CN101623643B - Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation - Google Patents
Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation Download PDFInfo
- Publication number
- CN101623643B CN101623643B CN2008100436087A CN200810043608A CN101623643B CN 101623643 B CN101623643 B CN 101623643B CN 2008100436087 A CN2008100436087 A CN 2008100436087A CN 200810043608 A CN200810043608 A CN 200810043608A CN 101623643 B CN101623643 B CN 101623643B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- styrene
- deactivated
- ethylbenzene dehydrogenation
- dehydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000001172 regenerating effect Effects 0.000 title abstract 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 12
- 238000009418 renovation Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 abstract description 14
- 238000011069 regeneration method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 150000003440 styrenes Chemical class 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- -1 Alkenyl arene Chemical class 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for regenerating a deactivated styrene catalyst through ethylbenzene dehydrogenation, which mainly solves the problems that the prior art is not related to the regeneration of the styrene catalyst deactivated due to kalium loss after the deactivated styrene catalyst is used and commonly and directly adopts a burying mode to process the waste catalyst to have large treatment capacity of the waste catalyst and generate certain pollution to the environment. The method carries out dipping treatment on the used ethylbenzene dehydrogenation catalyst by using soluble sylvite, can substantially improve the activity of the deactivated catalyst, thereby prolonging the service life of the catalyst and reducing the treating frequency of the waste catalyst; and the method well solves the problem and can be used for industrial production of ethylbenzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of renovation process of deactivated styrene catalyst through ethylbenzene dehydrogenation.
Background technology
Alkenyl arene is normally made by alkyl aromatics catalytic dehydrogenation, and the key of this method is to select a kind of high activity, high selectivity and stability good, the dehydrogenation of long service life.At present, industrial what generally adopt is the Fe-K-Ce-Mo-Mg series catalysts, Fe
2O
3Be main active component, K
2O is wherein most important accelerative activator, and Ce, Mo, Mg oxide are to selectivity and stable favourable.Though existing industrial catalyst has the good stable performance, but because in the industrial operation, usually adopt the way that improves constantly reaction temperature to keep certain conversion of ethylbenzene, so catalyst is after the time of use about 2 years, need high temperature and higher water than under operation, energy consumption obviously increases, and is unreasonable economically.In addition, after catalyst moved under hot conditions for a long time, main active constituent potassium had loss to a certain degree, ferripotassium phase K
2Fe
22O
34Also can be gradually to Fe
3O
4Change mutually, make the autonomous carbon removal ability drop of catalyst, surperficial carbon deposit increases, and the physicochemical property of catalyst descends, and this moment, many producers just considered more catalyst changeout.More catalyst changeout is except that need payment raw catelyst expense, and device needs the several weeks of stopping, and the loss of styrene output is also considerable.The processing of industrial such dead catalyst at present adopts the way of strange land landfill to solve usually.Although adopted the buried measure of Denging, inevitably natural environments such as soil, underground water and atmosphere are caused certain pollution.Mainly to form be the Fe-K-Ce-Mo of high potassium content to disclosed catalyst among document U.S. Pat 4758543 and the US5190906.Such catalyst demonstrates high activity at initial operating stage, but catalyst life is short.Disclose a kind of dehydrogenation of alkylaromatic hydrocarbon among the document Chinese patent ZL911009968, the catalyst body composition is Fe-K-Ce-Mo, and same catalyst is along with the continuous inactivation of operation meeting of device.The method that does not relate to catalyst regeneration in the document.Speak of in the document under abnormal operation situation such as stop in emergency and to avoid situation by feeding water vapour, its objective is the steady running rather than the regeneration of guard catalyst the catalyst damage.
Summary of the invention
Technical problem to be solved by this invention is not relate in the conventional art because of potassium lost inactivation dehydrogenation dead catalyst regeneration or the not good problem of regeneration effect, and a kind of renovation process of new deactivated styrene catalyst through ethylbenzene dehydrogenation is provided.This renovation process has the activity that can effectively improve decaying catalyst, the advantage that prolongs the service life of catalyst.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of renovation process of ethyl benzene dehydrogenation preparation of styrene decaying catalyst may further comprise the steps:
A) according to the definite amount of mending potassium of potassium content difference between fresh catalyst and decaying catalyst;
B) will need the soluble potassium salt of additional amount to be mixed with weight concentration and be at least 5% solution;
C) potassium in the solution is loaded to surperficial the regenerated catalyst presoma I of decaying catalyst;
D) regenerated catalyst presoma I roasting under the condition of 500～1000 ℃ of temperature was got regenerated catalyst in 0.5～48 hour.
