CN104232151A - Catalytic reforming method of naphtha - Google Patents
Catalytic reforming method of naphtha Download PDFInfo
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- CN104232151A CN104232151A CN201310247528.4A CN201310247528A CN104232151A CN 104232151 A CN104232151 A CN 104232151A CN 201310247528 A CN201310247528 A CN 201310247528A CN 104232151 A CN104232151 A CN 104232151A
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Abstract
The invention discloses a catalytic reforming method of naphtha. Naphtha is introduced into three or four reforming reactors which are connected with one another in series and are filled with a reforming catalyst; and reforming circulating hydrogen is introduced into the second reactor, or is divided into a plurality of strands, and is respectively introduced into the second reactor and various reactors on the downstream. According to the method, the reforming circulating hydrogen is not introduced into the first reactor, so that the total amount of carbon deposit of the catalyst can be reduced, the service life of the catalyst is prolonged, and the yield of a C5<+> liquid product is increased.
Description
Technical field
The present invention is a kind of hydroconversion process, specifically, is a kind of Benzin naphtha catalytic reforming method.
Background technology
Petroleum naphtha continuous catalytic reforming receives high, the high and aromatics yield high of hydrogen product with its liquid, is subject to the very big attention of people, and plays leading role by reforming process evolution from now in stop bracket gasoline and aromatics production.
Continuous reformer comprises reaction member and catalyst regeneration units.Dissimilar continuous reforming process adopts dissimilar catalyst regeneration units.At present, most of continuous reformer adopts four reactors in the world, also has small part reformer to adopt three reactors.The flow process of conventional continuous reformer reaction member is generally: after entering reformer from the refining petroleum naphtha of reformed pre-hydrogenated unit, mix with reforming cycle hydrogen, then enter in parallel feeding interchanger with reaction product heat exchange.Material after heat exchange is heated to after temperature of reaction through the first process furnace and enters the first reactor, then successively through the second process furnace, the second reactor, the 3rd process furnace, the 3rd reactor, the 4th process furnace, the 4th reactor.From last reforming reactor reaction product out parallel feeding interchanger with charging heat exchange, then after water cooler cools and makes wherein oil product condensation, enter reformate separating tank.Tank deck separates hydrogen-containing gas, and a part, as recycle hydrogen, returns the first reactor by compressor compresses with raw material after mix, another part as hydrogen product direct or after concentrate carrying device.
CN101921610A discloses a kind of catalystic reforming method of gasoline, comprises moving-bed catalytic reforming unit and the catalyst regeneration section of the reactor of employing three or four series windings.When employing three reactors, the effluent from regeneration unit catalyst reduction district is recycled to the top of the 3rd reactor; When catalytic reforming units adopts four reactors, reduction zone exporting hydrogen is recycled to the top of the 3rd reactor and/or the top of the 4th reactor.
CN102277190A discloses a kind of new catalytic reforming process.The method is for comprising the moving-bed continuous reformer of four moving-burden bed reactors of connecting and catalyst regeneration reduction zone.The gaseous effluent of the agent of autocatalysis in the future reduction step is partly recycled directly to the top of the first reactor, rest part is recycled to the entrance of the parallel feeding interchanger before the first reactor, by circulating hydrogen compressor, the hydrogen-containing gas from reformate gas-liquid separator is recycled to whole or in part the top of the 3rd and/or the 4th reactor, to increase the hydrogen/hydrocarbon ratio of subsequent reactor.
From the angle of reforming reaction chemistry, the principal reaction of the first reactor of reforming is cycloalkanes dehydrogenation reaction, and most naphthenic hydrocarbon completes dehydrogenation reaction wherein, therefore, the first reactor temperature drop is large, and average bed temperature is lower, self-produced amounts of hydrogen is large, and catalyzer coke content is very low, generally below 2%.But because the first reactor scale is less, during old device capacity expansion revamping, be often subject to the adherent restriction of the first reactor catalyst.
Summary of the invention
The object of this invention is to provide a kind of Benzin naphtha catalytic reforming method, this method does not pass into external hydrogen in reformation first reactor, thus can reduce catalyzer total carbon deposition, extending catalyst work-ing life, increases C5+ liquid product yield.
