CN117654548A - Method for regenerating catalyst for producing diamino dicyclohexyl methane - Google Patents
Method for regenerating catalyst for producing diamino dicyclohexyl methane Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 9
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000011069 regeneration method Methods 0.000 claims abstract description 29
- 230000008929 regeneration Effects 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- -1 carbon alcohol compound Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 230000000694 effects Effects 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000001994 activation Methods 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002798 polar solvent Substances 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
Abstract
The invention relates to a preparation method of diaminodiphenyl Methane (MDA) by hydrogenation under the action of a metal supported catalystH 12 A method for regenerating a catalyst in an MDA process, the method comprising the steps of: after the catalyst is used by a plurality of intermittent reactions, when H 12 The MDA yield is reduced to below 80%, the anti-trans isomer content exceeds 20%, the catalyst is taken out, a high carbon alcohol compound is added, roasting treatment is carried out at a certain temperature, then a high polar solvent is added for washing, and activation and regeneration are carried out under hydrogen. The regeneration method of the invention can obviously improve the service life of the catalyst, effectively keep the stability of the anti-isomeride and greatly reduce the production cost.
Description
Technical Field
The invention relates to a method for regenerating a catalyst in the production process of diamino dicyclohexyl methane.
Background
Diamino dicyclohexylmethane (H) 12 MDA) is an important cycloaliphatic diamine, mainly used for preparing alicyclic dicyclohexylmethane diisocyanate (H) 12 MDI) or directly as an epoxy curing agent. H 12 MDI can be used for processing various environment-friendly polyurethane coatings, adhesives and other surface materials with good transparency and yellowing resistance. From H 12 The MDA cured epoxy resin has excellent heat resistance, dielectric property, solvent resistance, mechanical property, optical property and weather resistance, and can be used in the fields of damping materials, optical materials, coatings, engineering plastics, adhesives and the like.
Preparation of H 12 MDA is mainly prepared by carrying a noble metal catalyst and carrying out a reaction of catalyzing and hydrogenating diaminodiphenyl Methane (MDA) in a fixed bed or autoclave reactor so as to meet higher product yield and lower anti-isomerism ratio. Because the cost of noble metal catalyst is higher, the catalyst needs to be continuously recycled and reused to reduce the production cost. However, the activity and selectivity of the catalyst are continuously reduced during the application of the catalyst. There are two main reasons for the attenuation of catalyst activity: firstly, because the catalyst runs for a long period, catalyst particles are continuously worn by a high-shear stirring paddle, so that catalyst particles become smaller and are lost into the reaction mother liquor to cause. The problem can be improved by selecting a high-strength catalyst carrier or optimizing gas mass transfer, reducing abrasion and the like; secondly, as the application times of the catalyst are increased, pore channels and active sites on the surface of the catalyst are covered by the continuously increased high-boiling tar, so that the activity and selectivity of the catalyst are gradually weakened, more secondary amine tar is further generated, and the proportion of anti-isomeride is continuously increased. Meanwhile, as the catalyst is wrapped by the viscous tar, the catalyst particles are more viscous, the filtering time of the product liquid is prolonged in multiple times, and even the catalyst is taken out and removed in advanceAnd the production efficiency is reduced, and the running cost is increased. This problem requires periodic regeneration of the deactivated catalyst, further reducing the cost of catalyst usage per ton of product.
US3071551a describes a means of regenerating rhodium catalysts by direct heat, by heating the poisoned deactivated Rh catalyst to 200-300 ℃ in a single step reaction and for 2-24 hours for regeneration. However, the technical scheme cannot avoid the problems that the catalyst micropores become smaller and the specific surface area becomes smaller due to the sintering of the carrier in the high-temperature heating process of the catalyst, so that the activity of the regenerated catalyst is influenced.
CN103816923a describes an ultrasonic cleaning regeneration scheme for ruthenium catalysts, which employs ultrasonic cleaning technology to remove tar adhering to the catalyst surface, followed by oxidative regeneration and dry reduction. However, due to the limitation of the ultrasonic technology, tar which goes deep into the catalyst pore canal cannot be thoroughly removed by ultrasonic cleaning.
CN113893866a describes an H 12 The MDA catalyst regeneration method adopts an acidic aqueous solution, and amine tar adsorbed on the catalyst is reacted at a certain temperature and pressure to generate hydroxyl substituted tar so as to eliminate the alkalinity of the tar, and the organic solvent is further utilized for washing, regenerating and activating, so that desorption and separation are realized with the catalyst. However, the technical scheme adopts an acidic aqueous solution and has higher requirements on the materials of production equipment, and simultaneously the hydroxyl substitution reaction of tar can not be ensured to be complete, and the regeneration effect of the catalyst can be influenced.
