CN101954263B - Trickle bed equipment for preparing m-Metaxylenediamine - Google Patents
Trickle bed equipment for preparing m-Metaxylenediamine Download PDFInfo
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- CN101954263B CN101954263B CN201010150741XA CN201010150741A CN101954263B CN 101954263 B CN101954263 B CN 101954263B CN 201010150741X A CN201010150741X A CN 201010150741XA CN 201010150741 A CN201010150741 A CN 201010150741A CN 101954263 B CN101954263 B CN 101954263B
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Abstract
The invention discloses trickle bed equipment for preparing m-Metaxylenediamine. A trickle bed is provided with a material inlet which is connected with a gas and liquid mixer for mixing gas and liquid materials and conveying the mixed materials to the material inlet; the gas and liquid mixer comprises a container shell; a bottom plate of the container shell is provided with a plurality of gas inlets; each gas inlet is connected with a vertical short pipe extending into the container; each vertical short pipe is provided with a plurality of gas outlets; the upper end of the container shell is provided with a liquid inlet; and the side face of the container shell is provided with a material outlet connected with the material inlet of the trickle bed. The gas and liquid can be fully mixed before entering a distributor, so the gas and liquid distribution condition in the trickle bed is improved, overlarge radial temperature difference and local overheat of the trickle bed are avoided, polymeric by-products are reduced, the service life of a catalyst is prolonged, the hydrogenation temperature and pressure are reduced, and the molar yield of the m-Metaxylenediamine is improved.
Description
Technical field:
The present invention relates to a kind of trickle bed equipment for preparing m-xylene diamine.
Background technology:
M-xylene diamine, English name meta-phenyldimethylamine or meta-Xylylenediamine,
Molecular formula C
8H
12N
2, molecular weight 136.1, CA registration number 1477-55-0, structural formula:
Colourless liquid has the almond flavor, reveals air for a long time and is yellow, water-soluble and organic solvent, 248 degrees centigrade of boiling points, proportion (d
20) 1.052, refractive index (nD
20) 1.5670, viscosity and dibatyl phithalate are approximate, are colourless transparent liquid.
Be mainly used in and make heat-resisting, nontoxic, underwater construction, the quick-setting high-performance epoxy resin curing agent of heating; Be the raw material of polyurethane resin, complex functionality epoxy resin, also being used for aspects such as rubber, photo-plastics, agricultural chemicals, coating, nylon products, fibre finish agent, antirust agent, chelating agent, lubricant, paper conversion also has application.
In the prior art, the m-xylene diamine synthetic method is generally uses isophthalodinitrile as initiation material, and hydrogenation makes under the situation that catalyst exists.Reaction equation:
Among the CN1285343; Through using the silica gel or the diatomite that contain cobalt, titanium and palladium to be catalyst, the mixture of forming with organic amine and aromatic hydrocarbons is a solvent, is 100～130 ℃ in reaction temperature; In the gauge pressure reaction pressure is under 6～10MPa condition, and using intermittently, the hydrogenation autoclave prepares m-xylene diamine.
CN1310043 has introduced and a kind ofly has been used for the skeleton nickel that batch process prepares the modification of m-xylene diamine and makes catalyst; Introduce tungsten on the skeleton nickel and be selected from that at least a and rare earth metal is as co-catalyst among Cr, Mo, Sn, Fe, Cu, Zr and the Ti, this catalyst is used for the autoclave reaction.
Among the CN1285236, the catalyst of working load type is used for autoclave and prepares m-xylene diamine, and the major metal element in the catalyst is cobalt, titanium and palladium.
Mitsubishi's gas prepares the method (JP2001215006, JP2002245222, JP20030061258, US2005004399, US2007270613 etc.) of benzene dimethylamine: use trickle bed technology; In the presence of the nickel or Co catalysts of support type, adopt the isophthalodinitrile continously hydrogen adding to prepare benzene dimethylamine.Reaction temperature is 60-130 ℃, and reaction pressure is 4-15Mpa, and the molar yield of m-xylene diamine is 85～92%.Wherein trickle bed equipment is not specialized.
Also there is similar serialization trickle bed technology (WO2005026098) in BASF AG; Reactant is the benzene dicarbonitrile of molten state; Solvent is an ammonia; Reaction temperature is 70-130 ℃, and pressure is 150-200bar, that catalyst is selected mixed manganese, phosphorus and alkali-metal load for use or not nickel, cobalt, the iron catalyst of load.Wherein trickle bed equipment is not specialized, the molar yield of m-xylene diamine about 90%.