Benzin naphtha catalytic reforming method provided by the invention, comprise and pass into petroleum naphtha in contact each other three or four reforming reactors of filling reforming catalyst, and pass into reforming cycle hydrogen in second reactor, or reforming cycle hydrogen is divided into each reactor that multiply passes into the second reactor and downstream respectively.
The inventive method does not introduce external hydrogen in reformation first reactor, but reforming cycle hydrogen is introduced the second reactor or introduce each reactor of the first reactor downstream respectively, can increase reformation C
5 +liquid yield, reduces catalyzer total carbon deposition, extending catalyst work-ing life, and the turndown ratio of device can be increased, the adherent problem of the first reactor catalyst during solving device expansion energy, Reforming recycle hydrogen compressor gangway pressure reduction declines simultaneously, and the operation energy consumption of device declines.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of reforming method of the present invention.
Embodiment
The flow process of conventional continuous reformer reaction member is generally: the hydrogen-containing gas separated from reformate splitter top, a part is as recycle hydrogen, through entering reforming reaction system by parallel feeding interchanger, the first process furnace, the first reactor by compressor compresses and after mixing with raw material, another part is as hydrogen product carrying device directly or after concentrate.
Due to reforming reaction, from the first reactor to subsequent reactor, catalyzer loading amount increases successively, and reaction time catalizer coke content also increases, and average bed temperature improves.The inventive method improves the supply mode of reforming cycle hydrogen, reforming cycle hydrogen is divided into and one or more strands ofly enters reforming reaction system from the reactor in the second reactor or the second reactor and its downstream respectively, even if the first reactor is being introduced without external hydrogen, self runs when producing hydrogen, also can effectively reduce catalyzer total carbon deposition, be conducive to the work-ing life of extending catalyst.In addition, circulating hydrogen is introduced the second reactor and subsequent reactor thereof, the gas flow entering the first reactor can also be reduced, when reformer expansion can need to improve inlet amount, effectively can solve the adherent problem of the first reactor catalyst.
Reforming cycle hydrogen of the present invention refers to from reformed gas liquid/gas separator, through the hydrogen-containing gas of Reforming recycle hydrogen compressor compression.Described circulating hydrogen heats through process furnace before passing into reactor, passes into reactor after preferably mixing with raw material.
In the present invention, circulating hydrogen does not pass into the first reactor, but passes into the second reactor and follow-up reactor.Described circulating hydrogen can be divided into one or more strands of.
When circulating hydrogen is one, whole circulating hydrogen all passes into the second reactor.
When circulating hydrogen is divided into multiply, pass into the second reactor and follow-up reactor respectively, after entering during continuous reactor, circulating hydrogen can be passed into respectively the second reactor and each follow-up reactor, also circulating hydrogen can be passed into the second reactor and some follow-up reactors.The circulating hydrogen entering the second reactor is 0.4 ~ 0.9, preferably 0.5 ~ 0.8 with the volume ratio of the whole recycle hydrogens entering reactor.
In the present invention, when reformer adopts four reactors, and when described circulating hydrogen is divided into multiply, preferably circulating hydrogen is passed into the second reactor and the 4th reactor.The circulating hydrogen entering the 3rd and/or the 4th reactor is 0.1 ~ 0.6, preferably 0.2 ~ 0.5 with the volume ratio of the whole circulating hydrogens entering reactor.
Described continuous reformer reaction member can have multiple reactor of contacting each other, preferably includes the moving bed radial reactor of three to four series connection.The arrangement mode of described multiple reactors can be mounted on top or places side by side.When employing four reactors, preferably two reactor mounted on top are become one group, then two group reaction devices are placed side by side, often between group, catalyst devator is set.
Catalytic reforming of the present invention is preferably CONTINUOUS REFORMER method, be applicable to various types of use with aluminum oxide or containing the aluminum oxide of zeolite be carrier, the continuous reformer of platinum tin catalyst series containing halogen.
The catalyzer of described CONTINUOUS REFORMER comprises carrier and the platinum metals of 0.01 ~ 2.0 quality %, preferably 0.1 ~ 1.0 quality % that is benchmark with butt carrier, the tin of 0.01 ~ 5.0 quality %, preferably 0.1 ~ 2.0 quality % and 0.1 ~ 5 quality %, preferably 0.1 ~ 3.0 quality % halogen.In addition, also the 3rd and/or the 4th metal constituent element can be contained, one or more in the preferred europium of the 3rd and/or the 4th metal constituent element, cerium and titanium.3rd and/or the 4th metal constituent element content is in the catalyst 0.01 ~ 5.0 quality %, preferably 0.1 ~ 2.0 quality %.
