1) or (2) gained is taken out aluminium with alkaline solution to be handled; Taking out the aluminium method is: a certain amount of alloy powder is mixed with sodium hydroxide solution, make the reaction of most of aluminium in the alloy and sodium hydroxide and extract out, form the bigger catalyst sample of surface-area; Take out the aluminium temperature and be room temperature-120 ℃, be preferably 50-100 ℃; Taking out the aluminium time is 0.5-3 hour, is preferably 1-2 hour; The consumption of alkali is a mother alloy: sodium hydroxide=1: (1-4) (weight ratio);
(4) washing
With the sample temperature of (3) gained is 20-100 ℃, preferred 60-100 ℃ water washing, and the pH value of washing back solution is 7-13; Washing back sample can be kept in the water or in the ethanol, and controlled atmosphere is preferably arranged.
The following examples will be described further method provided by the invention, but therefore not limit the present invention.
Embodiment 1
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
49 gram nickel, 49 gram aluminium, 1 gram iron, 1 gram molybdenum are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas alloy liquid being sprayed onto a rotating speed from the nozzle under this silica tube then is on 800 rev/mins of bell metal rollers, logical water coolant in the copper roller, alloy liquid forms the flakey band through cooling off fast and throwing away along copper roller tangent line, band is below 70 microns through being ground to diameter, obtains mother alloy.Mother alloy is heat-treated in ar gas environment, and thermal treatment temp is 600 ℃, and constant temperature time is 3 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 90 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 80 ℃ distilled water washs to pH value.Prepared catalyzer is numbered catalyzer-1, is kept in the water it standby.
Embodiment 2-6
These embodiment illustrate several Preparation of catalysts that the present invention is used.
Step according to embodiment 1 prepares catalyzer of the present invention, and just the temperature of proportioning, preparation condition such as the thermal treatment temp of catalyzer and time, the temperature and time of taking out aluminium, washing water etc. is different, and the preparation condition of each embodiment is listed in the table 1.The catalyzer of each embodiment gained is numbered catalyzer-2 respectively to catalyzer-6.
Each Preparation of catalysts condition of table 1
| Mother alloy is formed | Thermal treatment | Take out the aluminium activation | Washing | |||||
| Temperature (℃) | Time (hour) | Mother alloy/alkali (weight ratio) | Activation temperature (℃) | Time (hour) | The washing water temperature (℃) | Washing back pH value | ||
| Embodiment 2 | ?Ni 48Fe 1.5Cr 2.5Al 48 | ??600 | ???3 | ??1∶1 | ??100 | ????1 | ?80 | ??7 |
| Embodiment 3 | ?Ni 44Fe 1.5Cr 2.5Al 52 | ??600 | ???3 | ??1∶1 | ??100 | ????1 | ?80 | ??7 |
| Embodiment 4 | ?Ni 48Fe 1.5Cr 2.5Al 48 | ??600 | ???3 | ??1∶2 | ??50 | ????1 | ?80 | ??7 |
| Embodiment 5 | ?Ni 44Fe 2.5Cr 1.5Al 52 | ??700 | ???2 | ??1∶2 | ??100 | ????1.5 | ?100 | ??7 |
| Embodiment 6 | ?Ni 48Fe 2.5Cr 1.5Al 48 | ??700 | ???2 | ??1∶2 | ??100 | ????1.5 | ?100 | ??7 |
Embodiment 7
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
49 gram nickel, 50 gram aluminium, 1 gram iron are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas alloy liquid being sprayed onto a rotating speed from the nozzle under this silica tube then is on 800 rev/mins of bell metal rollers, logical water coolant in the copper roller, alloy liquid forms the flakey band through cooling off fast and throwing away along copper roller tangent line, band is below 70 microns through being ground to diameter, obtains mother alloy.Mother alloy is heat-treated in ar gas environment, and thermal treatment temp is 600 ℃, and constant temperature time is 3 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 90 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 100 ℃ distilled water washs to pH value, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-7.
Embodiment 8
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
49 gram nickel, 50 gram aluminium, 1 gram chromium are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas alloy liquid being sprayed onto a rotating speed from the nozzle under this silica tube then is on 800 rev/mins of bell metal rollers, logical water coolant in the copper roller, alloy liquid forms the flakey band through cooling off fast and throwing away along copper roller tangent line, band is below 70 microns through being ground to diameter, obtains mother alloy.Mother alloy is heat-treated in ar gas environment, and thermal treatment temp is 600 ℃, and constant temperature time is 3 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 90 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 100 ℃ distilled water washs to pH value, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-8.