Therefore, there is a need in the art to develop a method for regenerating catalyst in the production of diaminodicyclohexylmethane while overcoming the drawbacks of the prior art methods described above.
Disclosure of Invention
The invention aims to provide a regeneration process of a catalyst in the production process of preparing diamino dicyclohexyl methane by taking MDA as a raw material and carrying out hydrogenation reaction under the action of a metal supported catalyst, wherein the whole catalyst regeneration process is completed through roasting, washing and activating. The treatment process can obviously improve the service life of the catalyst, effectively keep the anti-isomerism stable and greatly reduce the production cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
h (H) 12 The catalyst regeneration method in the MDA production process comprises the following steps:
1) And (3) roasting: adding high-carbon alcohol compound into the catalyst, and roasting.
2) Washing: adding high-polarity organic solvent, washing and cleaning.
3) And (3) an activation step: hydrogen is added to perform activation regeneration.
The catalyst comprises a combination of a metal and a carrier, wherein the metal comprises any one or at least two of VIIIB metals; more preferably, the metal comprises any one or a combination of at least two of Pt, rh, ru, ir or Pd, further preferably Rh and/or Ru;
preferably, the support comprises any one or a combination of at least two of rare earth, diatomaceous earth, alumina, lithium aluminate, zirconia, spinel, silica or silica alumina, more preferably alumina and/or zirconia;
more preferably, the catalyst is Rh/Al 2 O 3 And/or Rh/ZrO 2 ，
More preferably, the metal is present in an amount of 3 to 6wt%, preferably 4 to 5wt%, based on the weight of the catalyst.
In the roasting step, adding high-carbon alcohol into the catalyst for roasting treatment;
preferably, the high carbon alcohol compound has the formula OH- (CH) 2 ) n -OH, 10.gtoreq.n.gtoreq.6, more preferably 1, 6-hexanediol and 1, 8-octanediol;
preferably, the addition amount of the high-carbon alcohol compound is 10-100 times, preferably 20-50 times, the mass of the catalyst;
preferably, the firing temperature is 300 ℃ to 400 ℃, preferably 320 ℃ to 350 ℃; the calcination time is 6h-24h, preferably 8h-12h.
In the washing step, the high-polarity organic solvent is selected from at least any one of methanol, ethanol, dioxane, dichloroethane, acetone and tetrahydrofuran, more preferably tetrahydrofuran; the addition amount of the high-polarity organic solvent is 50-500 times of the mass of the catalyst, preferably 100-200 times; the washing time is 1 to 5 hours, preferably 2 hours.
In the activation step, the hydrogen pressure is 2-10MPa, preferably 6-8MPa; the activation and regeneration reaction temperature is 150-250 ℃, preferably 180-200 ℃; the activation time is 1 to 10 hours, preferably 5 to 7 hours.
Preferably, the activation step and the hydrogenation reaction are both carried out in the same organic solvent; preferably, the solvent is at least any one selected from cyclohexane, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexylamine, methanol, ethanol, isopropanol, n-butanol, 2-butanol, or methylcyclohexane, and more preferably tetrahydrofuran. The solvent dosage in the activation step is 50-200 times of the catalyst mass.
Preferably, the invention is said H 12 In the MDA production process, a hydrogenation reaction raw material MDA comprises 96-100wt% of 4,4' -diaminodiphenyl methane, 0-2wt% of 2,4' -diaminodiphenyl methane and 0-2wt% of N-methyl-4, 4' -diaminodiphenyl methane, based on the weight of MDA; preferably comprises 99 to 100 wt.% 4,4' -diaminodiphenylmethane, 0 to 0.5 wt.% 2,4' -diaminodiphenylmethane and 0 to 0.5 wt.% N-methyl-4, 4' -diaminodiphenylmethane, based on the weight of MDA;
preferably, the catalyst is added in an amount of 0.5 to 5wt%, preferably 1 to 3wt%, further preferably 1.5 to 2wt%, based on the weight of the MDA;
preferably, the hydrogenation MDA concentration is from 30 to 60wt%, preferably from 40 to 50wt%, based on the total weight of the MDA and solvent;
preferably, the hydrogenation reaction temperature is 100-250 ℃, preferably 150-200 ℃, further preferably 170-190 ℃;
preferably, the absolute pressure of the hydrogenation reaction is 3-15MPa, preferably 5-10MPa, and more preferably 6-8MPa;
preferably, the reactor comprises a batch autoclave reactor with a catalyst filtration device;
preferably, the catalyst filtration device is an internal filter or an external filter, preferably an autoclave internal filter;
preferably, when H is in the product liquid 12 When the MDA content is reduced to below 80% or the anti-isomer content exceeds 20%, the catalyst activity is reduced, and the catalyst needs to be regenerated.
