CN102049320B - Regeneration method for preparing diphenylamine catalyst by continuous condensation of phenylamine - Google Patents
Regeneration method for preparing diphenylamine catalyst by continuous condensation of phenylamine Download PDFInfo
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Abstract
The invention discloses a regeneration method for preparing a diphenylamine catalyst by continuous condensation of phenylamine. The method is an in-situ regeneration method and comprises the following steps of: treating an inactivated catalyst by using an organic cleaning agent, and then performing combustion and regeneration by using oxygen-containing nitrogen, wherein the organic cleaning agent comprises propylene glycol methyl ether, butanol, ethanolamine and ethyl acetate and can contain ethanol and/or benzene serving as co-solvents. The regeneration method avoids the problems that the catalyst bed layer in step-by-step scorching and regeneration with single oxygen and nitrogen is easy to cause temperature runaway and the time is long. The regeneration method is simple and convenient to operate and has short regeneration time, and the physicochemical properties and active indexes of the regenerated catalyst are basically as same as those of the fresh catalyst.
Description
Technical field
The present invention relates to a kind of renovation process of catalyst for producing diphenylamine with phenylamine continuous condensation, particularly a kind of renovation process that contains the catalyst of H β zeolite and aluminium oxide.
Background technology
As everyone knows, diphenylamines has a variety of purposes, can be used as antioxidant and accelerant, the stabilizing agent of rubber, is the intermediate of a lot of chemical products.The conventional production methods that with aniline is the feedstock production diphenylamines is gap still formula, liquid-phase catalysis synthetic method; This method is owing to use alchlor to be catalyst, and equipment corrosion is serious aborning, and environment is contaminated; Reaction selectivity is low; Catalyst and product separation difficulty, raw material consumption is high, and product cost is big.
US44534348, US3118944 patent have been described in aniline vapor phase production diphenylamines process; Aluminium oxide is a catalyst, and reaction temperature is more than 450 ℃, and the aniline conversion ratio is low; And too high reaction temperature is prone to cause reaction mass pyrolysis and polymerization; Cause catalyst life to shorten, catalyst needs frequent regeneration, and the production cost is high.Its catalyst regeneration condition is in the presence of air, and temperature is at 500～625 ℃, and regeneration temperature is high, the regenerator material is required harsh.
CN1114240A has described in the aniline liquid phase and has prepared continuously in the diphenylamines process; The catalyst that has adopted H β zeolite and aluminium oxide to form; 320～370 ℃ of reaction temperatures, aniline conversion ratio and diphenylamines selectivity all are higher than above-mentioned patent, and its catalyst life reaches 1500 hours.
CN1289642A, CN200510047489.9 have described in the aniline liquid phase and have prepared continuously in the diphenylamines process; Catalyst to used H β zeolite and aluminium oxide composition improves again; In catalyst, add alkaline-earth metal and alkali metal respectively, regulated the acid centre of catalyst, reduced the strong acid center that is prone to polymerization reaction take place on the catalyst; Aniline conversion ratio and diphenylamines selectivity all improve, and catalyst life reaches 2800～4800 hours.
Can know by above-mentioned patent; Prepare continuously in the diphenylamines process in the aniline liquid phase; With H β zeolite and aluminium oxide is that the activity of such catalysts and the selectivity of main component is good, but such catalyst has just lost activity after using half a year, must regenerate or changes raw catelyst.The cost of changing raw catelyst is higher, generally is the decaying catalyst continued of regenerating is used, and the regeneration effect of such catalyst and regeneration times are directly connected to the output and the production cost of diphenylamines so.With containing oxygen nitrogen coke burning regeneration, need strict control oxygen content and temperature merely, the recovery time is long, and easy temperature runaway.
