CN106906000A - A kind of hydro carbons continuous reforming process - Google Patents
A kind of hydro carbons continuous reforming process Download PDFInfo
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- CN106906000A CN106906000A CN201510976471.0A CN201510976471A CN106906000A CN 106906000 A CN106906000 A CN 106906000A CN 201510976471 A CN201510976471 A CN 201510976471A CN 106906000 A CN106906000 A CN 106906000A
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- 238000002407 reforming Methods 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000008569 process Effects 0.000 title claims abstract description 51
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 26
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 222
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 230000008929 regeneration Effects 0.000 claims description 26
- 238000011069 regeneration method Methods 0.000 claims description 26
- 239000000428 dust Substances 0.000 claims description 22
- 230000001172 regenerating effect Effects 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000012958 reprocessing Methods 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000006057 reforming reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 230000008859 change Effects 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydro carbons continuous reforming process, the technique includes：At least three reforming reactors and at least one catalyst regenerator are set, wherein, last reforming reactor is referred to as second group of reactor, reactor in addition to last reforming reactor is referred to as first group of reactor, reaction feed is carried out relative to the conveying series connection of each reforming reactor, catalyst is that parallel connection is carried out with the circulation conveying between regenerator in first group of reactor and second group of reactor, and catalyst is that counter flow in series is carried out with the conveying between regenerator in first group of reactor.In the present invention, every group of reactor can be carried out separately adjustable using fresh high activated catalyst and on demand and change catalyst flow, can give full play to the activity of catalyst, improve the utilization rate of catalyst, improve reforming conversion and product yield.
Description
Technical field
The present invention relates to hydrocarbon reformation field, and in particular to a kind of hydro carbons continuous reforming process.
Background technology
CONTINUOUS REFORMER is a kind of oil secondary operation technology, and the raw material of processing is mainly the straight run of low octane rating
Naphtha, hydrotreated naphtha etc., using platinum Pt- tin Sn bimetallic catalysts, at 500 DEG C or so
Under high temperature, make molecule that rearrangement, isomery to occur, increase the yield of aromatic hydrocarbons, improve the technology of octane number.
Moving-burden bed reactor continuous regenerative reforming, abbreviation CONTINUOUS REFORMER.Industry should in the world at present
Main three CONTINUOUS REFORMER patented technologies provider is respectively Uop Inc. of the U.S., France Axens
With Chinese SEI.In continuous reformer, catalyst continuously flows successively through three (or four) of series connection
Moving-burden bed reactor, is generally from the reclaimable catalyst carbon content of last reactor outflow
2%-8% (mass fraction), reclaimable catalyst is transported to regenerator and is regenerated by gravity or gas lift.
Regenerated catalyst after activity recovery returns to first reactor and is reacted again, and catalyst is formed in system
One closed cycle.
By catalyst transport model split, existing industrialized continuous reforming process can be divided into " suitable
Stream " and " adverse current " two ways.
In the catalyst circulation conveying technique of " following current " CONTINUOUS REFORMER, reaction mass from first reactor according to
It is secondary to flow to most end reactor, reacted on the catalyst in each reactor.Catalyst is in each reactor
Between moving direction be consistent with reaction mass, that is, the high activated catalyst for regenerating is by reaction stream
Order is introduced into first reactor, then passes sequentially through second reactor, the 3rd reactor until most end is anti-
Device is answered, is gradually reduced to most end reactor pressure from first reactor, from the catalysis out of most end reactor
Agent activity is relatively low, is sent in regenerator and is regenerated, and the catalyst after regeneration is lifted to the first reaction again
Device completes the circulation of catalyst.In the technical process of this CONTINUOUS REFORMER, catalyst is in the reactor string
What connection was used, the catalyst into the first reforming reactor is just to have regenerated urging for " fresh " high activity
Agent, and reactor below is all the above reactor relatively low catalysis of used activity
Agent.
In the catalyst circulation conveying technique of " adverse current " CONTINUOUS REFORMER, reaction mass from first reactor according to
It is secondary to flow to most end reactor.And moving direction of the catalyst between each reactor is opposite with reaction mass
, that is, the order of the high activated catalyst back reaction logistics for regenerating is introduced into rearmost reactor, so
The direction of back reaction logistics is successively forward until first reactor afterwards, then is sent to regeneration from first reactor
Regenerated in device, the catalyst after regeneration lifts last reactor and completes following for catalyst again
Ring.The technical process of this adverse current CONTINUOUS REFORMER causes the difficult reaction for carrying out in high activated catalyst below
Reactor in carry out, reaction easy to perform is carried out in the reactor of low activity catalyst above.
But, either " following current " or " adverse current " continuous reforming process, catalyst reactor it
Between circulation conveying all using series connection by the way of, this mode of movement is only transported to first from regenerator
The catalyst of reactor is only " fresh " activity for just regenerating catalyst high, such as " following current " even
Continuous the first reforming reactor reformed, last reforming reactor of " adverse current " CONTINUOUS REFORMER.And its
Catalyst in his reforming reactor is all that above reactor is used to have dropped containing carbon distribution activity
Low catalyst, catalyst is conveyed in the backward, and its activity is lower, the work in the reactor that catalyst leaves
Property is minimum.The activity of catalyst can not give full play in all reactors as can be seen here.This catalyst
The mode of series connection conveying, the catalyst internal circulating load by each reactor is all identical, in all reactors
Catalyst must circular regeneration simultaneously, the catalyst flow of each reactor can not on demand carry out independence
Regulation and change, it is impossible to be individually circulated regeneration.
The content of the invention
It is an object of the invention to provide a kind of hydro carbons continuous reforming process, prior art is overcome to realize instead
Device is answered to be urged with can not on demand carry out separately adjustable and change using fresh high activated catalyst as needed
The disadvantage of agent flow, to give full play to the activity of catalyst, improves the utilization rate of catalyst, improves weight
Turn over rate and yield.
To achieve these goals, the present invention provides a kind of hydro carbons continuous reforming process, and the technique includes：
At least three reforming reactors and at least one catalyst regenerator being parallel to each other are set；Reaction feed phase
Conveying series connection for each reforming reactor is carried out, i.e., reaction feed passes sequentially through each and reforms instead
Answer device and reacted with catalyst therein；Wherein, flowed to according to reaction feed, at least three by described in
Individual reforming reactor is divided into first group of reactor and second group of reactor, and first group of reactor is included except last
All reforming reactors beyond one reforming reactor, second group of reactor is described last reformation
Reactor；Catalyst is with the circulation conveying between regenerator in first group of reactor and second group of reactor
What parallel connection was carried out, i.e., the reacted reclaimable catalyst in every group reactor is all individually delivered to regenerator
In carry out cyclic regeneration, and the regenerated catalyst after regenerating is transported in every group of reactor by parallel connection and uses again
In reaction；Catalyst is that counter flow in series is carried out with the conveying between regenerator in first group of reactor, i.e.,
Flowed to according to reaction feed, the reclaimable catalyst in the initial reactor in first group of reactor is delivered to
Cyclic regeneration is carried out in regenerator, and the regenerated catalyst after regenerating is transported in first group of reactor
Reacted in the reactor of end, and catalyst by the end reactor be countercurrently delivered to successively it is described
Reacted in beginning reactor and successively.
Preferably, the technique also includes：Independently control the catalysis to be generated from every group of reactor to regenerator
The conveying capacity of agent and/or conveying opportunity, and independently control to be urged from regenerator to the regeneration of every group of reactor
The conveying capacity of agent and/or conveying opportunity.