Compared with the prior art, the invention has the following positive effects:
the catalyst with reduced activity after repeated use is roasted, and tar adhered in the catalyst is thermally decomposed into small molecular compounds at a certain temperature, so that tar with high boiling point is converted into alkane products with low boiling point. Most of the decomposition products are gasified and separated from the catalyst during the roasting and heating processes. However, in the gasification process, due to the existence of surface tension, the pore channels of the porous carrier in the catalyst are very easy to shrink, so that part of the pore channels are sintered and collapse. In order to avoid the reduction of catalyst regeneration activity caused by pore canal sintering, the invention adds a high-carbon alcohol compound in the roasting process, and utilizes the characteristics of high boiling point, high decomposition temperature and low surface tension to fill the catalyst pore canal in the roasting process, thereby slowing down the pore canal sintering and collapse processes. Further, the invention continuously washes the residual small molecular compound and high carbon alcohol compound after roasting by high-polarity organic solvent, and finally completes the activation regeneration process by introducing high-pressure hydrogen.
The invention can effectively improve the regeneration activity of the catalyst, effectively maintain the stable content of the anti-isomeride, and greatly reduce the use cost of the noble metal catalyst.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw materials used in the following examples or comparative examples are all commercially available industrial-grade conventional raw materials, and the main raw materials and test instrument information are as follows, unless otherwise specified:
4wt％Rh/Al 2 O 3 and 5wt% Rh/ZrO 2 The catalyst was purchased from the company Sean Kaili, with wt% referring to the metal content.
MDA-100 is from Wanhua WANAMINE MDA-100. Wherein the content of 4,4' -MDA is 99.5wt%, the content of N-methyl-4, 4' -MDA is 0.35wt%, and the content of 2,4' -MDA is 0.15wt%.
The gas chromatograph is Agilent 7890 series, DB-5 capillary chromatographic column, FID detector temperature is 300 ℃, initial column temperature is 160 ℃,10 ℃/min rises to 300 ℃, stay for 20min.
Example 1
Into a 1L autoclave with built-in filter, 6g of Rh/Al having a metal content of 4wt% was charged 2 O 3 Catalyst, simultaneously with 200g of MDA-100 and 200g of tetrahydrofuran, with 1MPa (absolute) of N 2 After three substitutions, H of 1MPa (absolute pressure) was used again 2 Three substitutions, then H 2 Make up to 5MPa (absolute). Raising the temperature to 190 ℃, and continuously introducing H into the reaction kettle through a hydrogen flow controller in the reaction process 2 Ensuring that the reaction pressure is maintained at 6MPa (absolute pressure), and stopping introducing H when the hydrogen flow indication through the hydrogen flow controller is lower than 100sccm 2 And stopping the reaction when the pressure drop of the reaction kettle is less than 0.01MPa/min, and cooling and decompressing the reaction kettle. When the temperature of the reaction kettle is reduced to 50 ℃, N not exceeding 0.6MPa (absolute pressure) is adopted 2 And filtering and separating the product liquid from the catalyst through a built-in filter, and performing gas chromatographic analysis on the product liquid. After the product liquid is filtered and cleaned, 200g of MDA-100 and 200g of tetrahydrofuran are continuously added, and the steps are repeated for recycling the catalyst. The reaction results are shown in Table 1.
TABLE 1 results of the reaction for the catalyst sleeve of example 1
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 1 | 94.5 | 16.3 | 5.5 |
| 10 | 91.9 | 16.8 | 8.1 |
| 20 | 90.1 | 17.5 | 9.9 |
| 30 | 88.4 | 18.5 | 11.6 |
| 40 | 85.1 | 19.2 | 14.9 |
| 50 | 82.0 | 21.0 | 18.0 |
As can be seen from Table 1When the catalyst is applied for 50 times, H 12 MDA yield has been reduced to 82% and the trans-isomer content has exceeded 20% and catalyst activity has been significantly reduced.
