CN1915928A - Method for producing propylene continuously in switch mode - Google Patents
Method for producing propylene continuously in switch mode Download PDFInfo
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- CN1915928A CN1915928A CN 200510028806 CN200510028806A CN1915928A CN 1915928 A CN1915928 A CN 1915928A CN 200510028806 CN200510028806 CN 200510028806 CN 200510028806 A CN200510028806 A CN 200510028806A CN 1915928 A CN1915928 A CN 1915928A
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Abstract
This invention relates to a changeover method for continuously manufacturing propylene by C4+ alkenes catalytic cracking. The method adopts a reactor with a set of parallel fixed beds. Each fixed bed is operated according to a certain interval, and the products of all fixed bed are mixed and sent to the next process so that the reactant of the next process has stable composition. The method solves the problems of low catalyst activity and large change of product composition at the beginning and end of reaction, which leads to difficulties in stable quality and next process. The method can be used in propylene industrial manufacture by C4+ alkenes catalytic cracking.
Description
Technical field
The present invention relates to a kind of method of producing propylene continuously in switch mode, particularly about a kind of method that is used for carbon four and above olefins by catalytic cracking use fixed-bed reactor producing propylene continuously in switch mode.
Background technology
The major advantage of fixed-bed reactor is flowing near piston flow of bed inner fluid, and chemical reaction velocity is very fast; Available more a spot of catalyzer and less reactor volume obtain bigger throughput; The fluidic residence time can strict be controlled, and temperature distribution can suitably be regulated, and helps improving the transformation efficiency and the selectivity of chemical reaction.In addition, axially-located bed structure of reactor is simple, easy to operate, and investment cost is low, and catalyzer mechanical wear is little in the bed, can operate under High Temperature High Pressure, therefore obtains to use widely in petrochemical complex.
The used catalyzer of fixed-bed reactor all has certain life-span, inactivation is inevitable getting in the use of catalyzer, its active stabilization period of some catalyzer is long, composition in its active stabilization period reaction product is little with the variation of duration of service, can improve activity by adjusting reaction process condition even some changes also.But its active stabilization period of some catalyzer is shorter, and the inactivation of catalyzer is than very fast, and obvious variation takes place the reaction product composition in time.Catalyst deactivation often brings disadvantageous effect to Industrial processes than comparatively fast, the requirement relatively harsher to technical process, equipment and the operational condition etc. of catalytic reaction process.At present industrially all adopt two reactors to switch the method for using than catalytic reaction process faster, the catalyzer in every reactor is all used in the higher scope of specific activity this inactivation.But along with the inactivation of catalyzer, the composition of its reaction product is changing always, as wants to reduce the rangeability that reaction product is formed, and just needs frequent switching reactor fast, and this has increased operation easier and cost to a certain extent.All introduced fixed-bed reactor among document CN2075277U, US4938422, the US368597, but its not stable operation at how.
Summary of the invention
Technical problem to be solved by this invention is aborning because the catalyst deactivation ratio is very fast, initial stage and reaction product composition variation in latter stage are bigger, bring difficult problem for the operation of constant product quality and subsequent handling, a kind of method of producing propylene continuously in switch mode is provided.This suitching type quantity-produced method has the reaction product of making and forms that rangeability is little, the advantage of constant product quality.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing propylene continuously in switch mode, with the rich olefins that contains one or more carbon four and above alkene is raw material, makes olefin feedstock reactor and the silica alumina ratio SiO by one group of fixed bed parallel connection respectively
2/ Al
2O
3Be at least the contact of 10 crystal aluminosilicate catalyzer and generate the effluent that contains propylene, wherein used reactor is provided with 2～10 beds, each catalyst bed interlayer is and is connected in parallel, reaction raw materials can enter each beds respectively simultaneously, the reaction product of each beds can enter the reaction product house steward respectively simultaneously, when propene yield reduces by 50% in the reaction product of beds, this beds cuts out reactive system and regenerates, and has at least 1 beds to be used for regeneration in the whole reactor.