The preferred platinum in platinum metals in described catalyzer, the preferred chlorine of halogen, carrier preferential oxidation aluminium, more preferably gama-alumina.
Below in conjunction with accompanying drawing, the present invention being described, for stating conveniently, in figure, not relating to the detailed process of regeneration system rapidly.
In Fig. 1, from the refining petroleum naphtha of pipeline 1 through parallel feeding interchanger 2, pipeline 3, to reform the first process furnace 4, pipeline 5 enters reformation first reactor 6, contact with reforming catalyst and react, the reaction product of the first reactor is discharged through pipeline 7, after mixing with the reforming cycle hydrogen from pipeline 32, enter reformation second process furnace 8, reformation second reactor 10 is entered through pipeline 9, the reaction product of the second reactor is after pipeline 11 is discharged, enter reformation the 3rd process furnace 12, reformation the 3rd reactor 14 is entered through pipeline 13, the reaction product of the 3rd reactor is after pipeline 15 is discharged, enter reformation the 4th process furnace 33, reformation the 4th reactor 17 is entered through pipeline 16, parallel feeding interchanger 2 is entered through pipeline 18 from the 4th reactor reformate out, with from after the refining petroleum naphtha heat exchange of pipeline 1, through pipeline 22, air cooler 23, pipeline 24, water cooler 25, pipeline 26 enters reformed gas liquid/gas separator 27.In reformed gas liquid/gas separator 27, liquid phase is separated, and an isolated hydrogen-containing gas part sends into downstream hydrogen recycling unit through pipeline 28, and another part enters after Reforming recycle hydrogen compressor 20 compression through pipeline 21, sends into reforming reactor through pipeline 19.The isolated liquid product of reformed gas liquid/gas separator 27 is discharged by pipeline 29.
If reforming cycle hydrogen divides one to enter reactor, then enter reformation second process furnace 8 by pipeline 32, then enter reformation second reactor 10.If reforming cycle hydrogen is divided into multiply, circulating hydrogen then from pipeline 19 can divide three strands, first stock-traders' know-how pipeline 32 enters reformation second process furnace 8, enter reformation second reactor 10 again, after second stock-traders' know-how pipeline 30 enters reformation the 3rd process furnace 12, enter after reformation the 3rd reactor the 14, three stock-traders' know-how pipeline 31 enters reformation the 4th process furnace 33 again, then enter reformation the 4th reactor 17.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
Adopt the inventive method to carry out the reaction of petroleum naphtha CONTINUOUS REFORMER, the circulating hydrogen from continuous reformer compressor outlet does not enter the first reactor, all enters the second reactor.Use Hunan to build the continuous reforming catalyst RC011 of long catalyst Co. production, wherein containing Pt0.28 quality %, Sn0.41 quality %, carrier is gama-alumina.Refining petroleum naphtha character used in table 1, reaction conditions and the results are shown in Table 2.
Example 2
The inventive method is adopted to carry out the reaction of petroleum naphtha CONTINUOUS REFORMER, circulating hydrogen from continuous reformer compressor outlet does not enter the first reactor, be divided into two stocks and do not enter the second reactor and the 4th reactor, wherein the circulating hydrogen of 80 volume % enters the second reactor, and the circulating hydrogen of 20 volume % enters the 4th reactor.Used catalyst and petroleum naphtha all with example 1, reaction conditions and the results are shown in Table 2.
Comparative example 1
Adopt conventional continuous reforming process flow process, namely circulating hydrogen all enters reformer from the first reactor.Used catalyst and petroleum naphtha all with example 1, reaction conditions and the results are shown in Table 2.
Comparative example 2
Adopt the flow process of patent CN101921610A, (flow is 3800Nm to reduction zone exporting hydrogen
3/ h) after reformation parallel feeding interchanger, enter the 4th reactor, all remove the first reactor from Reforming recycle hydrogen compressor circulating hydrogen out, used catalyst and petroleum naphtha all with example 1, reaction conditions and the results are shown in Table 2.