CN1768955A has described a kind of renovation process of hydrogenation catalyst inactivation, and the main cause coke of hydrogenation catalyst inactivation generates, in hydrogenation process; Owing to contain alkene, alkadienes, condensed-nuclei aromatics, colloid, asphalitine and sulphur, nitrogen, oxygen compound in the raw material; Along with the prolongation of the duration of runs, the carbon deposit that forms owing to side reaction has covered the activity of such catalysts center gradually, has stopped up the catalyst aperture; Occupied the effective duct of catalyst, thereby activity of such catalysts is constantly failed.This patent adopts organic solvent to handle carbon deposition catalyst, can soak, distills, heat, and removes the part carbon distribution, carries out Regeneration Treatment then, and wherein solvent processing is carried out in different devices with Regeneration Treatment.Because it is obviously different with this hydrogenation catalyst that aniline prepares the deactivation cause of diphenylamines catalyst continuously, so its principle and method and be not suitable for the regeneration that inactivation aniline prepares the diphenylamines catalyst continuously.
CN101172262A discloses a kind of catalyst recovery process that is used for producing diphenylamine with phenylamine continuous condensation.This method is to adopt device to include the method for oxygen nitrogen substep coke burning regeneration.This method needs strict control regeneration temperature and oxygen content, otherwise occurs temperature runaway easily, and influence regeneration rear catalyst is active, can damage catalyst when serious, and the recovery time is long.
Summary of the invention
The invention provides the renovation process that a kind of aniline prepares the diphenylamines catalyst continuously.This renovation process is simple to operate, regeneration temperature is easy to control, favorable regeneration effect.
Described aniline prepares the diphenylamines catalyst continuously and is meant that with H β zeolite and aluminium oxide be the catalyst of main component, the catalyst of forming comprising the catalyst of being made up of H β zeolite and aluminium oxide, through alkali metal or alkali-earth metal modified H β zeolite and aluminium oxide.The composition of this catalyst comprises: the H β zeolite of 50wt%～90wt%, alkali metal or the alkaline-earth metal of 0～4.0wt%, 10wt%～50wt%Al
2O
3Wherein wt% representes mass fraction.
In the continuous liquid phase production diphenylamines of the aniline production process; Be accompanied by the side reaction of some polymerization, condensation, along with the prolongation of the duration of runs, the by-product compound generates the macromolecule polymer with nitrogen of carbon deposit and thickness through pyrolysis, condensation; Be deposited on catalyst surface; Stop up the catalyst micropore, covered the acid activity center of catalyst, caused catalyst activity to descend gradually.
The inventor finds through lot of test, aniline prepare continuously carbon deposit and nitrogen containing polymer polymer in the diphenylamines decaying catalyst to burn temperature different, the decomposition of macromolecule polymer with nitrogen is burnt temperature at 200～300 ℃; Carbon deposit burns temperature at 300～450 ℃, and both burnings are high heat releases, occurs the temperature runaway phenomenon easily; Especially when temperature was higher than 470 ℃, not only the crystal structure of catalyst can be destroyed, and sudden temperature rise can take place; Even all cut off oxygen; Still can not stop to heat up, maximum temperature can reach 870 ℃, consequently major injury catalyst and equipment.Nitrogen containing polymer polymer and carbon deposit are handled in different ways in the decaying catalyst, can control regeneration temperature effectively.
Based on above-mentioned discovery, the inventor adopts following renovation process.This renovation process is the method that adopts the reaction in-situ regeneration, handles decaying catalyst with the organic washing agent earlier, regenerates with containing the burning of oxygen nitrogen then, and it is following wherein to handle the decaying catalyst process with the organic washing agent:
At system pressure 1.0～5.0MPa, preferred 2.0～4.0MPa, volume space velocity 0.1～3.0h
-1, preferred 0.5～2.0h
-1, treatment temperature is lower than under the condition of organic washing agent azeotropic point, logical nitrogen in reactor, and the gas-solid volume ratio is 5～50, and is preferred 10～20, scavenging period is 0.5～8.0 hour, preferred 1.0～4.0 hours.After cleaning finishes, continue nitrogen and purge no organic washing agent component in tail gas.Promptly with conventional method of analysis, gas chromatography detects less than till the trace, generally need purge 2～8 hours with nitrogen.
The composition of used organic washing agent among the present invention, by volume comprises:
Propylene glycol monomethyl ether 5%～70% is preferably 10%～30%;
Butanols 0～70% is preferably 15%～50%;
Monoethanolamine 5%～70% is preferably 10%～40%;
Ethyl acetate 10%～70% is preferably 10%～45%.