In the technique scheme, the rich olefins mixture material of one or more carbon four or above alkene is from carbon four and above cut or the coproduction of a-alkene, MTO (methanol-to-olefins) and the carbon four of MTP by-products such as (preparing propylene from methanol) and the above rich olefins cut thereof of steam cracking device in plant catalytic cracker, the ethylene plant; Rich olefins mixture preferred version is C
4～C
12Normal olefine; The beds preferred version has 3～5, is to be connected in parallel, and wherein 1～2 beds is in reproduced state, and each beds is pressed certain hour operation successively at interval; The regeneration preferred version carries out successively by turns, when 2～4 beds carry out catalyzed reaction, has a beds to carry out the regenerative operation of catalyzer; The state of reactor is controlled by the inlet valve and the outlet valve of beds; The operational condition of reactor: temperature of reaction is 450～600 ℃, and weight space velocity is 10～40 hours
-1, reaction pressure is 0.02～0.6MPa.
At carbon four and above preparing propylene by catalytic cracking olefin method, the present invention proposes a kind of method of producing propylene continuously in switch mode, for example the method for this producing propylene continuously in switch mode adopts three beds, and schematic flow sheet is seen accompanying drawing 1.In operating process, open first beds earlier, proceed to half of catalyst life when reaction, when being half way, open second beds, when in first beds during catalyst deactivation, open the 3rd beds, simultaneously the catalyzer of inactivation in first beds is regenerated; When the catalyst deactivation in second beds, open first beds, simultaneously the catalyzer of inactivation in second beds is regenerated; When in the 3rd beds during catalyst deactivation, open second beds, simultaneously the catalyzer of inactivation in the 3rd beds is regenerated, so operate successively at interval by certain hour, after can guaranteeing the reaction product mixing of two beds, it is smaller that product is formed rangeability.If adopt the reactor of 4 beds or 5 beds to operate successively by above-mentioned flow process, the rangeability that mixed reaction product is formed is littler.
Carbon four and above preparing propylene by catalytic cracking olefin method adopt the method for producing propylene continuously in switch mode of the present invention, can make reaction product form little, the constant product quality of rangeability, have obtained better technical effect.
Description of drawings
Fig. 1 is the suitching type continuous production schematic flow sheet of three-section fixed-bed reactor of the present invention;
In Fig. 1,1 is raw material charging house steward; 2 is feed-pipe; 3 is inlet valve; 4 is reactor shell; 5 is first section fixed bed; 6 for being second section fixed bed; 7 for being three-section fixed-bed; 8 is outlet valve; 9 is outlet pipe; 10 is the reaction product house steward; 11 is the regeneration gas house steward; 12 is the regeneration gas feed-pipe; 13 is the regeneration gas feed valve; 14 is the exhanst gas outlet valve; 15 is fume pipe; 16 is the flue gas house steward; 17 is resurgent gases; 18 is raw material; 19 is product; 20 is flue gas.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Certain carbon four and above olefin catalytic cracking to produce propylene process using suitching type continuous production flow process as shown in Figure 1, reactor comprises three-section fixed-bed, and two sections fixed beds are used for reaction, and one section is used for regeneration.600 ℃ of temperature of reaction, air speed 14 hours
-1, normal pressure, catalyst life 48 hours, reactor switched once in promptly 48 hours, and every reactor switched at interval in 24 hours, adopted silica alumina ratio (SiO
2/ Al
2O
3) be 200 type ZSM 5 molecular sieve catalyzer, reaction raw materials is ethylene plant's etherificate carbon four, and the composition in reaction product initial stage and latter stage sees Table 1, and propene yield is 26.38～19.31%.
[embodiment 2]
Certain carbon four and above olefin catalytic cracking to produce propylene process using suitching type continuous production flow process as shown in Figure 1, reactor comprises four sections fixed beds, and three-section fixed-bed is used for reaction, and one section is used for regeneration.600 ℃ of temperature of reaction, air speed 14 hours
-1, normal pressure, catalyst life 48 hours, reactor switched once in promptly 48 hours, and every reactor switched at interval in 16 hours, adopted silica alumina ratio (SiO
2/ Al
2O
3) be 200 type ZSM 5 molecular sieve catalyzer, reaction raw materials is ethylene plant's etherificate carbon four, and the composition in reaction product initial stage and latter stage sees Table 1, and propene yield is 25.84～23.42%.