Batch process in the above-mentioned several kinds of technologies has the restriction of production capacity, can't expand production on a large scale.The shortcoming of trickle bed continuous process then is that reaction temperature and pressure are higher, and the m-xylene diamine yield is not high, traces it to its cause, and is because what time following:
1, the about 400KJ/mol m-xylene diamine of the main reaction reaction heat of this technology; Be strong exothermal reaction; The trickle bed diameter is crossed conference and is caused radial temperature difference excessive, hot-spot, and (side reaction mainly is the high-boiling components that imines class intermediate product and m-xylene diamine polymerization generate in the side reaction aggravation; Temperature is high more, and this polymerisation takes place more easily).
2, the imines class intermediate product on the catalyst just is not easy to continue hydrogenation and generates m-xylene diamine under the situation that does not have the excess hydrogen protection, thereby and can generate high-boiling components impurity with m-xylene diamine or other intermediate product polymerization reaction take place.
3, because the reaction heat of main reaction is very big, thus need excessive greatly hydrogen to take away the heat that reaction generates, otherwise just can cause the bed hot-spot, polymerizate generates in a large number.
4, catalyst particle size is too small, can cause bed pressure drop excessive, thereby is unfavorable for the smooth flow state of gas-liquid; And granularity is excessive, and then interior diffusion effect also can cause the polymerization high-boiling components in the catalyst duct, to generate, thereby catalysqt deactivation or bed pressure drop are increased.Therefore catalyst particle size has optimized scope, and corresponding with it trickle bed internal diameter also has optimum range.
Summary of the invention:
The object of the present invention is to provide a kind of gas and liquid of making before getting into reaction tube, to mix, improve the trickle bed equipment of the preparation m-xylene diamine of m-xylene diamine yield.
Technical solution of the present invention is:
A kind of trickle bed equipment for preparing m-xylene diamine comprises trickle bed, it is characterized in that: trickle bed has a material inlet, charging aperture with gas, liquid raw material are mixed after send into charging aperture air and liquid mixer be connected; Said air and liquid mixer comprises shell of tank; A plurality of air admission holes are set on the base plate of shell of tank; Each air admission hole vertical short tube interior with stretching into container is connected; Each vertical short tube is provided with a plurality of ventholes, and the upper end of shell of tank is provided with the liquid inlet, and the side of shell of tank is provided with the discharging opening that is connected with the trickle bed charging aperture.
A plurality of air admission holes of shell of tank base plate evenly distribute.
Said air admission hole, venthole are circular port.
The percent opening of air and liquid mixer base plate is 5～50%; The diameter of vertical short tube is 1: 10～1: 100 with the ratio of the diameter of air and liquid mixer base plate; The height of vertical short tube and air and liquid mixer discharging opening are 1: 5～1: 100 to the aspect ratio of base plate; The diameter of the venthole on the vertical short tube is 1: 10～1: 100 with the high ratio of vertical short tube, and the percent opening of the venthole of vertical short tube is 5%～30%; The inside diameter ranges of trickle bed is 50～300mm.
The present invention just can fully mix gas and liquid before getting into distributor, improved the inner gas-liquid distribution situation of trickle bed, avoids the trickle bed radial temperature difference excessive; Hot-spot; Reduce polymeric by-products and generate, prolonged catalyst life, thereby reduce (60 ℃ of hydrogenation temperature and pressure; 6MPa), improve the molar yield (reaching 95～97%) of m-xylene diamine.
Description of drawings:
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Fig. 1 is the configuration diagram of one embodiment of the invention.
Fig. 2 is the configuration diagram of air and liquid mixer.
Fig. 3 is the configuration diagram of vertical short tube.
The specific embodiment:
Embodiment 1
A kind of trickle bed equipment for preparing m-xylene diamine comprises air and liquid mixer 1, reactor shell 2, charging aperture 3, gas-liquid distributor 4, porcelain ball bed 5, beds 6, outlet distributor 7 and discharging opening 8;
Adopt following air and liquid mixer: the percent opening on the base plate 12 is 20%; The diameter on the diameter of short tube 13 and blender floor 12 is 1: 35; The height of short tube 13 and blender discharging opening 11 are 1: 30 to the aspect ratio of base plate 12; The diameter of the circular venthole on the short tube 13 is 1: 35 with the high ratio of short tube, and the percent opening of the venthole of short tube 13 is 15%; The trickle bed internal diameter is 150mm.Gas gets into from the gas access 9 of blender below, and liquid gets into from the liquid inlet 10 of top.
The trickle bed hydrogenation reaction that this air and liquid mixer is used for m-xylene diamine:
Adopt the nickel catalyst of support type; Mixed liquid with isophthalodinitrile, meta-xylene, ammonia is supplied with from trickle bed reaction tube top; Supply with hydrogen (excessive 200 times, purpose is to take away heat, and imines class impurity is protected in the excess hydrogen environment) from the reaction tube top simultaneously; At pressure 6MPa, temperature is carried out the continuous hydrogenation reaction for 60 ℃.Gained reactor outlet liquid is analyzed with the liquid chromatogram external standard method, and the conversion ratio of isophthalodinitrile is 100% as a result, and the molar yield of m-xylene diamine is 97.2%, and catalyst service time, the molar yield of m-xylene diamine was higher than 95% all the time within 2000h the time.
Comparative example 1
Except not equipping air and liquid mixer, other condition is all identical with embodiment 1, and the result is 100% for the conversion ratio of isophthalodinitrile, and the yield of m-xylene diamine is 94.9%, and the yield of m-xylene diamine begins to be lower than 93% behind the catalyst use 1500h.
Comparative example 2
The trickle bed internal diameter is 350mm, and all the other conditions are all identical with embodiment 1, and the result is 100% for the conversion ratio of isophthalodinitrile, and the yield of m-xylene diamine is 94.5%, and the yield of m-xylene diamine begins to be lower than 93% behind the catalyst use 1500h.
Adopt following air and liquid mixer: the percent opening on the base plate 12 is 10%; The diameter on the diameter of short tube 13 and blender floor 12 is 1: 20; The height of short tube 13 and blender discharging opening 11 are 1: 10 to the aspect ratio of base plate; The diameter of the circular venthole on the short tube 13 is 1: 20 with the high ratio of short tube, and the percent opening of the venthole of short tube 13 is 10%; The trickle bed internal diameter is 100mm.
The trickle bed hydrogenation reaction that this air and liquid mixer is used for m-xylene diamine:
Adopt the nickel catalyst of support type, supply with from trickle bed reaction tube top with the mixed liquid of isophthalodinitrile, meta-xylene, ammonia, supply with hydrogen (excessive 200 times) from the reaction tube top simultaneously, at pressure 6MPa, temperature is carried out the continuous hydrogenation reaction for 60 ℃.Gained reactor outlet liquid is analyzed with the liquid chromatogram external standard method, and the conversion ratio of isophthalodinitrile is 100% as a result, and the yield of m-xylene diamine is 96.5%, and catalyst service time, the yield of m-xylene diamine was higher than 95% all the time within 1800h the time.
Adopt following air and liquid mixer: the percent opening on the base plate 12 is 30%; The diameter of the diameter of short tube 13 and blender base plate 12 is 1: 50; The height of short tube 13 and blender discharging opening 11 are 1: 50 to the aspect ratio on floor; The diameter of the circular venthole on the short tube 13 is 1: 50 with the high ratio of short tube, and the percent opening of the venthole of short tube 13 is 20%; The trickle bed internal diameter is 200mm.
The trickle bed hydrogenation reaction that this air and liquid mixer is used for m-xylene diamine:
Adopt the nickel catalyst of support type, supply with from trickle bed reaction tube top with the mixed liquid of isophthalodinitrile, meta-xylene, ammonia, supply with hydrogen (excessive 200 times) from the reaction tube top simultaneously, at pressure 6MPa, temperature is carried out the continuous hydrogenation reaction for 60 ℃.Gained reactor outlet liquid is analyzed with the liquid chromatogram external standard method, and the conversion ratio of isophthalodinitrile is 100% as a result, and the yield of m-xylene diamine is 95.9%, and catalyst service time, the yield of m-xylene diamine was higher than 95% all the time within 1800h the time.
Embodiment 4:
A kind of trickle bed equipment for preparing m-xylene diamine comprises trickle bed, and trickle bed has a material inlet, charging aperture with gas, liquid raw material are mixed after send into charging aperture air and liquid mixer be connected; Said air and liquid mixer comprises shell of tank; A plurality of air admission holes are set on the base plate of shell of tank; Each air admission hole vertical short tube interior with stretching into container is connected; Each vertical short tube is provided with a plurality of ventholes, and the upper end of shell of tank is provided with the liquid inlet, and the side of shell of tank is provided with the discharging opening that is connected with the trickle bed charging aperture.A plurality of air admission holes of shell of tank base plate evenly distribute.Said air admission hole, venthole are circular port.