Above-mentioned organic washing agent has the ability of extremely strong cleaning nitrogen containing polymer polymer; But above-mentioned several kinds of component costs are higher; In order to reduce cost; Can also add lower-cost, that certain solvability is arranged cosolvent ethanol and/or benzene in the described organic washing agent, the volume of cosolvent occupies below 70% of machine cleaning agent volume, is preferably below 50%.Adopt ethanol and/or benzene cosolvent, make organic washing agent cost relatively low, reduced regeneration cost.
In the renovation process of the present invention, described usefulness contains oxygen nitrogen burning regenerates and can adopt a conventional step renovation process, also can adopt the stepwise regeneration method, and preferred the employing contains the oxygen nitrogen renovation process that burns step by step, and its step is following:
(a), nitrogen switched to contain oxygen nitrogen, simultaneously reactor inlet preheating section temperature is progressively risen to 300～320 ℃, constant temperature 1～12 hour, preferred 4～8 hours; Wherein contain in the oxygen nitrogen initial oxygen content less than 0.01v%, and progressively be promoted to 0.02v%～0.5v%; And the control regeneration temperature is below 350 ℃.
(b), reactor inlet preheating section temperature is progressively risen to 440～470 ℃, and progressively promote and contain in the oxygen nitrogen oxygen content to 0.5v%～2.0v%, constant temperature 1～12 hour, preferred 4～8 hours; And the control regeneration temperature is below 470 ℃.
Wherein, step (a) or (b) in, programming rate is 10～25 ℃/h.
In the step (a), contain in the oxygen nitrogen initial oxygen content, continue 1 hour at least, progressively be promoted to 0.02v%～0.50v% then less than 0.01v%.
In step (b), under 440～470 ℃ of temperature, oxygen content progressively is promoted to 0.5v%～2v% in the regeneration gas, and beds does not continue consume oxygen, and beds does not have temperature rise, CO in the tail gas
2Content less than 0.04v% after, preferred 4～8 hours of constant temperature time.
Behind the described burning regeneration ending, system lowers the temperature and can adopt following method with inert gas replacement oxygen: will contain oxygen nitrogen and switch to nitrogen, and be cooled to 200～230 ℃ with 10～25 ℃/h speed simultaneously, oxygen content is less than 0.1v% in tail gas.
Organic washing agent among the present invention contains the mode that oxygen nitrogen all adopts charging with regeneration and gets into the reactor regenerative system.
Renovation process of the present invention is to handle, contain the oxygen nitrogen method of burning and regenerate according to organic washing agent in the characteristics selector of the composition of producing diphenylamine with phenylamine continuous condensation decaying catalyst and inactivation; Avoided the catalyst device loss in transfer process of regenerating outward; Reaction goes into operation-catalyst regeneration, and process is switched flexibly.Compare with the method that CN101172262A adopts device to include oxygen nitrogen substep coke burning regeneration; Renovation process of the present invention in regenerative process since carbon deposit and nitrogen containing polymer polymer to burn temperature different and all be high exothermic reaction, so adopt two to go on foot the method for regenerating; Earlier the nitrogen containing polymer polymer is handled with the organic washing agent; Make the follow-up oxygen nitrogen coke burning regeneration that contains reduce thermal discharge significantly, the temperature when helping controlling its regeneration has been avoided temperature runaway; Easy and simple to handle, recovery time is short, and regeneration rear catalyst physico-chemical property, activity index are basic identical with fresh catalyst.
The specific embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation, it should be noted that following examples are not the restriction to protection domain of the present invention.
Embodiment 1
Catalyst is formed as follows: the H β zeolite (SiO of 68wt%
2/ Al
2O
3Mol ratio is 68), alkaline-earth metal Ca accounts for the 1.7wt% of catalyst, and all the other are γ-Al
2O
3
Prepare catalyst 100g by patent CN1289642A method, numbering B-1.300～350 ℃ of reaction temperatures; Pressure 2.0MPa; Air speed 0.6h
-1Carry out the reaction of producing diphenylamine with phenylamine continuous condensation under the process conditions, when aniline conversion ratio＜15% (mol), be regarded as catalysqt deactivation, stop work, prepare to carry out catalyst regeneration by the shut-down scheme.