Embodiment 9
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
80 gram nickel, 20 gram phosphorus are placed crucible, the heating make its voluntarily alloying make the Ni-P alloy, get this alloy 48 grams, add in the silica tube with 50 gram aluminium, 2 gram iron, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas alloy liquid being sprayed onto a rotating speed from the nozzle under this silica tube then is on 800 rev/mins of bell metal rollers, logical water coolant in the copper roller, alloy liquid is through cooling off fast and throwing away along copper roller tangent line, form the flakey band, band is under ventilated environment below the efflorescence to 50 micron.Get 50 these mother alloys of gram and slowly add in the solution that 110 gram sodium hydroxide and 450 gram water are made into, 0 ℃ was stirred 10 minutes down, stirred 60 minutes down at 40 ℃ then.After stopping heating and stirring, decantation liquid, being washed with distilled water to the pH value is 7, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-9.
Embodiment 10
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
80 gram nickel, 20 gram phosphorus are placed crucible, the heating make its voluntarily alloying make the Ni-P alloy, get this alloy 48 grams, add in the silica tube with 50 gram aluminium, 2 gram iron, it is heated to fusion more than 1450 ℃ in high frequency furnace, make its alloying, with the indifferent gas of 0.08 MPa alloy liquid being sprayed onto a rotating speed from the nozzle under this silica tube then is on 1000 rev/mins of bell metal rollers, logical water coolant in the copper roller, alloy liquid is through cooling off fast and throwing away along copper roller tangent line, form the flakey band, band is below 70 microns through being ground to diameter, obtains mother alloy.Get 50 these mother alloys of gram and slowly add in the solution that 50 gram sodium hydroxide and 250 gram water are made into, placed 1 hour under the room temperature, be warming up to 80 ℃ then and stirred 2 hours down.After stopping heating and stirring, decantation liquid, being washed with distilled water to the pH value is 7, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-10.
Comparative Examples 1-2
This Comparative Examples provides the conventional Raney Ni comparative catalyst who uses in two kinds of prior aries.
Comparative Examples 1 used Raney Ni catalyzer is produced by Liaoyang FCFC and is sold, and Comparative Examples 2 used Raney Ni catalyzer are sold by the catalyst plant production of Yangzhou, Jiangsu Province.
Embodiment 11
Present embodiment illustrates that catalyzer provided by the invention and comparative catalyst are used for the activity and the selectivity of adipic dinitrile hydrogenation preparing hexanediamine.
In 250 milliliters of autoclaves, add 100 milliliters of adiponitrile-ethanolic soln and 2 grams catalyzer provided by the invention that contain 30 weight % adiponitriles, feed hydrogen, regulating the still internal pressure is 2.0 MPas, and heating and constant temperature are at 70 ℃, stirred 30 minutes, stirring velocity is 630 rev/mins.Take out reacted liquid and, try to achieve transformation efficiency and selectivity thus with its composition of gas chromatographic analysis.
Hydrogenation effect when table 2 adopts different catalysts
| Numbering | Catalyzer is formed (weight %) | Adiponitrile transformation efficiency (weight %) | Hexanediamine selectivity (weight %) |
| Catalyzer-1 | ?Ni 79Fe 2Mo 1.8Al 17.2 | ?99.2 | ?88.7 |
| Catalyzer-2 | ?Ni 87Fe 1Cr 2Al 10 | ?100 | ?97.4 |
| Catalyzer-3 | ?Ni 80Fe 1.5Cr 3.5Al 15 | ?100 | ?96.7 |
| Catalyzer-4 | ?Ni 82Fe 5Mo 3.5Al 9.5 | ?98.5 | ?90.1 |
| Catalyzer-5 | ?Ni 85Fe 3.5Cr 1.5Al 10 | ?100 | ?100 |
| Catalyzer-6 | ?Ni 85Fe 3.5Mo 1.5Al 10 | ?98.3 | ?92.2 |
| Catalyzer-7 | ?Ni 88Fe 2Al 10 | ?98.2 | ?87.2 |
| Catalyzer-8 | ?Ni 85Cr 2Al 13 | ?97.4 | ?89.4 |
| Catalyzer-9 | ?Ni 75.8Fe 4.9P 2.8Al 16.5 | ?94.2 | ?90.4 |
| Catalyzer-10 | ?Ni 78.4Fe 2.0P 19.6 | ?98.7 | ?94.4 |
| Comparative Examples-1 | ?Ni 85Cr 2Al 13 | ?92.3 | ?61.4 |
| Comparative Examples-2 | ?Ni 86.4Al 13.6 | ?96.2 | ?70.5 |
Embodiment 12
Present embodiment illustrates that catalyzer provided by the invention and comparative catalyst are used for the activity and the selectivity of adipic dinitrile hydrogenation preparing hexanediamine.