[comparative example 1～2]
Axial insulation fix bed reactor of certain carbon four and above preparing propylene by catalytic cracking olefin, other processing condition are identical with embodiment 1-2, and the composition in reaction product initial stage and latter stage sees Table 1, and propene yield is 26.67～12.53%.
The composition in table 1 reaction product initial stage and latter stage
| Product is formed (weight %) | ||||||
| Embodiment 1 | Embodiment 2 | Comparative example 1-2 | ||||
| Project | 3 sections fixed beds | 4 sections fixed beds | The separate unit reactor | |||
| Initial stage | Latter stage | Initial stage | Latter stage | Initial stage | Latter stage | |
| Hydrogen | 0.11 | 0.06 | 0.10 | 0.08 | 0.12 | 0.03 |
| Methane | 0.61 | 0.39 | 0.60 | 0.51 | 0.64 | 0.21 |
| Ethane | 0.59 | 0.38 | 0.56 | 0.50 | 0.57 | 0.15 |
| Ethene | 9.85 | 5.59 | 9.71 | 7.92 | 10.95 | 2.44 |
| Propane | 2.57 | 1.48 | 2.46 | 2.04 | 2.77 | 0.60 |
| Propylene | 26.38 | 19.31 | 25.84 | 23.42 | 26.67 | 12.53 |
| Trimethylmethane | 5.59 | 4.95 | 5.53 | 5.28 | 5.7 | 4.42 |
| Normal butane | 15.39 | 14.8 | 15.27 | 15.08 | 15.37 | 14.19 |
| Instead-2-butylene | 6.95 | 10.73 | 7.05 | 8.32 | 6.91 | 14.47 |
| Butene-1 | 5.78 | 8.88 | 5.84 | 6.88 | 5.78 | 11.98 |
| Iso-butylene | 9.47 | 13.45 | 9.69 | 11.36 | 8.46 | 16.42 |
| Suitable-2-butylene | 5.32 | 8.12 | 5.39 | 6.31 | 5.36 | 10.95 |
| Pentane | 0.44 | 0.27 | 0.44 | 0.39 | 0.43 | 0.09 |
| Iso-pentane | 0.4 | 0.27 | 0.39 | 0.34 | 0.42 | 0.16 |
| Skellysolve A | 0.28 | 0.19 | 0.28 | 0.25 | 0.29 | 0.11 |
| Amylene | 8.31 | 9.40 | 8.51 | 9.11 | 7.62 | 9.80 |
| Carbon is more than six | 1.95 | 1.69 | 2.00 | 1.93 | 1.94 | 1.42 |
Claims (7)
1, a kind of method of producing propylene continuously in switch mode is a raw material with the rich olefins that contains one or more carbon four and above alkene, makes olefin feedstock pass through the reactor and the silica alumina ratio SiO of one group of fixed bed parallel connection respectively
2/ Al
2O
3Be at least the contact of 10 crystal aluminosilicate catalyzer and generate the effluent that contains propylene, it is characterized in that used reactor is provided with 2～10 beds, each catalyst bed interlayer is and is connected in parallel, reaction raw materials can enter each beds respectively simultaneously, the reaction product of each beds can enter the reaction product house steward respectively simultaneously, when propene yield reduces by 50% in the reaction product of beds, this beds cuts out reactive system and regenerates, and has at least 1 beds to be used for regeneration in the whole reactor.
2,, it is characterized in that carbon four and above cut or the carbon four of by-products such as a-alkene coproduction, MTO and MTP and the above rich olefins cut thereof of the rich olefins mixture material of one or more carbon four or above alkene from steam cracking device in plant catalytic cracker, the ethylene plant according to the method for the described producing propylene continuously in switch mode of claim 1.
3,, it is characterized in that the rich olefins mixture is C according to the method for right 1 described producing propylene continuously in switch mode
4～C
12Normal olefine.