The percent opening of air and liquid mixer base plate is 5～50% (examples 5%, 25%, 50%); The diameter of vertical short tube is 1: 10～1: 100 (example 1: 10,1: 50,1: 100) with the ratio of the diameter of air and liquid mixer base plate; The height of vertical short tube and air and liquid mixer discharging opening are 1: 5～1: 100 (example 1: 5,1: 50,1: 100) to the aspect ratio of base plate; The diameter of the venthole on the vertical short tube is 1: 10～1: 100 (example 1: 10,1: 50,1: 100) with the high ratio of vertical short tube, and the percent opening of the venthole of vertical short tube is 5%～30% (example 5%, 15%, 30%); The inside diameter ranges of trickle bed is 50～300mm (routine 50mm, 150mm, 300mm).
Claims (3)
1. a trickle bed equipment for preparing m-xylene diamine comprises trickle bed, it is characterized in that: trickle bed has a material inlet, charging aperture with gas, liquid raw material are mixed after send into charging aperture air and liquid mixer be connected; Said air and liquid mixer comprises shell of tank; A plurality of air admission holes are set on the base plate of shell of tank; Each air admission hole vertical short tube interior with stretching into container is connected; Each vertical short tube is provided with a plurality of ventholes, and the upper end of shell of tank is provided with the liquid inlet, and the side of shell of tank is provided with the discharging opening that is connected with the trickle bed charging aperture; The percent opening of air and liquid mixer base plate is 5～50%; The diameter of vertical short tube is 1:10～1:100 with the ratio of the diameter of air and liquid mixer base plate; The height of vertical short tube and air and liquid mixer discharging opening are 1:5～1:100 to the aspect ratio of base plate; The diameter of the venthole on the vertical short tube is 1:10～1:100 with the high ratio of vertical short tube, and the percent opening of the venthole of vertical short tube is 5%～30%; The inside diameter ranges of trickle bed is 50～300mm.
2. the trickle bed equipment of preparation m-xylene diamine according to claim 1 is characterized in that: a plurality of air admission holes of shell of tank base plate evenly distribute.
3. the trickle bed equipment of preparation m-xylene diamine according to claim 1 is characterized in that: said air admission hole, venthole are circular port.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010150741XA CN101954263B (en) | 2010-04-20 | 2010-04-20 | Trickle bed equipment for preparing m-Metaxylenediamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010150741XA CN101954263B (en) | 2010-04-20 | 2010-04-20 | Trickle bed equipment for preparing m-Metaxylenediamine |
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| CN101954263A CN101954263A (en) | 2011-01-26 |
| CN101954263B true CN101954263B (en) | 2012-09-05 |
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| CN104667831B (en) * | 2015-02-05 | 2016-08-24 | 天津奥展兴达化工技术有限公司 | Trickle bed reaction unit gas-liquid distributor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159361A (en) * | 1995-12-13 | 1997-09-17 | 普拉塞尔技术有限公司 | improved liquid distributor for packed columns |
| CN1443593A (en) * | 2002-03-07 | 2003-09-24 | 刘乃瑞 | Gas cleaning device and its method |
| CN101422717A (en) * | 2008-11-21 | 2009-05-06 | 中国蓝星（集团）股份有限公司 | Gas liquid mixed feeding distributor and polyphenylene oxide reaction device using the same |
-
2010
- 2010-04-20 CN CN201010150741XA patent/CN101954263B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159361A (en) * | 1995-12-13 | 1997-09-17 | 普拉塞尔技术有限公司 | improved liquid distributor for packed columns |
| CN1443593A (en) * | 2002-03-07 | 2003-09-24 | 刘乃瑞 | Gas cleaning device and its method |
| CN101422717A (en) * | 2008-11-21 | 2009-05-06 | 中国蓝星（集团）股份有限公司 | Gas liquid mixed feeding distributor and polyphenylene oxide reaction device using the same |
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| CN101954263A (en) | 2011-01-26 |
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Address after: 226407 Rudong City, Jiangsu Province, Yang mouth chemical industrial park Patentee after: Nantong Taihe chemical Limited by Share Ltd Address before: 226407 Rudong City, Jiangsu Province, Yang mouth chemical industrial park Patentee before: Nantong Taihe Chemical Co., Ltd. |