In 2 liters of autoclaves, add 369 restrain oneself dintrile, 370 milliliters of ethanol, 7.5 milliliter of 30 weight % aqueous sodium hydroxide solution and 26 grams catalyzer provided by the invention, feed hydrogen, regulating the still internal pressure is 2.2 MPas, and heating and constant temperature are at 93 ℃, stirred 20 minutes, stirring velocity is 100 rev/mins.Take out reacted liquid and, try to achieve transformation efficiency and selectivity thus with its composition of gas chromatographic analysis.
Hydrogenation effect when table 3 adopts different catalysts
| Numbering | Catalyzer is formed (weight %) | Adiponitrile transformation efficiency (weight %) | Hexanediamine selectivity (weight %) |
| Catalyzer-5 | ??Ni 85Fe 3.5Cr 15Al 10 | ???87.6 | ??27.8 |
| Contrast medium-1 | ??Ni 86.4Al 13.6 | ???72.7 | ??11.6 |
Embodiment 13-15
Present embodiment illustrates the hydrogenation effect of method provided by the invention under the differential responses condition.
Table 4 has been listed the reaction result when changing hydrogenation conditions.Be reflected in 250 milliliters of autoclaves and carry out, adopt catalyzer 5, stirring velocity is 630 rev/mins.
Hydrogenation effect under the table 4 differential responses condition
| Embodiment | Temperature (℃) | Pressure (MPa) | Agent material ratio | Adiponitrile transformation efficiency (weight %) | Hexanediamine selectivity (weight %) |
| ??13 | ??90 | ??0.5 | ??1 | ??96.2 | ??80.7 |
| ??14 | ??90 | ??3.0 | ??1 | ??100 | ??100 |
| ??15 | ??50 | ??3.0 | ??1.5 | ??98.3 | ??97.7 |
Embodiment 16
Present embodiment illustrates the hydrogenation effect when method provided by the invention is carried out in different reactor.The catalyzer that uses in the different reactor is catalyzer-5.The still reaction condition is identical with embodiment 12, the magnetically stabilized bed reactor internal diameter is 14 millimeters, four internal diameters are 55 millimeters, external diameter for 165 millimeters, height for 35 millimeters, the number of turn for 370 coil along the reactor axial arranging so that uniform magnetic field to be provided, distance is 27.5 millimeters between the coil, and magneticstrength is 200 oersteds during operation, and the catalyzer loading amount is 10 milliliters, feed liquid is entered by the bottom, and flow out on top.
Hydrogenation effect during table 5 different reactor
| Tank reactor | Magnetically stabilized bed reactor | |
| Temperature (℃) | ????70 | ????70 |
| Pressure (Mpa) | ????2 | ????2 |
| Hydrogen/raw material (volume ratio) | ????-- | ????100 |
| Catalyst/feed (weight ratio) | ????1 | ????-- |
| Air speed (hour -1) | ????-- | ????16 |
| Adiponitrile transformation efficiency (weight %) | ????87.6 | ????99.2 |
| Hexanediamine selectivity (weight %) | ????27.8 | ????78.4 |
Claims (7)
1, a kind of method of adipic dinitrile hydrogenation preparing hexanediamine, be under the adipic dinitrile hydrogenation processing condition with a kind of catalyzer in the presence of will contain adiponitrile ethanolic soln contact with hydrogen, it is characterized in that said catalyzer is the amorphous alloy catalyst that contains Ni, in being 20-80 ° scope, 2 θ only locate to occur a diffuse maximum at 45 ± 1 °, the Ni that consists of 50-95 weight % of this catalyzer in the X-ray diffractogram of this catalyzer, the Al of 0-30 weight %, the P of 0-25 weight %, the iron of 0-25 weight %, and being selected from of 0-10 weight % by Co, Cr, a kind of metal in the group of being formed with Mo; Wherein the amount of Al, P, Fe and Co, Cr or Mo is not zero simultaneously.