Comparative example 3
Adopt the flow process of patent CN102277190A, (flow is 3800Nm to reduction zone exporting hydrogen
3/ h) after reformation parallel feeding interchanger, enter the first reactor, all remove the 4th reactor from Reforming recycle hydrogen compressor circulating hydrogen out, used catalyst and petroleum naphtha all with example 1, reaction conditions and the results are shown in Table 2.Table 1
Table 2
* hydrogen/hydrocarbon mol ratio is the amount of substance of the hydrogen entering this reactor and the ratio of the amount of substance of catalytic reforming feedstock.
Claims (9)
1. a Benzin naphtha catalytic reforming method, comprise and pass into petroleum naphtha in contact each other three or four reforming reactors of filling reforming catalyst, reforming cycle hydrogen is passed in second reactor, or reforming cycle hydrogen is divided into multiply, pass into each reactor in the second reactor and downstream respectively.
2. in accordance with the method for claim 1, it is characterized in that described circulating hydrogen is from reformate gas-liquid separator.
3. in accordance with the method for claim 1, it is characterized in that described circulating hydrogen heats through process furnace before passing into reactor.
4., in accordance with the method for claim 1, when it is characterized in that described circulating hydrogen is divided into multiply, the circulating hydrogen entering the second reactor is 0.4 ~ 0.9 with the volume ratio of the whole recycle hydrogens entering reactor.
5. in accordance with the method for claim 1, it is characterized in that when employing four reactors, and when described circulating hydrogen is divided into multiply, the circulating hydrogen entering the 3rd and/or the 4th reactor is 0.1 ~ 0.6 with the volume ratio of the whole recycle hydrogens entering reactor.
6. in accordance with the method for claim 1, it is characterized in that, when employing four reactors, two reactor mounted on top being become one group, then two group reaction devices being placed side by side.
7. in accordance with the method for claim 1, it is characterized in that described catalytic reforming is continuous catalytic reforming method.
8. in accordance with the method for claim 7, it is characterized in that the catalyzer of CONTINUOUS REFORMER comprise carrier and the platinum metals of 0.01 ~ 2.0 quality % that is benchmark with butt carrier, the tin of 0.01 ~ 5.0 quality % and 0.1 ~ 5 quality % halogen.
9. in accordance with the method for claim 8, it is characterized in that described platinum metals is platinum, halogen is chlorine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316029A (en) * | 2014-07-29 | 2016-02-10 | Ifp新能源公司 | Reforming process with optimized distribution of the catalyst |
| CN106753548A (en) * | 2015-11-21 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
| CN114426871A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic reforming method for naphtha |
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| US5203988A (en) * | 1991-08-19 | 1993-04-20 | Exxon Research & Engineering Company | Multistage reforming with ultra-low pressure cyclic second stage |
| US5318689A (en) * | 1992-11-16 | 1994-06-07 | Texaco Inc. | Heavy naphtha conversion process |
| CN101107055A (en) * | 2005-01-21 | 2008-01-16 | 埃克森美孚研究工程公司 | Improved catalytic reformer unit and unit operation |
| CN101376823A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Benzin naphtha catalytic reforming method |
| CN102041092A (en) * | 2011-01-13 | 2011-05-04 | 中国石油天然气华东勘察设计研究院 | Method for widening catalytic reforming feedstock |
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2013
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5203988A (en) * | 1991-08-19 | 1993-04-20 | Exxon Research & Engineering Company | Multistage reforming with ultra-low pressure cyclic second stage |
| US5318689A (en) * | 1992-11-16 | 1994-06-07 | Texaco Inc. | Heavy naphtha conversion process |
| CN101107055A (en) * | 2005-01-21 | 2008-01-16 | 埃克森美孚研究工程公司 | Improved catalytic reformer unit and unit operation |
| CN101376823A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Benzin naphtha catalytic reforming method |
| CN102041092A (en) * | 2011-01-13 | 2011-05-04 | 中国石油天然气华东勘察设计研究院 | Method for widening catalytic reforming feedstock |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316029A (en) * | 2014-07-29 | 2016-02-10 | Ifp新能源公司 | Reforming process with optimized distribution of the catalyst |
| CN105316029B (en) * | 2014-07-29 | 2019-08-06 | Ifp 新能源公司 | The reforming method of catalyst distribution with optimization |
| CN106753548A (en) * | 2015-11-21 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
| CN106753548B (en) * | 2015-11-21 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of Benzin naphtha catalytic reforming method of by-product also protohydrogen |
| CN114426871A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic reforming method for naphtha |
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