4, according to the method for right 1 described producing propylene continuously in switch mode, it is characterized in that beds has 3～5, be to be connected in parallel, wherein 1～2 beds is in reproduced state, and each beds is pressed certain hour operation successively at interval.
5, according to the method for right 4 described producing propylene continuously in switch mode, it is characterized in that regenerating and carry out by turns successively, when 2～4 beds carry out catalyzed reaction, there is a beds to carry out the regenerative operation of catalyzer.
6,, it is characterized in that the state of reactor is controlled by the inlet valve and the outlet valve of beds according to the method for right 1 described producing propylene continuously in switch mode.
7, according to the method for right 1 described producing propylene continuously in switch mode, it is characterized in that the operational condition of reactor: temperature of reaction is 450～600 ℃, and weight space velocity is 10～40 hours
-1, reaction pressure is 0.02～0.6MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100288062A CN100368358C (en) | 2005-08-15 | 2005-08-15 | Method for producing propylene continuously in switch mode |
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|---|---|---|---|
| CNB2005100288062A CN100368358C (en) | 2005-08-15 | 2005-08-15 | Method for producing propylene continuously in switch mode |
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| CN1915928A true CN1915928A (en) | 2007-02-21 |
| CN100368358C CN100368358C (en) | 2008-02-13 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060648A (en) * | 2010-12-30 | 2011-05-18 | 洛阳市科创石化科技开发有限公司 | Method and device for producing propylene and petrol by catalytic pyrolysis of carbon olefins |
| US8137631B2 (en) | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
| CN101328100B (en) * | 2008-06-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene by converting oxygen-containing compound |
| US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| US8889076B2 (en) | 2008-12-29 | 2014-11-18 | Uop Llc | Fluid catalytic cracking system and process |
| CN104437268A (en) * | 2014-11-06 | 2015-03-25 | 南京大学 | Multistage parallel intensified fixed bed reactor and using method thereof |
| CN104607112A (en) * | 2015-01-04 | 2015-05-13 | 南京大学 | Multistage enhanced fixed bed reactor and use method thereof |
| CN109925972A (en) * | 2019-04-23 | 2019-06-25 | 宁波巨化新材料有限公司 | A kind of multisection type fixed bed reactors reacted for synthesizing normal propyl alcohol |
| CN113443955A (en) * | 2021-06-28 | 2021-09-28 | 江苏斯尔邦石化有限公司 | Method for preparing propylene by catalytic cracking of C4-C6 olefin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151105C (en) * | 2001-10-22 | 2004-05-26 | 中国石油化工股份有限公司 | Method for producing propene using C4 and its above colefines |
| CN1274645C (en) * | 2003-10-27 | 2006-09-13 | 中国石油化工股份有限公司 | Method for producing propene for C4 and more olefin catalytic cracking |
-
2005
- 2005-08-15 CN CNB2005100288062A patent/CN100368358C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328100B (en) * | 2008-06-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene by converting oxygen-containing compound |
| US8137631B2 (en) | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
| US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| US8889076B2 (en) | 2008-12-29 | 2014-11-18 | Uop Llc | Fluid catalytic cracking system and process |
| CN102060648A (en) * | 2010-12-30 | 2011-05-18 | 洛阳市科创石化科技开发有限公司 | Method and device for producing propylene and petrol by catalytic pyrolysis of carbon olefins |
| CN104437268A (en) * | 2014-11-06 | 2015-03-25 | 南京大学 | Multistage parallel intensified fixed bed reactor and using method thereof |
| CN104607112A (en) * | 2015-01-04 | 2015-05-13 | 南京大学 | Multistage enhanced fixed bed reactor and use method thereof |
| CN109925972A (en) * | 2019-04-23 | 2019-06-25 | 宁波巨化新材料有限公司 | A kind of multisection type fixed bed reactors reacted for synthesizing normal propyl alcohol |
| CN113443955A (en) * | 2021-06-28 | 2021-09-28 | 江苏斯尔邦石化有限公司 | Method for preparing propylene by catalytic cracking of C4-C6 olefin |
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|---|---|
| CN100368358C (en) | 2008-02-13 |
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