Example 2
Into a 1L autoclave with built-in filter, 2g of Rh/ZrO with a metal content of 5wt% was charged 2 Catalyst, simultaneously with 200g of MDA-100 and 300g of tetrahydrofuran, with 1MPa (absolute) of N 2 After three substitutions, H of 1MPa (absolute pressure) was used again 2 Three substitutions, then H 2 Make up to 5MPa (absolute). Raising the temperature to 170 ℃, and continuously introducing H into the reaction kettle through a hydrogen flow controller in the reaction process 2 Ensuring that the reaction pressure is maintained at 8MPa (absolute pressure), and stopping introducing H when the hydrogen flow indication through the hydrogen flow controller is lower than 100sccm 2 And stopping the reaction when the pressure drop of the reaction kettle is less than 0.01MPa/min, and cooling and decompressing the reaction kettle. When the temperature of the reaction kettle is reduced to 50 ℃, N not exceeding 0.6MPa (absolute pressure) is adopted 2 And filtering and separating the product liquid from the catalyst through a built-in filter, and performing gas chromatographic analysis on the product liquid. After the product liquid is filtered and cleaned, 200g of MDA-100 and 300g of tetrahydrofuran are continuously added, and the steps are repeated for recycling the catalyst. The reaction results are shown in Table 2.
TABLE 2 results of the reaction for the catalyst sleeve of example 2
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 1 | 92.1 | 14.7 | 7.9 |
| 10 | 90.5 | 15.3 | 9.5 |
| 20 | 88.3 | 15.9 | 11.7 |
| 30 | 85.9 | 16.6 | 14.1 |
| 40 | 83.2 | 17.3 | 16.8 |
| 50 | 81.2 | 18.2 | 18.8 |
| 55 | 78.9 | 19.0 | 21.1 |
As can be seen from Table 2, H when the catalyst is applied up to 55 times in batches 12 MDA yield has been reduced to 8Below 0%, the trans-trans isomer content increases to 19% and the catalyst activity has been significantly reduced.
Example 3
Into a 1L autoclave with built-in filter, 10g of Ru/Al having a metal content of 4wt% was charged 2 O 3 Catalyst, simultaneously with 200g of MDA-100 and 200g of tetrahydrofuran, with 1MPa (absolute) of N 2 After three substitutions, H of 1MPa (absolute pressure) was used again 2 Three substitutions, then H 2 Make up to 5MPa (absolute). Raising the temperature to 150 ℃, and continuously introducing H into the reaction kettle through a hydrogen flow controller in the reaction process 2 Ensuring that the reaction pressure is maintained at 10MPa (absolute pressure), and stopping introducing H when the hydrogen flow indication through the hydrogen flow controller is lower than 100sccm 2 And stopping the reaction when the pressure drop of the reaction kettle is less than 0.01MPa/min, and cooling and decompressing the reaction kettle. When the temperature of the reaction kettle is reduced to 50 ℃, N not exceeding 0.6MPa (absolute pressure) is adopted 2 And filtering and separating the product liquid from the catalyst through a built-in filter, and performing gas chromatographic analysis on the product liquid. After the product liquid is filtered and cleaned, 200g of MDA-100 and 200g of tetrahydrofuran are continuously added, and the steps are repeated for recycling the catalyst. The reaction results are shown in Table 3.
TABLE 3 results of the reaction for the catalyst sleeve of example 3
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 1 | 96.5 | 18.2 | 3.5 |
| 10 | 95.9 | 18.8 | 4.1 |
| 20 | 93.1 | 18.5 | 6.9 |
| 30 | 90.1 | 19.1 | 9.9 |
| 40 | 86.7 | 19.6 | 13.3 |
| 50 | 83.5 | 19.8 | 16.5 |
| 60 | 80.8 | 19.8 | 19.2 |
| 70 | 77.2 | 20.1 | 22.8 |
As can be seen from Table 3, when the catalyst is applied in batches up to 70 times, H 12 MDA yield has been reduced to 77.2% and the trans-isomer content has exceeded 20% and catalyst activity has been significantly reduced.
Example 4
When the catalyst of example 1 was applied in 50 batches, a significant decrease in catalyst activity occurred. At this time, 120g of 1, 6-hexanediol was added to the reaction vessel, the reaction vessel was kept open to the atmosphere by keeping the feed valve and the vent valve open, and the reaction vessel was heated to 300℃and maintained for 12 hours. Then the reaction kettle is cooled to below 40 ℃, 600g of tetrahydrofuran is added to wash the catalyst for about 2 hours, and the tetrahydrofuran washing liquid is filtered out of the reaction kettle through a built-in filter. Finally, 300g of tetrahydrofuran is added into the reaction kettle to activate the catalyst for 5 hours at 200 ℃ under 6MPa of hydrogen.