2, according to the process of claim 1 wherein the Fe of P, 1-20 weight % of Al, 0-20 weight % of the Ni that consists of 65-90 weight %, 5-20 weight % of said catalyzer and Cr or the Mo of 0-10 weight %.
3, according to the process of claim 1 wherein that the concentration of said adiponitrile ethanolic soln is 5-95 weight %.
4, according to the method for claim 3, the concentration of wherein said adiponitrile ethanolic soln is 10-40 weight %.
5, according to the process of claim 1 wherein that said adipic dinitrile hydrogenation processing condition are that temperature is 40-120 ℃, pressure is the 0.1-4.0 MPa, and the volume ratio of hydrogen and adiponitrile ethanolic soln is 10-200.
6, according to the method for claim 5, wherein said adipic dinitrile hydrogenation processing condition are that temperature is 50-90 ℃, and pressure is the 0.3-3.0 MPa, and the volume ratio of hydrogen and adiponitrile ethanolic soln is 50-150.
7, according to the process of claim 1 wherein that said contact carries out in the tank reactor or carry out at intermittence in magnetically stabilized bed reactor.
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| CNB011342633A CN1191231C (en) | 2001-10-30 | 2001-10-30 | Hexanedinitrile hydrogenating process of preparing hexanediamine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744083A (en) * | 2012-06-26 | 2012-10-24 | 华烁科技股份有限公司 | Preparation method and activation method of Raney nickel-aluminum-X catalyst specially for hydrogenation preparation of 1,4-butanediol from 1,4-butynediol |
| CN102050742B (en) * | 2009-10-27 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethylamino propylamine through hydrogenating dimethylamino propionitrile in presence of nickel |
| CN109821572A (en) * | 2019-02-14 | 2019-05-31 | 上海释颉化工技术合伙企业(有限合伙) | Porous microsphere Polymer-supported metal catalyst and its preparation method and application |
| CN112321438A (en) * | 2020-11-25 | 2021-02-05 | 重庆华峰化工有限公司 | Synthesis method of hexamethylene diamine |
| CN113620813A (en) * | 2021-08-13 | 2021-11-09 | 中国天辰工程有限公司 | Preparation method of N, N-dimethyl-1, 3-propane diamine |
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2001
- 2001-10-30 CN CNB011342633A patent/CN1191231C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050742B (en) * | 2009-10-27 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethylamino propylamine through hydrogenating dimethylamino propionitrile in presence of nickel |
| CN102744083A (en) * | 2012-06-26 | 2012-10-24 | 华烁科技股份有限公司 | Preparation method and activation method of Raney nickel-aluminum-X catalyst specially for hydrogenation preparation of 1,4-butanediol from 1,4-butynediol |
| CN102744083B (en) * | 2012-06-26 | 2015-11-18 | 华烁科技股份有限公司 | The preparation of the special Raney's nickel-aluminium-X catalyst of Isosorbide-5-Nitrae-butynediols Hydrogenation BDO and activation method |
| CN109821572A (en) * | 2019-02-14 | 2019-05-31 | 上海释颉化工技术合伙企业(有限合伙) | Porous microsphere Polymer-supported metal catalyst and its preparation method and application |
| CN109821572B (en) * | 2019-02-14 | 2022-08-19 | 上海释颉化工技术合伙企业(有限合伙) | Porous microsphere polymer supported metal type catalyst and preparation method and application thereof |
| CN112321438A (en) * | 2020-11-25 | 2021-02-05 | 重庆华峰化工有限公司 | Synthesis method of hexamethylene diamine |
| CN112321438B (en) * | 2020-11-25 | 2024-04-16 | 重庆华峰化工有限公司 | Synthesis method of hexamethylenediamine |
| CN113620813A (en) * | 2021-08-13 | 2021-11-09 | 中国天辰工程有限公司 | Preparation method of N, N-dimethyl-1, 3-propane diamine |
| CN113620813B (en) * | 2021-08-13 | 2024-02-06 | 中国天辰工程有限公司 | Preparation method of N, N-dimethyl-1, 3-propanediamine |
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