CN102039174A - Decolorization regeneration method of deactivated molecular sieve catalyst - Google Patents
Decolorization regeneration method of deactivated molecular sieve catalyst Download PDFInfo
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- CN102039174A CN102039174A CN2009102357648A CN200910235764A CN102039174A CN 102039174 A CN102039174 A CN 102039174A CN 2009102357648 A CN2009102357648 A CN 2009102357648A CN 200910235764 A CN200910235764 A CN 200910235764A CN 102039174 A CN102039174 A CN 102039174A
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- molecular sieve
- aqueous solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000011069 regeneration method Methods 0.000 title abstract description 9
- 238000004042 decolorization Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 3
- 235000019253 formic acid Nutrition 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 8
- 238000009418 renovation Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 51
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 235000011054 acetic acid Nutrition 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 20
- 230000001172 regenerating effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a decolorization regeneration method of a deactivated molecular sieve catalyst, wherein the volume ratio of the deactivated catalyst to an aqueous solution of a decolorizing agent is 1: 1-10, the deactivated catalyst and the aqueous solution of the decolorizing agent are heated to 80-100 ℃, soaked for 2-6 hours, taken out and dried, heated to 540 ℃ at the heating rate of 1.5 ℃/min, and kept for 4 hours, and kept for 1 hour at 300 ℃ and 400 ℃ respectively; the decoloring agent is one or a mixture of one of citric acid, formic acid, acetic acid and oxalic acid and ammonium salt, the ammonium salt is one or a mixture of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium oxalate or ammonium carbonate, the mass fraction of the organic acid in the decoloring agent aqueous solution is 1-5%, and the mass fraction of the ammonium salt is 1-10%; the carbon deposition amount of the deactivated molecular sieve catalyst treated by the method is reduced to below 0.3 percent, and the catalyst contains Fe2O3、SO3The catalyst is removed, the catalyst is recovered to be white, the single-pass conversion rate of benzene is recovered, and the activity is close to the level of a fresh catalyst.
Description
Technical field:
The present invention relates to the decolouring renovation process of deactivated molecular sieve catalyst in the reaction of a kind of benzene and propylene liquid-phase alkylation.
Background technology:
Phenol has purposes widely at aspects such as agricultural chemicals, dyestuff, medicine, explosive and synthetic resin.The first step of synthesizing phenol production is benzene and propylene alkylated reaction synthesizing iso-propylbenzene.
In the synthesizing iso-propylbenzene process, the main catalyst of alchlor, solid phosphoric acid catalyst Ceng Zuowei synthesizing iso-propylbenzene.But since they in use all various degrees be difficult to problems such as the etching apparatus that thoroughly solves and contaminated environment.Under the situation of environmental requirement increasingly stringent, the popularization of these technology is restricted.Molecular sieve liquid phase alkylation methods because reaction condition mitigations, conversion ratio height, selectivity is good, impurity is few, pollution-free, do not have corrosion, mainly the accessory substance polyisopropylbenzene can be converted into isopropylbenzene through reverse alkylation, makes the isopropylbenzene productive rate up to more than 99%.Thereby, since the sixties in 20th century, the new technology that each major company of the world progressively turns to pollution-free, the eco-friendly solid acid catalysis of the no burn into of exploitation to produce isopropylbenzene.Present result of study shows, the β zeolite is a highest active catalyst in the synthesizing iso-propylbenzene technology, is that the UOP technology of catalyst main active component has obtained to use widely with the β zeolite.
Industrial catalyst certainly exists problems such as active decline even inactivation in the process of long-term operation.In the actual moving process of full-scale plant, the method that adopts hot benzene to wash, i.e. benzene and propylene alkylated reaction running is hundreds of or after thousands of hours, when the productive rate of isopropylbenzene is reduced to certain index, stop propylene feed, continue to enter benzene, reaction temperature is increased to 230 ℃, keeps some hrs, dissolve away the previous thing of coke of solubility, or, be degraded to the product of solubility with the previous thing degraded of insoluble coke, the catalyst of part loss of activity is restored.Treat that molecular sieve catalyst is long running time, when insoluble material rolled up coke, the method was inapplicable, carried out external regeneration with regard to catalyst being unloaded.Bibliographical information, in the synthetic reaction of isopropylbenzene, the inactivation of beta-zeolite catalyst is mainly caused by carbon distribution (degree of depth alkylate), makes charcoal and it can be regenerated by temperature programming.
In industrial production, because the report of raw material sources impure or unconventional technological operation causing isopropylbenzene synthetic catalyst inactivation and regeneration seldom.This mainly is because often contain Fe on the molecular sieve catalyst of inactivation
2O
3, SO
3Deng material, the method that only adopts the roasting mode that carbon distribution is burnt, the result is unsatisfactory in regeneration.