After the catalyst regeneration process was completed, hydrogenation was performed according to the feed ratio and the reaction conditions of example 1, and the reaction results are shown in table 4.
TABLE 4 results of the reaction for the catalyst sleeve of example 4
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 51 | 92.5 | 16.8 | 7.5 |
| 60 | 90.7 | 17.3 | 9.3 |
| 70 | 88.2 | 17.8 | 11.8 |
| 80 | 86.3 | 18.2 | 13.7 |
| 90 | 83.1 | 19.0 | 16.9 |
| 100 | 81.7 | 19.4 | 18.3 |
| 105 | 78.2 | 19.8 | 21.8 |
As can be seen from Table 4, the catalyst activity was significantly recovered, H in Run51 12 MDA yield increased to 92.5% to 105 batch, H 12 The MDA yield was reduced to below 80%.
Example 5
When the catalyst was applied in 55 batches in example 2, a significant decrease in catalyst activity occurred. At this time, 100g of 1, 8-octanediol was added to the reaction vessel, the reaction vessel was kept open to the atmosphere with the feed valve and the vent valve, and the reaction vessel was warmed to 400℃and maintained for 8 hours. Then the reaction kettle is cooled to below 40 ℃, 400g of tetrahydrofuran is added to wash the catalyst for about 2 hours, and the tetrahydrofuran washing liquid is filtered out of the reaction kettle through a built-in filter. Finally, 300g of tetrahydrofuran is added into the reaction kettle to activate the catalyst for 7 hours at 180 ℃ under 8MPa of hydrogen.
After the catalyst regeneration process was completed, hydrogenation was performed according to the feed ratio and the reaction conditions of example 2, and the reaction results are shown in table 5.
TABLE 5 results of the reaction for the catalyst sleeve of example 5
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 56 | 91.7 | 16.9 | 8.3 |
| 60 | 90.8 | 17.2 | 9.2 |
| 70 | 88.5 | 17.8 | 11.5 |
| 80 | 86.5 | 18.0 | 13.5 |
| 90 | 84.2 | 18.2 | 15.8 |
| 100 | 81.8 | 18.9 | 18.2 |
| 110 | 77.8 | 19.4 | 22.2 |
As can be seen from Table 5, the catalyst activity was significantly recovered, H in Run56 12 MDA yield increased to 91.7% to 110 batch, H 12 The MDA yield was reduced to below 80%.
Example 6
When the catalyst was applied in 70 batches in example 3, a significant decrease in catalyst activity occurred. At this time, 200g of 1, 8-hexanediol was added to the reactor, and the reactor feed valve and the vent valve were kept open and vented to atmosphere, and the reactor was warmed to 400℃and maintained for 12 hours. The reactor was then cooled to below 40 ℃, 500g of methanol was added to wash the catalyst for about 5 hours, and the methanol wash was filtered out of the reactor through a built-in filter. Finally, 500g of tetrahydrofuran is added into the reaction kettle to activate the catalyst for 5 hours at 200 ℃ under 6MPa of hydrogen.
After the catalyst regeneration process was completed, hydrogenation was performed according to the feed ratio and the reaction conditions of example 3, and the reaction results are shown in table 6.
TABLE 6 results of the reaction for the catalyst sleeve of example 6
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 71 | 94.8 | 18.9 | 5.2 |
| 80 | 92.7 | 19.2 | 7.3 |
| 90 | 88.2 | 19.6 | 11.8 |
| 100 | 84.3 | 19.8 | 15.7 |
| 110 | 79.8 | 20.0 | 20.2 |
As can be seen from Table 6, the catalyst activity was significantly recovered, H in Run71 12 MDA yield increased to 94.8% up to 110 batch, H 12 The MDA yield was reduced to below 80%.
Comparative example 1
The reaction results are shown in Table 7, except that 1, 6-hexanediol was not added, and the conditions were the same as in example 4.
Table 7 results of the reaction for the catalyst of comparative example 1
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 110 | 80.7 | 20.5 | 19.3 |
| 120 | 77.8 | 22.9 | 22.2 |
| 130 | 73.8 | 23.1 | 26.2 |
As can be seen from Table 7, when the catalyst activity is not effectively recovered during the calcination, e.g., without the addition of 1, 6-hexanediol, H 12 MDA yield continues to decrease.