Embodiment 2
Adopt the reaction in-situ regeneration, feed process in the employing is handled with the organic washing agent earlier, and the 1# cleaning agent of preparation is formed as follows:
Table 1 1# cleaning agent is formed
| The organic washing agent is formed | % (volume fraction) |
| Propylene glycol monomethyl ether | 10 |
| Butanols | 30 |
| Monoethanolamine | 10 |
| Ethyl acetate | 20 |
| Ethanol and benzene (1: 1) | 30 |
At system pressure 2.0MPa; Air speed (v) 1.0h
-1Temperature is led to nitrogen in reactor in the time of 80 ℃, gas-solid volume ratio 20 is advanced cleaning agent to reactor, scavenging period 4 hours.After cleaning finishes, continue nitrogen and purge, do not have the cleaning agent component until tail gas.Promptly with conventional method of analysis, gas chromatography detects less than till the trace.
The oxygen nitrogen regenerative process of burning step by step is following with containing:
(a), nitrogen switched to contain oxygen nitrogen, simultaneously reactor inlet preheating section temperature progressively is warming up to 300 ℃ with the speed of 15 ℃/h; Wherein contain in the oxygen nitrogen initial oxygen content less than 0.01v%, and progressively be promoted to 0.3v%, after beds does not have temperature rise, constant temperature 4 hours; Regeneration temperature is below 320 ℃ in the control step (a).
(b), progressively be warming up to 450 ℃, and progressively promote and contain that oxygen content is to 2.0v% in the oxygen nitrogen, beds does not continue consume oxygen, and beds does not have temperature rise, CO in the tail gas with the programming rate of 15 ℃/h
2Content less than 0.04v% after constant temperature time 4 hours, regeneration temperature is below 470 ℃ in the control step (b).
At last, will contain oxygen nitrogen and switch to nitrogen, cyclic permutation contains oxygen nitrogen, is cooled to 230 ℃ with 15 ℃/h speed simultaneously, and oxygen content finishes regenerative process less than 0.1v% in the tail gas, keeps system pressure with nitrogen.By the requirements for starting construction running that feeds intake.
Reactivity is seen table 2 before and after the B-1 catalyst regeneration
Table 2
| Embodiment | Catalyst | Aniline average conversion, (mol) % | Diphenylamines selectivity, (mol) % | Service cycle, h |
| 1 | New B-1 | 24.9 | 97.7 | 2780 |
| 2 | Regeneration B-1 | 24.6 | 97.4 | 2780 |
Embodiment 3
Catalyst is formed as follows: the H β zeolite (SiO of 85.3wt%
2/ Al
2O
3Molecular proportion is 68), alkali metal K accounts for the 1.95wt% of catalyst, and all the other are γ-Al
2O
3
Prepare catalyst 100g by patent CN200510047489.9 method, numbering B-2.300～350 ℃ of reaction temperatures; Pressure 4.0MPa; Air speed 0.4h
-1Carry out the reaction of producing diphenylamine with phenylamine continuous condensation under the process conditions, when aniline conversion ratio＜15% (mol), be regarded as catalysqt deactivation, stop work, prepare to carry out catalyst regeneration by the shut-down scheme.
Embodiment 4
Adopt the reaction in-situ regeneration, feed process in the employing is handled with the organic washing agent earlier, and the 2# cleaning agent of preparation is formed as follows:
Table 3 2# cleaning agent is formed
| The organic washing agent is formed | % (volume fraction) |
| Propylene glycol monomethyl ether | 25 |
| Butanols | 15 |
| Monoethanolamine | 20 |
| Ethyl acetate | 20 |
| Ethanol and benzene (1: 1) | 20 |
At system pressure 3.0MPa; Air speed (v) 1.5h
-1Temperature is led to nitrogen in reactor in the time of 85 ℃, gas-solid volume ratio 30 is advanced cleaning agent to reactor, scavenging period 3 hours.After cleaning finishes, continue nitrogen and purge, do not have the cleaning agent component until tail gas.Promptly with conventional method of analysis, gas chromatography detects less than till the trace.
The oxygen nitrogen regenerative process of burning step by step is following with containing:
(a), nitrogen switched to contain oxygen nitrogen, simultaneously reactor inlet preheating section temperature progressively is warming up to 310 ℃ with the speed of 20 ℃/h; Wherein contain in the oxygen nitrogen initial oxygen content less than 0.01v%, and progressively be promoted to 0.5v%, after beds does not have temperature rise, constant temperature 4 hours
(b), reactor inlet preheating section temperature progressively is warming up to 440 ℃, and progressively promote and contain that oxygen content is to 2.0v% in the oxygen nitrogen, beds does not continue consume oxygen, and beds does not have temperature rise, CO in the tail gas with the programming rate of 20 ℃/h
2Content less than 0.04v% after, constant temperature time 4 hours.
Regeneration temperature is below 320 ℃ in the control step (a), and regeneration temperature is below 470 ℃ in the step (b).
At last, will contain oxygen nitrogen and switch to nitrogen, cyclic permutation contains oxygen nitrogen, is cooled to 230 ℃ with 20 ℃/h speed simultaneously, and oxygen content finishes regenerative process less than 0.1v% in the tail gas, keeps system pressure with nitrogen.By the requirements for starting construction running that feeds intake.
Reactivity is seen table 4 before and after the B-2 catalyst regeneration
Table 4
| Embodiment | Catalyst | Aniline average conversion, (mo1) % | Diphenylamines selectivity, (mol) % | Service cycle, h |
| 3 | New B-2 | 26.8 | 97.5 | 4800 |
| 4 | Regeneration B-2 | 26.1 | 97.6 | 4800 |
Embodiment 5
Catalyst is formed as follows: the H β zeolite (SiO of 75wt%
2/ Al
2O
3Molecular proportion is 68), alkali metal K accounts for the 2.15wt% of catalyst, and all the other are γ-Al
2O
3
Prepare catalyst 100g by patent CN200510047489.9 method, numbering B-3.300～350 ℃ of reaction temperatures; Pressure 3.0MPa; Air speed 1.0h
-1Carry out the reaction of producing diphenylamine with phenylamine continuous condensation under the process conditions, when aniline conversion ratio＜15% (mol), be regarded as catalysqt deactivation, stop work, prepare to carry out catalyst regeneration by the shut-down scheme.
Embodiment 6
Adopt the reaction in-situ regeneration, feed process in the employing is handled with the organic washing agent earlier, and the 3# cleaning agent of preparation is formed as follows:
Table 5 3# cleaning agent is formed
| The organic washing agent is formed | % (volume fraction) |
| Propylene glycol monomethyl ether | 20 |
| Butanols | 30 |
| Monoethanolamine | 20 |
| Ethyl acetate | 30 |
At system pressure 2.5MPa; Air speed (v) 0.8h
-1Temperature is led to nitrogen in reactor in the time of 85 ℃, gas-solid volume ratio 30 is advanced cleaning agent to reactor, scavenging period 5 hours.After cleaning finishes, continue nitrogen and purge, do not have the cleaning agent component until tail gas.Promptly with conventional method of analysis, gas chromatography detects less than till the trace.
The oxygen nitrogen regenerative process of burning step by step is following with containing:
(a), nitrogen switched to contain oxygen nitrogen, simultaneously reactor inlet preheating section temperature progressively is warming up to 310 ℃ with the speed of 20 ℃/h; Wherein contain in the oxygen nitrogen initial oxygen content less than 0.01v%, and progressively be promoted to 0.5v%, after beds does not have temperature rise, constant temperature 4 hours
(b), progressively be warming up to 460 ℃, and progressively promote and contain that oxygen content is to 2.0v% in the oxygen nitrogen, beds does not continue consume oxygen, and beds does not have temperature rise, CO in the tail gas with the programming rate of 20 ℃/h
2Content less than 0.04v% after, constant temperature time 4 hours.
