CN1165712A - Method for regeneration of amination catalyst - Google Patents
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- CN1165712A CN1165712A CN 96105035 CN96105035A CN1165712A CN 1165712 A CN1165712 A CN 1165712A CN 96105035 CN96105035 CN 96105035 CN 96105035 A CN96105035 A CN 96105035A CN 1165712 A CN1165712 A CN 1165712A
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Abstract
A process for regenerating the aminating catalyst which is composed of carrier (alumina) and two or more of Ni, Cu, Cr, Ti and Re or their oxides features that the deactivated catalyst can be calcined and/or washed and/or immersed in liquid to recover its activity. The regenerated catalyst can be used to prepare morpholine compound with diglycol as raw material or the high-boiling-point substance as by-product during preparing morpholine as raw material.
Description
The invention belongs to catalyst technical field.Exactly be about being carrier with the aluminium oxide, be used for the method for regenerating behind the aminating reaction inactivation with two or more metal or the catalyst formed of its oxide that is selected among Ni, Cu, Cr, Ti and the Re.
The aminating reaction catalyst is meant the catalyst that is used to make organic amine compound, and organic amine comprises primary amine, and secondary amine and tertiary amine can be that straight-chain fatty amine is or/and the branched aliphatic amines compounds can be a heterocyclic amine compound also, as morpholinium compound.Make the method for morpholinium compound and used catalyst at CN87105892 by two alkylidene glycol and ammonia, existing report in detail among the CN87105893.The disclosed aminating reaction catalyst of CN87105833 is by δ-or θ-or arbitrary proportion (δ+θ)-Al
2O
3Load Ni, Cu, Cr and/or Re isoreactivity component are formed.People such as K.Jiratova have reported renovation process (the Proceedings of the 10 th Intemational Congress onCatalysis 19-24 July that on nickel-loaded catalyst diethylene glycol (DEG) amination prepares activity, selectivity and the catalyst of morpholine, 1992, Budapest, Hungary), this catalyst contains the NiO of 70wt%, is a kind of at NiO/SiO
2Or NiO/TiO
2On soak PdCl
2Solution is used 0.1wt%Pd
2+Improved catalyst, the renovation process of this catalyst are to use raw material diethylene glycol (DEG) and the high-boiling components that is adsorbed on catalyst surface to react to remove high-boiling components (not advance raw material NH this moment
3), why inactivation has three reasons to make catalyst recover active amination catalysts: the one, owing in the aminating reaction process, generate a certain amount of high-boiling components, be adsorbed in catalyst surface and make its active decline, as preparing in the morpholine process in diethylene glycol (DEG) (DEG) amination, there is the high-boiling components of 20-30% to generate, mainly be morpholinyl diethylene glycol (DEG) (MDEG), morpholinyl diglycolamine (MDGA), two morpholinyl diethylene glycol (DEG)s (BMDEG) and diglycolamine condensation product etc., these high-boiling components are adsorbed on catalyst surface, cause catalyst contamination, make its active reduction or inactivation.Second reason is aminating reaction catalyst carrier Al
2O
3Part or all of crystal transition takes place in the amination process, promptly rehydrated phenomenon, thus cause catalyst activity reduction or inactivation.The 3rd reason is that the gathering of metal constituent element causes catalysqt deactivation.
The renovation process that the purpose of this invention is to provide a kind of amination catalysis, particularly owing to pollutant (as high-boiling components), catalyst metals constituent element sintering and carrier structure change (as Al
2O
3Phase change) renovation process of caused inactivation amination catalysis.
The present invention realizes by following proposal: will by alumina support and be selected among Ni, Cu, Cr, Ti and the Re two or more metal or the catalyst formed of its oxide be used for inactivation behind the aminating reaction catalyst through roasting or/and washing makes it to recover activity or/and maceration extract soaks
The said renovation process of the present invention, can only adopt above-mentioned a kind of operating process, also can adopt any combination of above-mentioned several operating process, this operation can be implemented in the use of aminating reaction catalyst any time, particularly uses at catalyst and implements later in 2000 hours.Implementing this operation can carry out in reactor, carry out after also catalyst can being drawn off reactor, but acid soak can not be implemented in the aminating reaction device.When making up coupling, decaying catalyst must carry out roasting again after acid soak.