In the technique scheme, the weight ratio of soluble potassium salt and decaying catalyst is (with K
2O calculating) preferable range is 1/30～1/10; The sintering temperature preferable range of dipping rear catalyst is between 600～850 ℃, and the roasting time preferable range is 2～7 hours.
The used dehydrogenation of the present invention comprises and consists of (percentage by weight): Fe
2O
340～80%, K
2O10%～30%, Ce
2O
33～12%, Mo
2O
30.5～5%, MgO0.5～5%.The Preparation of catalysts method is after Fe, K, Ce, Mo, Mg, adhesive, perforating agent by the proportioning weighing are evenly mixed, the deionized water that adds aequum, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 60～120 ℃ of dryings 5 hours, 500～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.The used sample of regeneration test is the dehydrogenation that the commercial plant running was pulled down after 2 years.
Preparation, regeneration gets catalyst carry out activity rating in the isotherm formula fixed bed as stated above, and for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyst.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result sees Table 2.
The catalyst ageing experimental condition is: reaction pressure is that normal pressure, 6.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 1.5 (weight ratio).Evaluation result sees Table 3
The present invention is by handling decaying catalyst surface impregnation potassium, thereby can effectively replenish because potassium migration and running off makes the catalyst surface ability drop of powering cause the decline of catalyst activity.Use method of the present invention, decaying catalyst regenerated handle the back and under 620 ℃ of reaction temperatures, the condition of water, check and rate than (water/ethylbenzene) 2.0 (weight ratio), activity of such catalysts improves more than 8%, and obtained prolongation the service life of catalyst, obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing 5 gram potash and be dissolved in the medium volume of 25 gram deionized waters dipping 200 gram inactivation catalyst for phenylethylene dehydrogenation, 80 ℃ of dryings 12 hours, roasting is 2 hours under 600 ℃ of conditions.
[embodiment 2～5]
The method for preparing catalyst of embodiment 2,3,4,5 is that potassium source and sintering temperature are different with embodiment 1, specifically sees Table 1, and the contrast of catalyst dehydrogenation sees Table 2 before and after the regeneration, and the contrast of catalyst stability energy sees Table 3 before and after the regeneration.
[comparative example 1]
Catalyst after commercial plant turned round 2 years, contrast of catalyst dehydrogenation sees Table 2 before and after its regeneration, and the contrast of catalyst stability energy sees Table 3 before and after the regeneration.
Table 1 catalyst regeneration condition
The contrast of catalyst dehydrogenation before and after table 2 regeneration
The contrast of catalyst stability energy before and after table 3 regeneration
Claims (3)
1. the renovation process of an ethyl benzene dehydrogenation preparation of styrene decaying catalyst may further comprise the steps:
A) according to the definite amount of mending potassium of potassium content difference between fresh catalyst and decaying catalyst;
B) will need the soluble potassium salt of additional amount to be mixed with weight concentration and be at least 5% solution;
C) potassium in the solution is loaded to surperficial the regenerated catalyst presoma I of decaying catalyst;
D) regenerated catalyst presoma I roasting under the condition of 500～1000 ℃ of temperature was got regenerated catalyst in 0.5～48 hour.
2. the renovation process of ethyl benzene dehydrogenation preparation of styrene decaying catalyst according to claim 1, the weight ratio that it is characterized in that soluble potassium salt and decaying catalyst is with K
2O counts 1/30～1/10.