Regeneration temperature is below 320 ℃ in the control step (a), and regeneration temperature is below 470 ℃ in the step (b).
At last, will contain oxygen nitrogen and switch to nitrogen, cyclic permutation contains oxygen nitrogen, is cooled to 230 ℃ with 20 ℃/h speed simultaneously, and oxygen content finishes regenerative process less than 0.1v% in the tail gas, keeps system pressure with nitrogen.By the requirements for starting construction running that feeds intake.
Reactivity is seen table 6. before and after the B-3 catalyst regeneration
Table 6
| Embodiment | Catalyst | Aniline average conversion, (mol) % | Diphenylamines selectivity, (mol) % | Service cycle, h |
| 5 | New B-3 | 23.8 | 97.1 | 1800 |
| 6 | Regeneration B-3 | 23.5 | 96.9 | 1800 |
Embodiment 7
Decaying catalyst is with embodiment 5; Decaying catalyst (carbon distribution weight content 10.12% and weight nitroxide content 1.55%) is handled with 3#～9# organic washing agent respectively; Treatment conditions are with embodiment 5, and catalyst carbon deposition and nitrogen content after organic washing agent 3#～9# composition and the cleaning are seen table 7.
Regenerate respectively then, regeneration condition and operating process are with embodiment 6, and the result after the regeneration sees table 8.
Table 7
| Cleaning agent is formed, % (volume fraction) | 3# | 4# | 5# | 6# | 7# | 8# |
| Propylene glycol monomethyl ether | 20 | 12 | 10 | 10 | 15 | - |
| Butanols | 30 | 18 | 30 | 26 | - | - |
| Monoethanolamine | 20 | 12 | 20 | 18 | 40 | - |
| Ethyl acetate | 30 | 18 | 40 | 36 | 20 | - |
| Ethanol and benzene (1: 1) | - | 40 | - | 10 | 25 | 100 |
| Clean back carbon distribution content, % | 8.75 | 8.76 | 8.72 | 8.73 | 8.78 | 9.87 |
| Clean the long-pending nitrogen content in back, % | 0.32 | 0.38 | 0.31 | 0.34 | 0.37 | 0.98 |
Can find out that from table 7 compare with the decaying catalyst of only using ethanol and benzene (1: 1) to handle, with the catalyst that organic washing agent of the present invention was handled, the nitrogen containing polymer polymer content significantly descends, carbon deposition quantity also decreases.
It can also be seen that from table 7, better when in the organic washing agent, not adding ethanol and benzene (1: 1) to the polymer with nitrogen cleaning performance, but exist the cleaning cost higher relatively, increase the problem of catalyst regeneration cost.When adding adequate amount of ethanol and/or benzene in organic cleaning agent, can reduce the cost of cleaning agent significantly, cleaning performance is also fine simultaneously.
Table 8 uses the result after 3#～8# cleaning agent regeneration
Can find out that from table 8 adopt organic washing agent cleaning nitrogen containing polymer polymer of the present invention and contain the method that oxygen nitrogen burns the regeneration of two steps, decaying catalyst all can recover activity and selectivity.
Claims (12)
1. the renovation process of a catalyst for producing diphenylamine with phenylamine continuous condensation; Adopt the method for reaction in-situ regeneration; Process comprises: earlier handle decaying catalyst with the organic washing agent, then with containing the regeneration of burning of oxygen nitrogen, wherein following with organic washing agent processing decaying catalyst process:
At system pressure 1.0～5.0MPa, volume space velocity 0.1～3.0h
-1, treatment temperature is lower than under the condition of organic washing agent azeotropic point, logical nitrogen in reactor, and the gas-solid volume ratio is 5～50, scavenging period is 0.5～8.0 hour, after cleaning finishes, continues nitrogen and purges no organic washing agent component in tail gas;
Described aniline prepares the diphenylamines catalyst continuously and forms, and the weight in catalyst comprises: 50%～90% H β zeolite, 0～4.0% alkali metal or alkaline-earth metal, 10%～50%Al
2O
3
Used organic washing agent is formed, and by volume comprises:
Propylene glycol monomethyl ether 5%～70%;
Butanols 0～70%;
Monoethanolamine 5%～70%;
Ethyl acetate 10%～70%.