When in reactor, implementing baking operation, can under hydrogen atmosphere, carry out, also can under inert gas such as blanket of nitrogen, carry out, can also carry out under the mixed atmosphere by the arbitrary proportion composition at hydrogen and inert gas.Roasting condition is: pressure 0.1～3.0MPa, preferably 0.5～1.5Mpa; Gas agent volume ratio 400～2000: 1, preferably 600～1200: 1; 100～500 ℃ of sintering temperatures, preferably 250～450 ℃; 10～100 ℃/hour of programming rates, preferably 40～60 ℃/hour; Roasting time 1.0～25 hours, preferably 10～20 hours.
When outside reactor, implementing baking operation, can in air, carry out, also can under inert atmosphere such as blanket of nitrogen, carry out, or carry out under air and the mixed atmosphere of inert gas by the arbitrary proportion composition.Operating pressure can be normal pressure, also can be decompression, under reduced pressure carry out roasting can make the high-boiling components evaporation that is adsorbed on catalyst surface or divide solve faster.Roasting condition outside reactor: pressure 0.1～3.0MPa, preferably 0.5～1.5MPa; 100～500 ℃ of temperature, preferably 250～450 ℃; 10～100 ℃/hour of programming rates, preferably 40～60 ℃/hour; Roasting time 0.5～10 hour, preferably 3～6 hours.
The said washing process of the present invention is meant that the two or more mixture a kind of or that form with arbitrary proportion that is selected from water, morpholine, oxolane, the diethylene glycol (DEG) is a solvent, carries out intermittently or the operating process of continuous extraction.Extraction temperature is the boiling temperature or the azeotropic temperature of selected solvent, and the volume ratio of solvent and catalyst is 0.5～10, preferably 1.0～3.0, and 1.0～40 hours extraction time, preferably 4.0～15 hours.
The said maceration extract immersion process of the present invention is meant that with acid concentration be 3～60m%, the acid solution of 15～30m% preferably, and preferably salpeter solution is a maceration extract, is 1: 1～20 in the volume ratio of maceration extract and catalyst, preferably 1: 1～3; 0.1～10 hour time, preferably 0.5～2 hour, 10～50 ℃ of temperature, the preferably operating process of soaking under 15～35 ℃ the condition.Said maceration extract also can mix the electrolyte of forming by hydrochloric acid, glycerine and methyl alcohol by arbitrary proportion.
The present invention has the following advantages:
1. can the resolved vector aluminium oxide be that crystalline phase changes caused catalyst activity reduction problem with method of roasting owing to rehydrated phenomenon.
2. adopt the acid solution immersion process that the metal component that has accumulated on the catalyst is disperseed again.
3. use method of roasting or/and the polar solvent washing methods can be removed the high-boiling components of catalyst surface absorption.
4. can use two alkylidene glycol (as diethylene glycol (DEG)) to carry out aminating reaction as raw material with the aminating reaction catalyst after the method for the invention regeneration makes morpholine kind compound, can also use the high-boiling components of making by-product in the morpholine process to make morpholine kind compound as raw material.
The following examples will the invention will be further described.
Example 1
Amination catalysis (this fresh catalyst is numbered AM-1A according to CN 87105833 described methods preparations) with using after 4000 hours adopts method of roasting to regenerate in the aminating reaction device, makes regenerated catalyst R-Cat-1.
Roasting condition: Hydrogen Vapor Pressure 1.0MPa, gas agent volume ratio 800: 1,40 ℃/hour of programming rates stopped 3 hours at 120 ℃, and 240 ℃ stopped 4 hours, and 360 ℃ stopped 6 hours, reduced to reaction temperature then and stopped 1 hour.
On the fixed bed evaluating apparatus, R-Cat-1 estimates to regenerated catalyst, the aminating reaction raw material is respectively diethylene glycol (DEG) (chemical pure, Military Medical Science Institute MED SUP station) and prepare the high-boiling components (abbreviation high-boiling components) of by-product in the morpholine process according to CN 87105892 described methods, the purpose product is a morpholine, loaded catalyst 60ml, the draw ratio of evaluating apparatus 15: 1, before the reaction catalyst is reduced processing according to a conventional method, the material composition is analyzed with gas chromatograph, and its dummy suffix notation meaning is as follows:
Diethylene glycol (DEG) (DEG); Morpholine (MOR); Ethyl morpholine (EtMOR); Single morpholinyl diethylene glycol (DEG) (MDEG); Two morpholinyl diethylene glycol (DEG)s (BMDEG).With the diethylene glycol (DEG) is that raw material is made the appreciation condition of morpholine and be the results are shown in Table 1, is that raw material is made the appreciation condition of morpholine and be the results are shown in Table 2 with the high-boiling components.
Example 2
This example adopts the outer roasting method of aminating reaction device to prepare regenerated catalyst R-Cat-2.