3. the renovation process of ethyl benzene dehydrogenation preparation of styrene decaying catalyst according to claim 1, the sintering temperature that it is characterized in that regenerated catalyst presoma I is between 600～850 ℃, roasting time is 2～7 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100436087A CN101623643B (en) | 2008-07-08 | 2008-07-08 | Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100436087A CN101623643B (en) | 2008-07-08 | 2008-07-08 | Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101623643A CN101623643A (en) | 2010-01-13 |
| CN101623643B true CN101623643B (en) | 2011-07-20 |
Family
ID=41519724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100436087A Active CN101623643B (en) | 2008-07-08 | 2008-07-08 | Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101623643B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728376A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | Method for preparing alkyl aromatic dehydrogenation catalyst from waste catalyst |
| WO2013064956A1 (en) * | 2011-10-31 | 2013-05-10 | Basf Se | Method for regenerating spent styrene catalysts |
| CN105797788B (en) * | 2016-03-18 | 2018-07-20 | 辽宁石油化工大学 | A kind of regeneration method of alkane dehydrogenating catalyst |
| CN115999647A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Method for recycling diethylbenzene dehydrogenation catalyst waste and diethylbenzene dehydrogenation catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5461179A (en) * | 1993-07-07 | 1995-10-24 | Raytheon Engineers & Constructors, Inc. | Regeneration and stabilization of dehydrogenation catalysts |
| CN1141218A (en) * | 1995-07-25 | 1997-01-29 | 中国石油金陵石化公司烷基苯厂 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
| CN1589970A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Regeneration method of dehydrogen catalyst |
| CN1681751A (en) * | 2002-09-05 | 2005-10-12 | 弗纳技术股份有限公司 | Method for extending catalyst life in processes for preparing vinyl aromatic hydrocarbons |
| US20060183953A1 (en) * | 2005-02-15 | 2006-08-17 | Fina Technology, Inc. | Method and apparatus for addition of aqueous solutions to high temperature processes |
-
2008
- 2008-07-08 CN CN2008100436087A patent/CN101623643B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5461179A (en) * | 1993-07-07 | 1995-10-24 | Raytheon Engineers & Constructors, Inc. | Regeneration and stabilization of dehydrogenation catalysts |
| CN1141218A (en) * | 1995-07-25 | 1997-01-29 | 中国石油金陵石化公司烷基苯厂 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
| CN1681751A (en) * | 2002-09-05 | 2005-10-12 | 弗纳技术股份有限公司 | Method for extending catalyst life in processes for preparing vinyl aromatic hydrocarbons |
| CN1589970A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Regeneration method of dehydrogen catalyst |
| US20060183953A1 (en) * | 2005-02-15 | 2006-08-17 | Fina Technology, Inc. | Method and apparatus for addition of aqueous solutions to high temperature processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101623643A (en) | 2010-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104945262B (en) | A kind of method that catalytic methanol reduces dilute nitric acid to prepare methyl nitrite | |
| CN105777480B (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| CN103769152B (en) | The catalyst for phenylethylene dehydrogenation of the low water ratio of high activity, preparation method and application thereof | |
| CN101623643B (en) | Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation | |
| CN105060456A (en) | Sewage wet catalytic oxidation treatment apparatus and method thereof | |
| CN103769151B (en) | High activity ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof | |
| CN103028419A (en) | Catalyst for low-water ratio ethylbenzene dehydrogenation | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN101992094B (en) | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN102371161B (en) | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof | |
| CN104941638A (en) | Dehydrogenation catalyst as well as preparation and application methods thereof | |
| CN101279266B (en) | Energy-saving catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene | |
| CN103977797B (en) | A kind of preparation method and application of the catalyst for preparing propylene by dehydrogenating propane | |
| CN103028418A (en) | High-activity low-water ratio ethylbenzene dehydrogenation catalyst and preparation method | |
| CN103058809A (en) | Method for preparing low-carbon alkenes by low-carbon alkane dehydrogenation | |
| CN103725312B (en) | A kind of catalysis conversion method reducing rich benzoline component benzene content | |
| CN102040463B (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| CN106944059B (en) | A kind of preparation method of synthesis gas full methanation catalyst | |
| CN106582691B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof | |
| CN103058808A (en) | Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation | |
| CN106582827A (en) | High activity and low water ratio ethylbenzene dehydrogenation catalyst | |
| CN1268432C (en) | Regeneration method of dehydrogen catalyst | |
| CN102040464B (en) | Method for preparing styrene from crude ethylbenzene by dehydrogenation | |
| JP2009034659A (en) | Hydrocarbon synthesis catalyst, method for producing the same, and method for producing hydrocarbons using the same | |
| CN102000587A (en) | Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |