CN1046867C - Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst - Google Patents
Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst Download PDFInfo
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- CN1046867C CN1046867C CN94112115A CN94112115A CN1046867C CN 1046867 C CN1046867 C CN 1046867C CN 94112115 A CN94112115 A CN 94112115A CN 94112115 A CN94112115 A CN 94112115A CN 1046867 C CN1046867 C CN 1046867C
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- catalyst
- roasting
- nitrogen
- regenerating method
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 13
- DTDQFVRSJWCWNK-UHFFFAOYSA-N [Fe].[Bi].[Mo] Chemical compound [Fe].[Bi].[Mo] DTDQFVRSJWCWNK-UHFFFAOYSA-N 0.000 title description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000005078 molybdenum compound Substances 0.000 claims description 11
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 10
- 230000002779 inactivation Effects 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- -1 molybdate compound Chemical class 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 230000008929 regeneration Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009418 renovation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009466 transformation Effects 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
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a reactivating and regenerating method for deactivated ammoxidation catalysts of a Mo-Bi-Fe system; a Mo compound containing NH4 <+> is added to deactivated catalysts; the addition amount is calculated and determined according to the measured value of the loss of Mo elements in the deactivated catalysts. After being uniformly mixed, the Mo compound and the deactivated catalysts are put in a regenerator of a fluidized bed or a calcination converter for calcination; the mixture of nitrogen and air is simultaneously led to the calcined Mo compound and deactivated catalysts, and the ratio of the nitrogen to the air is 1: (0.5 to 5.0). The present invention well integrates the existing Mo compensation method, the nitrogen regenerating method and the reduction-oxidation method and makes up the disadvantages of the three methods, so that the performance of the catalysts after regeneration completely recovers to the level of fresh catalysts.
Description
The present invention relates to the regeneration or the reactivation of catalyst, particularly the oxide with Mo, Bi, Fe is the regeneration or the reactivation of the catalyst of main active constituent.
Prepare unsaturated nitrile by olefin ammoxidation, particularly by the propylene production acrylonitrile, mostly using Mo-Bi-Fe is multicomponent catalyst, and it has higher conversion ratio and selectivity preferably.General this class catalyst uses 2 years in commercial plant after,, inactivation reduces about 4% because of will causing single receipts of principal product.Because the costing an arm and a leg of catalyst, normally the catalyst of inactivation is carried out activating and regenerating in the production, make its performance obtain coming into operation again after to a certain degree the recovery, to reduce production costs.
It is generally acknowledged that the reason that causes above-mentioned catalysqt deactivation mainly contains following three aspects, the one, in the course of reaction in the catalyst Mo element generate molybdic acid with molybdenum trioxide form distillation and with the steam effect and lose, destroyed the best proportioning of each element in the catalyst; The 2nd, trivalent Fe ion has reduced the conduction of electronics in the catalyst along with the carrying out of reaction is reduced into divalence Fe ion gradually; The 3rd, active phase structure mainly is β-Bi with the variation that taken place of reaction in the catalyst
2Mo
2O
9Change into α-Bi
2Mo
3O
12, and thereby the latter is because the lower degradation that makes catalyst of selectivity.
At above-mentioned three kinds of deactivation causes, three kinds of main renovation process have been produced in the prior art.The one, molybdenum complementing method promptly adds the compound contain molybdenum in decaying catalyst, and as patent US 3,882,159, it is directly to add molybdenum oxide in reactor, or by certain process means with the molybdenum oxide appendix at SiO
2Add molybdenum element on the carrier; The 2nd, the nitrogen regeneration method is about to catalyst and carries out roasting at a certain temperature, feeds nitrogen in the time of roasting, and it can be effectively with α-Bi
2Mo
3O
12Change into the higher β-Bi of selectivity
2Mo
2O
9,, it is said that its regeneration effect ratio air regenesis method in the past improves significantly as the special public clear 55-67335 of Japan Patent; The 3rd, the reduction-oxidation method, it is the catalyst roasting a period of time under the atmosphere of reducibility gas with inactivation, and then roasting under air atmosphere, is introduced as patent US 4,425,255.The reduction-oxidation method can be optimized Fe in the catalyst
2+/ Fe
3+Ratio, thereby improve selection of catalysts.
Yet owing to the inactivation of catalyst is the result of three aspect reason comprehensive functions, existing three kinds of main renovation process all only are aimed at part deactivation cause wherein, to by the former of others thereby cause the inactivation of catalyst, but do not have significantly effect.Therefore,, all can not make catalyst recover original performance comprehensively, make the level that reaches fresh catalyst after the decaying catalyst regeneration when the above-mentioned a kind of renovation process of independent use.
The object of the present invention is to provide a kind of new inactivation Mo-Bi-Fe is the activating and regenerating method of ammoxidation catalyst, and it combines the advantage of existing three kinds of main renovation process, and operating process is then easier.
Method provided by the invention comprises following process:
In decaying catalyst, add earlier and contain NH
4 +Molybdenum compound and mix, the addition of molybdenum compound is calculated decision according to the measured value of molybdenum element loss amount in the decaying catalyst.Then this mixture is carried out roasting, roasting can be carried out in fluid bed regenerator or roasting converter, and sintering temperature is 550～690 ℃.Feed nitrogen, air gas mixture in the time of roasting, roasting time is 0.5～3.0 hour, and serves as better with 0.75～2.0 hour.
And different, when using the roasting converter, maximum feeding amount should not make catalyst fines be the fluidisation attitude to the feeding amount of mist, generally can be controlled in (0.3～6.0) milliliter/gram catalyst branch according to the kind of calciner and internal capacity; When using fluid bed regenerator, then gas feeding amount generally can be controlled in (0.02～3.0) milliliter/gram catalyst branch so that catalyst fines just reaches comparatively ideal of fluidisation attitude.
Also outbalance of the control of nitrogen and AIR Proportional in the gaseous mixture, nitrogen amount is very few and only rely on airborne nitrogen component, and the regeneration rear catalyst optionally improves obvious inadequately.And air capacity is very few, then Fe
2+/ Fe
3+Ratio will can not get optimizing, generally at nitrogen: air=1: all be feasible in the scope of (0.5～5.0), but nitrogen: air=1: (0.8～2.5) effect can be better.
In addition, the control of sintering temperature also has bigger influence to the regeneration effect of catalyst, should be specifically noted that, 690 ℃ is high threshold, surpass this temperature after, molybdenum element is with MoO
3The speed of form distillation is sharply accelerated, and catalyst is with very fast weightlessness.
The above-mentioned NH that contains
4 +Molybdenum compound can select ammonium heptamolybdate or ammonium tetramolybdate.
Owing to contain NH in the molybdenum compound that adds
4 +, molybdenum compound decomposes in roasting process, the NH that emits
4 +Impel the partial reduction of catalyst granules surface mass.And fed nitrogen, air Mixture, after molybdenum compound decomposed fully, catalyst just entered oxidation and crystalline phase transformation stage, α-Bi
2Mo
3O
12Be gradually transformed into the higher β-Bi of selectivity
2Mo
2O
9, Fe
2+/ Fe
3+Ratio also be optimized simultaneously.
Compared with prior art, the present invention with molybdenum complementing method, nitrogen regeneration method and reduction-oxidation method organically in conjunction with as a whole, remedied their shortcomings separately, the Mo-Bi-Fe ammoxidation catalyst of inactivation is behind activating and regenerating, and performance can return to the level of fresh catalyst fully.
To further specify good effect of the present invention by some embodiment and comparative example below.One, the evaluation system of catalyst and appreciation condition
Adopting diameter is that the fluidized-bed reactor of 38.1mm is as evaluation system;
Appreciation condition is:
Reaction raw materials: propylene: ammonia: air=1: 1.2: 10.5 (mol ratio)
Reaction temperature: 440 ℃
Reaction pressure: 5.7 * 10
2MPa
WWH=0.045 (propylene feed weight/catalyst weight hour)
The each investigation with 550 gram catalyst.