Patent CN1565739 discloses the decolouring renovation process of deactivated molecular sieve catalyst in a kind of benzene and the ethene liquid phase alkylation reaction, this method is after deactivator is handled in the decolorizer aqueous solution or distilled water, by 300～700 ℃ air and/or oxygen atmosphere, wherein said decolorizer is selected from HCl, H
2C
2O
4And H
2O
2In a kind of or mixture of any one and ammonium salt wherein.This method can be reduced to the deactivator carbon content below the 0.1 heavy %, and regenerative agent not only appearance color is restored, and ethylbenzene selectivity and diethylbenzene conversion ratio can reach respectively more than 98% and 99%.But in practical operation, the oxidation coke-burning regeneration has many shortcomings: (1) operating time is long, operating temperature is high, and operating process is wayward; (2) byproducts such as water of Chan Shenging at high temperature carry out degradation to catalyst easily, thereby destroy catalyst structure, make the catalyst activity forfeiture.For avoiding occurring above-mentioned situation, the inventor guarantees that by the control oxygen-supplying amount catalyst burning does not take place is not damaged in operation in processing procedure.
Summary of the invention
The purpose of this invention is to provide a kind of method that the deactivated molecular sieve catalyst decolouring can be regenerated, by the catalyst of the method regeneration, not only appearance color becomes white, and its activity of such catalysts is near the fresh catalyst level simultaneously.Recover its activity by regeneration, reuse, reduce the operating cost of production with this.
The decolouring renovation process of the molecular sieve catalyst of inactivation in benzene provided by the invention and the propylene liquid-phase alkylation reaction, the decolorizer that uses is a kind of or wherein a kind of and mixture ammonium salt in citric acid, formic acid, acetate, the oxalic acid, and said ammonium salt is a kind of in ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium oxalate or the ammonium carbonate or their mixture.The volume ratio of the aqueous solution of decaying catalyst and decolorizer is 1: (1～10), preferred 1: (2～5).Decolorizer aqueous solution pH is preferred 〉=and 2, wherein the organic acid mass fraction of the decolorizer aqueous solution is 1-5%, preferred 1.5-3%, the mass fraction of ammonium salt is 1-10%, preferred 3-5%.Be heated to 80～100 ℃, soaked preferred 3～4 hours 2～6 hours.Take out oven dry, under inert gas (nitrogen, rare gas such as argon gas or the helium) atmosphere of the oxygen that contains 2%-15%% (volume), be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.The time of the constant temperature charcoal burning step of 300 ℃ and 400 ℃ helps the recovery of catalyst activity in the proper extension industry coke-burning regeneration process.Because 400 ℃ pairing learns the carbonaceous organic materials " easily carbon removal " that suction-operated is deposited on the catalyst by physical absorption and reduction and transform to " difficult carbon removal " easily through high-temperature roasting, promptly the weightless section of high temperature is corresponding passes through the extensive chemical suction-operated and is deposited on carbon-containing sediment on the catalyst.
Handle deactivated molecular sieve catalyst through the inventive method, its carbon deposition quantity drops to below 0.3%.Deactivated molecular sieve catalyst contains Fe
2O
3, SO
3Removed wholly or in part, make catalyst revert to white.The conversion per pass of the benzene of regenerated catalyst is recovered preferably, and the activity of regenerated catalyst is near the level of fresh catalyst.
The specific embodiment
The decaying catalyst that the present invention adopts is to be the QZ2000 alkylation decaying catalyst of main active component with the β zeolite.
Embodiment 1
Get deactivated molecular sieve catalyst 200ml and be put in the 800ml aqueous solution that is dissolved with 2% citric acid, be heated to 80 ℃ and soaked 3 hours.Take out oven dry, under the nitrogen atmosphere that contains 8% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.The regenerative agent note is made A.Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Embodiment 2
Get deactivated molecular sieve catalyst 200ml and be put in the 800ml aqueous solution that is dissolved with 2% oxalic acid, be heated to 80 ℃ and soaked 3 hours.Take out oven dry, under the nitrogen atmosphere that contains 12% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.The regenerative agent note is made B.Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Embodiment 3
Get deactivated molecular sieve catalyst 200ml and be put in the 600ml mixed solution that is dissolved with 1.5% citric acid and 3% ammonium nitrate, be heated to 80 ℃ and soaked 3 hours.Take out oven dry, under the nitrogen atmosphere that contains 8% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.The regenerative agent note is made C.Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Comparative Examples 1
Get deactivated molecular sieve catalyst 200ml in Muffle furnace, under the nitrogen atmosphere that contains 12% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.The regenerative agent note is made D.Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Comparative Examples 2
Get deactivated molecular sieve catalyst 200ml in Muffle furnace, under the nitrogen atmosphere that contains 8% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.Be put in the 800ml aqueous solution that is dissolved with 2% citric acid, be heated to 80 ℃ and soaked 3 hours.Take out oven dry.The regenerative agent note is made A1.Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Comparative Examples 3
Get deactivated molecular sieve catalyst 200ml in Muffle furnace, under the nitrogen atmosphere that contains 8% (volume) oxygen, be warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, 300 ℃ and 400 ℃ respectively stop 1h therebetween.After stopping heating, take out the cooling back naturally.Be put in the 800ml aqueous solution that is dissolved with 2% citric acid and 3% ammonium nitrate, be heated to 80 ℃ and soaked 3 hours.Take out oven dry.The regenerative agent note is made B
1Do the analysis of impurity content, specific surface and benzene conversion ratio.The results are shown in table 1.
Table 1
As can be seen from Table 1, the regenerative agent decolorizing effect ideal that method of the present invention obtains, the benzene conversion per pass reaches more than 32.5%.And the regenerative agent that obtains with present method, the conversion per pass of benzene is 25.6%.
Claims (3)
1. the decolouring renovation process of a deactivated molecular sieve catalyst, it is characterized in that: the volume ratio of the aqueous solution of decaying catalyst and decolorizer is 1: (1～10); Decolorizer aqueous solution pH 〉=2 are heated to 80～100 ℃, soak 2～6 hours, take out oven dry, are warming up to 540 ℃ with the heating rate of 1.5 ℃/min, stop 4h, and 300 ℃ and 400 ℃ respectively stop 1h therebetween;
Decolorizer is a kind of or wherein a kind of and mixture ammonium salt in citric acid, formic acid, acetate, the oxalic acid, and said ammonium salt is a kind of in ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium oxalate or the ammonium carbonate or their mixture;
The organic acid mass fraction of the decolorizer aqueous solution is 1-5%, and the mass fraction of ammonium salt is 1-10%.
2. according to the decolouring renovation process of the described a kind of deactivated molecular sieve catalyst of claim 1, it is characterized in that: the organic acid mass fraction of the decolorizer aqueous solution is 1.5-3%, and the mass fraction of ammonium salt is 3-5%.
3. according to the decolouring renovation process of the described a kind of deactivated molecular sieve catalyst of claim 1, it is characterized in that: the volume ratio of the aqueous solution of decaying catalyst and decolorizer is 1: (2～5).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102357648A CN102039174A (en) | 2009-10-13 | 2009-10-13 | Decolorization regeneration method of deactivated molecular sieve catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102357648A CN102039174A (en) | 2009-10-13 | 2009-10-13 | Decolorization regeneration method of deactivated molecular sieve catalyst |
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| CN102039174A true CN102039174A (en) | 2011-05-04 |
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ID=43905908
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| CN2009102357648A Pending CN102039174A (en) | 2009-10-13 | 2009-10-13 | Decolorization regeneration method of deactivated molecular sieve catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962096A (en) * | 2012-12-04 | 2013-03-13 | 神华集团有限责任公司 | Method for regenerating catalyst for preparing propylene from methanol or dimethyl ether |
| CN105195239A (en) * | 2015-10-24 | 2015-12-30 | 中国海洋石油总公司 | Demetallized regeneration method for reformed aromatic refining catalyst |
| CN105413758A (en) * | 2015-10-24 | 2016-03-23 | 中国海洋石油总公司 | Regeneration method for reformed aromatic hydrocarbon refining catalyst |
| CN109692706A (en) * | 2017-10-24 | 2019-04-30 | 中国石油天然气股份有限公司 | Regeneration method of molecular sieve catalyst |
| CN113019472A (en) * | 2019-12-24 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method and application of deactivated transalkylation catalyst |
-
2009
- 2009-10-13 CN CN2009102357648A patent/CN102039174A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962096A (en) * | 2012-12-04 | 2013-03-13 | 神华集团有限责任公司 | Method for regenerating catalyst for preparing propylene from methanol or dimethyl ether |
| CN102962096B (en) * | 2012-12-04 | 2015-01-07 | 神华集团有限责任公司 | Method for regenerating catalyst for preparing propylene from methanol or dimethyl ether |
| CN105195239A (en) * | 2015-10-24 | 2015-12-30 | 中国海洋石油总公司 | Demetallized regeneration method for reformed aromatic refining catalyst |
| CN105413758A (en) * | 2015-10-24 | 2016-03-23 | 中国海洋石油总公司 | Regeneration method for reformed aromatic hydrocarbon refining catalyst |
| CN109692706A (en) * | 2017-10-24 | 2019-04-30 | 中国石油天然气股份有限公司 | Regeneration method of molecular sieve catalyst |
| CN109692706B (en) * | 2017-10-24 | 2022-02-01 | 中国石油天然气股份有限公司 | Regeneration method of molecular sieve catalyst |
| CN113019472A (en) * | 2019-12-24 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method and application of deactivated transalkylation catalyst |
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Application publication date: 20110504 |