Comparative example 2
The reaction results are shown in Table 8 under the same conditions as in example 5 except that the catalyst was washed without tetrahydrofuran.
Table 8 results of the reaction for the catalyst of comparative example 2
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 120 | 86.2 | 18.5 | 13.8 |
| 125 | 83.6 | 18.8 | 16.4 |
| 130 | 81.6 | 19.3 | 18.4 |
| 135 | 78.6 | 19.8 | 21.4 |
As can be seen from Table 8, the effect of the reaction of example 5 was not achieved although the catalyst activity was recovered when the washing was not performed with tetrahydrofuran.
Comparative example 3
The reaction results are shown in Table 9, except that the hydrogen activation was not performed under the same conditions as in example 6.
Table 9 results of the reaction for the catalyst of comparative example 3
| batch/Run of sleeve | H 12 MDA content/% | Anti-trans isomer content/% | Other content/% |
| 115 | 77.8 | 20.5 | 22.2 |
| 120 | 75.6 | 21.3 | 24.4 |
As can be seen from Table 9, the catalyst activity was not effectively recovered when high-pressure hydrogen activation was not performed, H 12 MDA yield was still below 80%.
Claims (10)
1. H (H) 12 A method for regenerating a catalyst in an MDA production process, characterized in that when the catalyst activity is reduced, the catalyst is regenerated by a method comprising the steps of:
1) And (3) roasting: adding a high-carbon alcohol compound into the catalyst, and roasting;
2) Washing: adding a high-polarity organic solvent, and washing and cleaning;
3) And (3) an activation step: hydrogen is added to perform activation regeneration.
2. The catalyst regeneration process of claim 1, wherein the catalyst comprises a combination of metal and support:
the metal comprises any one or at least two combinations of group VIIIB metals, preferably the metal comprises any one or at least two combinations of Pt, rh, ru, ir or Pd, more preferably Rh and/or Ru;
the carrier comprises any one or a combination of at least two of rare earth, diatomite, alumina, lithium aluminate, zirconia, spinel, silicon oxide or silicon aluminum oxide, more preferably alumina and/or zirconia; more preferably, the catalyst is Rh/Al 2 O 3 And/or Rh/ZrO 2 ，
More preferably, the metal is present in an amount of 3 to 6wt% based on the weight of the metal supported catalyst.
3. The catalyst regeneration process according to any one of claims 1 to 2, wherein the higher alcohol compound has the formula OH- (CH) 2 ) n OH, 10.gtoreq.n.gtoreq.6, more preferably 1,6-Hexanediol and/or 1, 8-octanediol.
4. A catalyst regeneration process according to any one of claims 1 to 3, characterized in that the amount of the higher alcohol compound added is 10 to 100 times, preferably 20 to 50 times the mass of the catalyst.
5. The method for regenerating a catalyst according to any one of claims 1 to 4, wherein the temperature of the calcination treatment is 300 ℃ to 400 ℃ for 6 hours to 24 hours.
6. The catalyst regeneration method according to any one of claims 1 to 5, wherein in the washing step, the highly polar organic solvent is at least one selected from the group consisting of methanol, ethanol, dioxane, dichloroethane, acetone and tetrahydrofuran, more preferably tetrahydrofuran.
7. The catalyst regeneration method according to any one of claims 1 to 6, wherein the amount of the highly polar organic solvent added is 50 to 500 times, preferably 100 to 200 times, the mass of the catalyst; preferably, the washing and cleaning time is 1-5h.
8. The catalyst regeneration method according to any one of claims 1 to 7, wherein the hydrogen pressure in the activation step is 2 to 10MPa, the activation and regeneration reaction temperature is 150 to 250 ℃ and the time is 1 to 10 hours.
9. The catalyst regeneration process according to any one of claims 1 to 8, characterized in that the solvent of the activation step is selected from at least one of cyclohexane, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexylamine, methanol, ethanol, isopropanol, n-butanol, 2-butanol or methylcyclohexane, more preferably tetrahydrofuran;
preferably, the solvent used in the activation step is 50-200 times the mass of the catalyst.
10. According to any one of claims 1-9A catalyst regeneration method as set forth in, wherein H is present in the product liquid 12 When the MDA content was reduced to less than 80%, or the trans-isomer content was more than 20%, it was found that the catalyst activity was reduced.
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