To use the amination catalysis after 4000 hours in air, to carry out roasting, 40 ℃/hour of programming rates, stopped 2 hours at 200 ℃, 280 ℃ stopped 4 hours, 410 ℃ stopped 2 hours, and gas agent volume ratio is 800: 1, makes R-Cat-2, its appreciation condition is with example 1, and evaluation result sees Table 1 and table 2.
Example 3
This example adopts the outer roasting of device-maceration extract immersion-roasting method regenerated catalyst.
To use the amination catalysis after 4000 hours in air, to carry out roasting, 40 ℃/hour of programming rates stopped 2 hours at 200 ℃, and 280 ℃ stopped 4 hours, salpeter solution with isopyknic 46m% soaked 2 hours then, carry out 40 ℃/hour of roasting programming rates after the drying again in air, stopped 1 hour at 200 ℃, 360 ℃ stopped 2 hours, 430 ℃ stopped 2 hours, obtain regenerated catalyst R-Cat-3 after the processing, its appreciation condition is with example 1, and evaluation result sees Table 1 and table 2.
By table 1, table 2 as can be seen: the catalyst R-Cat-1 after regeneration, R-Cat-2 compares with fresh catalyst AM-1A with R-Cat-3, is used for the diethylene glycol (DEG) amination and makes morpholine, and is quite active, is used for the high-boiling components amination and makes morpholine, effect is also better.
Table 1
| The catalyst numbering | ???AM-1A | ??R-Cat-1 | ??R-Cat-2 | ??R-Cat-3 | |
| Reaction condition | Pressure (MPa) | ????3.0 | ????3.0 | ????3.1 | ????3.0 |
| Temperature (℃) | ????225 | ????225 | ????225 | ????230 | |
| LHSV(h -1) | ????0.30 | ????0.30 | ????0.30 | ????0.30 | |
| NH 3/DEG(molar) | ????14 | ????14 | ????14 | ????14 | |
| H 2/DEG(molar) | ????8 | ????8 | ????8 | ????8 | |
| Product is formed m% | MOR | ????43.3 | ????34.7 | ????30.4 | ????42.8 |
| EtMOR | ????9.6 | ????2.1 | ????1.7 | ????8.4 | |
| DEG | ????12.0 | ????33.7 | ????34.2 | ????12.6 | |
| MDEG | ????3.3 | ????5.1 | ????3.1 | ????4.9 | |
| BMDEG | ????27.8 | ????13.1 | ????26.6 | ????26.9 | |
| Other * | ????4.0 | ????11.3 | ????4.0 | ????4.4 | |
Annotate: (1) LHSV (Lipuid hourly space velocity) liquid hourly space velocity (LHSV).
(2) raw material is the diethylene glycol (DEG) aqueous solution of 90m%.
*(3) " other " comprise diethylene glycol (DEG) and (or) condensation product and a certain amount of little molecule organic amine and the hydroxyethyl morpholine etc. of diglycolamine, down with.
Table 2
| The catalyst numbering | ???AM-1A | ??R-Cat-1 | ??R-Cat-2 | ??R-Cat-3 | |
| Reaction condition | Pressure (MPa) | ????4.0 | ????4.0 | ????4.0 | ????4.0 |
| Temperature (℃) | ????260 | ????280 | ????260 | ????260 | |
| LHSV(h -1) | ????0.38 | ????0.38 | ????0.38 | ????0.38 | |
| NH 3/ high-boiling components (molar) | ????10 | ????10 | ????10 | ????10 | |
| H 2/ high-boiling components (molar) | ????20 | ????20 | ????20 | ????20 | |
| Raw material is formed m% | MOR | ????- | ????- | ????- | ????- |
| EtMOR | ????- | ????- | ????- | ????- | |
| DEG | ????9.6 | ????9.6 | ????3.0 | ????3.0 | |
| MDEG | ????22.2 | ????22.2 | ????14.5 | ????14.5 | |
| BMDEG | ????54.2 | ????54.2 | ????69.9 | ????69.9 | |
| Other ** | ????14 | ????14 | ????12.6 | ????12.6 | |
| Product is formed m% | MOR | ????20.8 | ????16.4 | ????19.5 | ????16.3 |
| EtMOR | ????16.3 | ????16.7 | ????15.8 | ????26.0 | |
| DEG | ????1.3 | ????6.9 | ????- | ????0.7 | |
| MDEG | ????1.3 | ????5.7 | ????1.2 | ????0.8 | |
| BMDEG | ????39.5 | ????37.0 | ????54.6 | ????45.7 | |
| Other * | ????20.8 | ????17.3 | ????8.9 | ????10.5 | |
Annotate: (1) raw material high-boiling components is the 50m% aqueous solution.
*(2) " other " in the raw material mainly be meant contain diethylene glycol (DEG) and (or)
Two molecule condensation products of diglycolamine.
*(3) " other " during product is formed is the same.
Example 4
This example adopts washing extraction regenerated catalyst.
At the bottom of being housed, reflux condenser (1), extractor (2) and garden in the extraction equipment of flask (3), use the amination catalysis Cat of washing methods regeneration of deactivated, as shown in Figure 1.
Get the decaying catalyst Cat that 20ml used 4000 hours, in the continuous extraction device (2) of packing into, in flask at the bottom of the garden (3), add the 50ml deionized water, be heated to the water boiling, reflux extraction 10 hours is filtered, 120 ℃ of dryings 3 hours, make regenerated catalyst R-Cat-4.
To fresh catalyst AM-1A, decaying catalyst Cat, and regenerated catalyst R-Cat-1, R-Cat-2 and R-Cat-4 carry out thermogravimetric and divide watchman's clapper with conventional thermogravimetry, and its difference quotient thermogravimetric curve is seen Fig. 2.
The explanation of Fig. 2 difference quotient thermogravimetric curve:
1.＜150 ℃ be the weightless peak of desorption of the empty G﹠W of catalyst absorption.
2. 150 ℃～400 ℃ the weightless peaks of desorption for catalyst absorption high-boiling components.
3. 400～600 ℃ is Al
2O
3The weightless peak of rehydrated product boehmite dehydration phase transformation.
As seen from Figure 2: decaying catalyst Cat, cause inactivation owing to having adsorbed high-boiling components, simultaneously, its carrier A l
2O
3Because the rehydrated crystalline phase that causes becomes boehmite.The R-Cat-1 regenerated catalyst is because the high-boiling components of absorption can only be removed in its sintering temperature＜400 ℃ therefore.High-boiling components had both been removed, also with Al in R-Cat-2 sintering temperature＞400 ℃
2O
3Rehydrated product boehmite is transformed into its dehydration product, and its difference quotient thermogravimetric curve and fresh catalyst AM-1A are basic identical.R-Cat-4 regenerates with the solvent wash extraction, can remove high-boiling components, and its difference quotient thermogravimetric curve and R-Cat-1 are basic identical.
Claims (8)
1. the renovation process of an aminating reaction catalyst, it is characterized in that and by alumina support and to be selected from Ni, Cu, Cr, the catalyst that the metal of two or more among Ti and the Re or its oxide are formed be used for the aminating reaction inactivation after roasting or/and washing or/and maceration extract soaks the regeneration that makes it to recover active catalyst can carry out in the aminating reaction device, also can outside device, carry out, when in the aminating reaction device, regenerating, roasting is at hydrogen or/and carry out under the inert atmosphere, roasting condition is: pressure 0.1～3.0MPa, gas agent volume ratio 400～2000: 1,100～500 ℃ of temperature, 10～100 ℃/hour of programming rates, 1.0～25 hours time, hydrogen can any ratio mix with inert gas; Said washing is meant and is selected from water, morpholine, oxolane, a kind of in the diethylene glycol (DEG) or undertaken intermittently or the operating process of continuous extraction by the two or more solvent that arbitrary proportion is formed, extraction temperature is the boiling temperature or the azeotropic temperature of selected solvent, the volume ratio of solvent and catalyst is 0.5～10,1.0～40 hours extraction time, said maceration extract soaks to be meant with acid concentration to be that the acid solution of 3～60m% is immersion liquid, volume ratio at maceration extract and catalyst is 1: 1～20,10～50 ℃ of temperature, the process of soaking under the condition of 0.1～10 hour time.
2. according to the renovation process of the said catalyst of claim 1, when it is characterized in that in the aminating reaction device, regenerating, roasting condition is: pressure 0.5～1.5MPa, gas agent volume ratio 600～1200: 1,40～60 ℃/hour of programming rates, 250～450 ℃ of sintering temperatures, roasting time 10～20 hours.
3. according to the renovation process of the said catalyst of claim 1, when it is characterized in that outside the aminating reaction device, regenerating, roasting is at air or/and carry out under the inert atmosphere, pressure 0.1～3.0MPa, 100～500 ℃ of temperature, 10～100 ℃/hour of programming rates, 0.5～10 hour time, air can any ratio mix with inert gas.
4. according to the renovation process of the said catalyst of claim 3, it is characterized in that the roasting condition outside the aminating reaction device is: pressure 0.5～1.5MPa, 40～60 ℃/hour of programming rates, 250～450 ℃ of temperature, 3～6 hours time.
5. according to the renovation process of the said catalyst of claim 1, it is characterized in that the volume ratio of solvent and catalyst is 1.0～3.0 in the washing process, the time is 4.0～15 hours.
6. according to the renovation process of the said catalyst of claim 1, it is characterized in that the used maceration extract of immersion process is a salpeter solution.
7. according to the renovation process of the said catalyst of claim 1, the acid concentration that it is characterized in that maceration extract is 15～30m%, and the volume ratio of maceration extract and catalyst is 1: 1～3, soak time 0.5～2 hour, 15～35 ℃ of soaking temperatures.
8. according to the renovation process of the said catalyst of claim 1, it is characterized in that roasting and washing and maceration extract immersion process can make up arbitrarily, when making up coupling, maceration extract must carry out roasting after soaking again.
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|---|---|---|---|
| CN96105035A CN1062491C (en) | 1996-05-20 | 1996-05-20 | Method for regeneration of amination catalyst |
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|---|---|---|---|
| CN96105035A CN1062491C (en) | 1996-05-20 | 1996-05-20 | Method for regeneration of amination catalyst |
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| CN1165712A true CN1165712A (en) | 1997-11-26 |
| CN1062491C CN1062491C (en) | 2001-02-28 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974393A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
| US20150087837A1 (en) * | 2012-03-27 | 2015-03-26 | Dow Global Technologies Llc | Rhenium recovery from used reductive amination catalysts |
| WO2017132938A1 (en) * | 2016-02-04 | 2017-08-10 | Rhodia Operations | Macroporous catalyst for the preparation of aliphatic amines |
| CN107961797A (en) * | 2017-11-22 | 2018-04-27 | 万华化学集团股份有限公司 | It is a kind of to face the renovation process that hydrogen amination prepares the amination catalysis of polyetheramine for polyether polyol |
| CN108452648A (en) * | 2017-12-22 | 2018-08-28 | 江苏梅兰化工有限公司 | A kind of dead catalyst comprehensive reutilization method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409399A (en) * | 1981-12-09 | 1983-10-11 | Millmaster Onyx Group, Inc. | Process for producing aliphatic amines |
| CN1010284B (en) * | 1987-08-29 | 1990-11-07 | 中国石油化工总公司石油化工科学研究院 | Catalyst for ammoniation |
| CN1017876B (en) * | 1988-11-07 | 1992-08-19 | 中国石油化工总公司 | Prodn process of catalyst for synthesizing morpholine and its derivatives |
| EP0652207B1 (en) * | 1993-11-02 | 1998-04-08 | Nippon Shokubai Co., Ltd. | Process for preparation of alkanolamine, catalyst used in the process and process for preparation of the catalyst |
| JPH1023226A (en) * | 1996-07-04 | 1998-01-23 | Matsushita Electric Ind Co Ltd | Image reader |
-
1996
- 1996-05-20 CN CN96105035A patent/CN1062491C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150087837A1 (en) * | 2012-03-27 | 2015-03-26 | Dow Global Technologies Llc | Rhenium recovery from used reductive amination catalysts |
| US10399064B2 (en) * | 2012-03-27 | 2019-09-03 | Dow Global Technologies Llc | Rhenium recovery from used reductive amination catalysts |
| CN102974393A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
| CN102974393B (en) * | 2012-11-21 | 2014-10-15 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
| WO2017132938A1 (en) * | 2016-02-04 | 2017-08-10 | Rhodia Operations | Macroporous catalyst for the preparation of aliphatic amines |
| US11084776B2 (en) | 2016-02-04 | 2021-08-10 | Rhodia Operations | Macroporous catalyst for the preparation of aliphatic amines |
| CN107961797A (en) * | 2017-11-22 | 2018-04-27 | 万华化学集团股份有限公司 | It is a kind of to face the renovation process that hydrogen amination prepares the amination catalysis of polyetheramine for polyether polyol |
| CN107961797B (en) * | 2017-11-22 | 2021-01-15 | 万华化学集团股份有限公司 | Regeneration method of amination catalyst for preparing polyether amine by hydroamination of polyether polyol |
| CN108452648A (en) * | 2017-12-22 | 2018-08-28 | 江苏梅兰化工有限公司 | A kind of dead catalyst comprehensive reutilization method |
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