2. according to the described method of claim 1, it is characterized in that describedly handling in the decaying catalyst process with the organic washing agent, operating condition is following: system pressure 2.0～4.0MPa, volume space velocity 0.5～2.0h
-1, logical nitrogen in reactor, the gas-solid volume ratio is 10～20, scavenging period is 1.0～4.0 hours.
3. according to the described method of claim 1, it is characterized in that used organic washing agent composition, by volume comprises:
Propylene glycol monomethyl ether 10%～30%;
Butanols 15%～50%;
Monoethanolamine 10%～40%;
Ethyl acetate 10%～45%.
4. according to claim 1 or 3 described methods, it is characterized in that containing cosolvent ethanol and/or benzene in the described organic washing agent, the volume of cosolvent occupies below 70% of machine cleaning agent volume.
5. according to claim 1 or 3 described methods, it is characterized in that containing cosolvent ethanol and/or benzene in the described organic washing agent, the volume of cosolvent occupies below 50% of machine cleaning agent volume.
6. according to the described method of claim 1, it is characterized in that described usefulness contains the regeneration of burning of oxygen nitrogen and adopts a step renovation process or adopt the stepwise regeneration method.
7. according to the described method of claim 6, it is characterized in that described employing stepwise regeneration method step is following:
(a), nitrogen switched to contain oxygen nitrogen, simultaneously reactor inlet preheating section temperature is progressively risen to 300～320 ℃, constant temperature 1～12 hour; Wherein contain in the oxygen nitrogen initial oxygen content less than 0.01v%, and progressively be promoted to 0.02v%～0.5v%; And the control regeneration temperature is below 350 ℃;
(b), reactor inlet preheating section temperature is progressively risen to 440～470 ℃, and progressively promote and contain in the oxygen nitrogen oxygen content to 0.5v%～2.0v%, constant temperature 1～12 hour; And the control regeneration temperature is below 470 ℃.
8. according to the described method of claim 6, it is characterized in that step (a) or (b) in, programming rate is 10～25 ℃/h.
9. according to the described method of claim 6, it is characterized in that in the step (a), contain in the oxygen nitrogen initial oxygen content, continue 1 hour at least, progressively be promoted to 0.02v%～0.50v% then less than 0.01v%.
10. according to the described method of claim 6, it is characterized in that in step (b), under 440～470 ℃ of temperature, oxygen content progressively is promoted to 0.5v%～2v% in the regeneration gas, beds does not continue consume oxygen, and beds does not have temperature rise, CO in the tail gas
2Content less than 0.04v% after, constant temperature time 4～8 hours.
11., it is characterized in that described organic washing agent and regeneration get into the reactor regenerative system with containing the mode that oxygen nitrogen all adopts charging according to the described method of claim 6.
12. according to the described method of claim 6; It is characterized in that behind the described burning regeneration ending system's cooling and contain oxygen oxygen adopting following method: will contain oxygen nitrogen and switch to nitrogen with inert gas replacement; Simultaneously be cooled to 200～230 ℃ with 10～25 ℃/h speed, oxygen content is less than 0.1v% in tail gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114240A (en) * | 1994-06-29 | 1996-01-03 | 中国石油化工总公司抚顺石油化工研究院 | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof |
| CN1289642A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Catalyst for continuously synthesizing diphenylamine from phenylamine and its preparing process |
| EP1312596A1 (en) * | 2001-10-30 | 2003-05-21 | Fina Technology, Inc. | Process for alkylating benzene in which a silica-supported zeolite beta is used as catalyst |
-
2009
- 2009-10-27 CN CN200910188131A patent/CN102049320B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114240A (en) * | 1994-06-29 | 1996-01-03 | 中国石油化工总公司抚顺石油化工研究院 | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof |
| CN1289642A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Catalyst for continuously synthesizing diphenylamine from phenylamine and its preparing process |
| EP1312596A1 (en) * | 2001-10-30 | 2003-05-21 | Fina Technology, Inc. | Process for alkylating benzene in which a silica-supported zeolite beta is used as catalyst |
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