Propylene conversion, acrylonitrile selectivity and single the receipts are defined as follows among the evaluation analysis result:
Two, the activity of fresh catalyst is investigated
The catalyst elements composition of selecting has following empirical formula:
Cs
0.06K
0.1Fe
3Co
5Ni
2.5Bi Mo
12Mg Sb
0.5O
8(50%SiO
2Carrier)
Estimate in " one " described evaluation system and under the appreciation condition, its result is: the activity of propylene conversion=99.12% acrylonitrile selectivity=78.48% acrylonitrile once through yield=77.79% 3, decaying catalyst is investigated
" two " described fresh catalyst is after the running in 2 years of commercial plant, the loss of Mo constituent content accounts for 0.7% of gross weight in the catalyst, estimate in " one " described evaluation system and under the appreciation condition, its result is: propylene conversion=99.40% acrylonitrile selectivity=72.97% acrylonitrile once through yield=72.56% 4, embodiment
Take by weighing " three " described decaying catalyst 800 grams, add and contain NH
4 +Molybdenum compound mix, insert roasting in the roasting converter then, the roaster rotating speed is 4 rev/mins, feeds nitrogen, air Mixture, the feeding amount is 2 a milliliters/gram catalyst branch.Be warming up to roasting behind the design temperature, cooling after roasting is finished.Catalyst after the regeneration is estimated in " one " described evaluation system and under the appreciation condition, and shown in the following table is the regeneration condition of embodiment 1～8 and the evaluation result of regenerated catalyst performance.
Annotate: in the foregoing description, embodiment 1～7 adds contains NH
4 +Molybdenum compound is 10.4 grams
| Nitrogen: air | Sintering temperature (℃) | Roasting time (hour) | Evaluation result | |||
| Propylene conversion | The acrylonitrile selectivity | Single-pass yield of acrylonitrile | ||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 | 1∶2 1∶2 1∶2 1∶2 1∶2 1∶4 1∶0.6 1∶2 | 610 610 610 676 570 610 610 610 | 2.0 3.0 0.75 2.0 2.0 2.0 2.0 2.0 | 98.06％ 98.14％ 98.52％ 97.35％ 98.21％ 99.60％ 98.01％ 98.23％ | 79.24％ 78.21％ 77.86％ 76.66％ 76.99％ 77.88％ 77.46％ 79.18％ | 77.70％ 77.31％ 77.03％ 76.00％ 76.23％ 77.21％ 76.89％ 77.49％ |
Ammonium heptamolybdate, embodiment 8 be 9.1 the gram ammonium tetramolybdates.Five, the comparative example comparative example 1:
Take by weighing 800 gram " three " described decaying catalysts, add 8.47 gram MoO
3Mix, get this mixture and estimate in " one " described evaluation system and under the appreciation condition, its result is: propylene conversion=99.40% acrylonitrile selectivity=73.13% acrylonitrile once through yield=72.61% comparative example 2:
Get comparative example 1 described mixture and insert in the roasting converter, be warming up to 610 ℃ after roasting 2 hours, feed nitrogen in the time of roasting, (nitrogen: air=1: 2), roasting finishes the back cooling to air gas mixture.Catalyst after the regeneration is estimated in " one " described evaluation system and under the appreciation condition, and its result is: propylene conversion=99.25% acrylonitrile selectivity=76.99% acrylonitrile once through yield=76.02% comparative example 3:
Get 800 gram " three " described decaying catalysts and insert the roasting converter, the rotating speed of roasting converter is 4 rev/mins, and feeds nitrogen, and the feeding amount is 2 a milliliters/gram catalyst branch, be warming up to 610 ℃ after roasting 2 hours, cooling.Catalyst after the regeneration is estimated in " one " described evaluation system and under the appreciation condition, and its result is: propylene conversion=98.25% acrylonitrile selectivity=76.75% acrylonitrile once through yield=75.86%.
Claims (6)
1, a kind of Mo-Bi-Fe of inactivation is the activating and regenerating method of ammoxidation catalyst, is included in to add the compound that contains molybdenum in the catalyst of inactivation, carries out roasting after mixing, and roasting can be carried out in fluid bed regenerator or roasting converter, it is characterized in that:
The molybdate compound that adds is for containing NH
4 +Molybdenum compound;
Feed nitrogen, air gas mixture during roasting, the gaseous mixture ratio is: nitrogen: air=1: (0.5～5.0),
Sintering temperature is 550～690 ℃, and roasting time is 0.5～3.0 hour, and the addition of molybdenum compound is calculated decision according to the measured value of molybdenum element loss amount in the decaying catalyst.
2, according to the activating and regenerating method of the described catalyst of claim 1, it is characterized in that the described NH of containing
4 +Molybdenum compound be ammonium heptamolybdate or ammonium tetramolybdate.
3,, it is characterized in that the ratio of described nitrogen, air gas mixture is: nitrogen: air=1: (0.8～2.5) according to the activating and regenerating method of the described catalyst of claim 1.
4,, it is characterized in that described roasting time is (0.75～2.0) hour according to the activating and regenerating method of the described catalyst of claim 1.
5, according to the activating and regenerating method of the described catalyst of claim 1, it is characterized in that described roasting carries out in the roasting converter, the feeding amount of nitrogen, air gas mixture is (0.3～6.0) milliliter/gram catalyst branch.
6, according to the activating and regenerating method of the described catalyst of claim 1, it is characterized in that described roasting carries out in fluid bed regenerator, the feeding amount of nitrogen, air gas mixture is (0.02～3.0) milliliter/gram catalyst branch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112115A CN1046867C (en) | 1994-04-11 | 1994-04-11 | Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112115A CN1046867C (en) | 1994-04-11 | 1994-04-11 | Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110193A CN1110193A (en) | 1995-10-18 |
| CN1046867C true CN1046867C (en) | 1999-12-01 |
Family
ID=5035919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112115A Expired - Fee Related CN1046867C (en) | 1994-04-11 | 1994-04-11 | Reactivating or regenerating method for molybdenum-bismuth-iron system ammoxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046867C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767013B (en) * | 2009-01-07 | 2012-05-30 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation method |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063098C (en) * | 1996-08-06 | 2001-03-14 | 中国石油化工总公司 | Utilizing technology for acrylonitrile fluidized bed waste catalyst |
| US5877108A (en) * | 1997-12-05 | 1999-03-02 | The Standard Oil Company | Performance of used molybdenum based catalysts by the addition of ammonium dimolybdate |
| JP4650354B2 (en) * | 2006-06-28 | 2011-03-16 | 住友化学株式会社 | Method for regenerating unsaturated aldehyde and / or unsaturated carboxylic acid production catalyst, and method for producing unsaturated aldehyde and / or unsaturated carboxylic acid |
| CN101992128B (en) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | Regeneration method of ammoxidation fluid catalyst |
| CN117583036A (en) * | 2023-11-24 | 2024-02-23 | 无锡熙源工程技术有限公司 | Iron-molybdenum catalyst regeneration process and application of regenerated iron-molybdenum catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3882159A (en) * | 1973-08-20 | 1975-05-06 | Standard Oil Co | Reactivation of molybdenum containing oxidation catalysts in fluid bed reactors |
| US4425255A (en) * | 1980-09-20 | 1984-01-10 | Mitsui Toatsu Chemicals, Inc. | Regeneration method of catalysts |
| CN1038034A (en) * | 1988-05-28 | 1989-12-20 | 日本触媒化学工业株式会社 | The process for reactivation of catalyst |
-
1994
- 1994-04-11 CN CN94112115A patent/CN1046867C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3882159A (en) * | 1973-08-20 | 1975-05-06 | Standard Oil Co | Reactivation of molybdenum containing oxidation catalysts in fluid bed reactors |
| US4425255A (en) * | 1980-09-20 | 1984-01-10 | Mitsui Toatsu Chemicals, Inc. | Regeneration method of catalysts |
| CN1038034A (en) * | 1988-05-28 | 1989-12-20 | 日本触媒化学工业株式会社 | The process for reactivation of catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767013B (en) * | 2009-01-07 | 2012-05-30 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1110193A (en) | 1995-10-18 |
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