Preferably, the technique also includes：Reclaimable catalyst reprocessing and distribution system WCTS are set, often
Group reactor in reclaimable catalyst it is elevated in the way of parallel side-by-side be delivered to the WCTS,
Mixed in WCTS, dust elutriation and locking transformation process, be then transferred to be carried out in regenerator
Regeneration；And regenerated catalyst reprocessing and distribution system RCTS are set, and regenerated catalyst is by from regeneration
Device is promoted to the RCTS and carries out dust elutriation, reduction and redistribution process, then with the side of parallel side-by-side
Formula is respectively delivered to be used for chemical reaction process in each group reactor from RCTS.
Preferably, the technique includes, sets four reforming reactors being parallel to each other and a regenerator,
That is the first reforming reactor, the second reforming reactor, tri-reforming device, fourth reforming reactor and
Regenerator, and the technique also includes setting regenerated catalyst reprocessing and distribution system RCTS, to be generated
Catalyst is reprocessed and distribution system WCTS, reclaimable catalyst lifting blower fan and regenerated catalyst lifting
Blower fan；First, second, and third reforming reactor is first group of reactor, and the fourth reforming is anti-
It is second group of reactor to answer device；Reaction feed sequentially pass through the first reforming reactor, the second reforming reactor,
Tri-reforming device and fourth reforming reactor；Regenerated catalyst regenerated catalyst lifts blower fan from again
Raw device is promoted to RCTS；RCTS is connected with the third and fourth reforming reactor respectively；Urged with to be generated
Reclaimable catalyst in first and fourth reforming reactor is promoted to WCTS by agent lifting blower fan respectively；
WCTS is connected by 1 tremie pipe with regenerator；Catalyst is in first group of reactor by
Tri-reforming device flows to the second reforming reactor and the first reforming reactor successively.
Preferably, regenerated catalyst by from regenerator be promoted to RCTS carry out dust elutriation, reduction and again
Assigning process, is then respectively delivered to each group and reacts from RCTS in the way of parallel side-by-side by tremie pipe
It is used for chemical reaction process in device；From RCTS to every group of conveying capacity of the regenerated catalyst of reactor and/
Or conveying opportunity is individually controllable.
Preferably, first and fourth reforming reactor in reclaimable catalyst carried in the way of parallel side-by-side
Rise and be delivered to WCTS, mixed in WCTS, dust elutriation and locking transformation process, then
Regenerator is delivered to by tremie pipe to be regenerated；From every group of reactor to the reclaimable catalyst of WCTS
Lifting conveying capacity and/or conveying opportunity are individually controllable.
Preferably, the operating pressure of RCTS less than regenerator operating pressure, such that it is able to by catalyst
From regenerator lifting to RCTS；The position of RCTS bottoms is higher than the position on each group reactor top simultaneously,
The operating pressure of RCTS is higher than tri-reforming device and the operating pressure of fourth reforming reactor so that
Catalyst can be flowed into every group of reactor from RCTS.
Preferably, the position of WCTS bottoms is higher than the position on regenerator top, and it is two pressures that WCTS is divided to
Power area, the upper zone before transformation is low-pressure area, and pressure is less than the first reforming reactor and fourth reforming
Reactor, can be low to this from the first reforming reactor and the lifting of fourth reforming reactor by reclaimable catalyst
Nip；Lower region after transformation is higher-pressure region, and pressure is higher than regenerator, and reclaimable catalyst can be from
The higher-pressure region is flowed into regenerator.
The circulation conveying mode that continuous reforming process of the invention is combined using catalyst parallel connection and serial connection,
So that the catalyst in the reactor reacted into the third and fourth two difficulties is all just to regenerate
" fresh " catalyst, and the reaction carried out in the first and second reactors above is relatively easy, the 3rd
Catalyzer coke content in reforming reactor is relatively low, and first for being delivered to above is lifted by counter flow series
Applied with second reactor, it is smaller on reaction influence, using this catalyst parallel connection of the invention and string
The circulation conveying mode that connection is combined, flow is relatively easy, and the average coke content of reactor is low, catalyst
Effect can more be not fully exerted.
The present invention is overcome by changing circulation conveying mode of the catalyst between multiple reforming reactors
The shortcoming that each catalyst reactor activity can not give full play in existing industrialized technology.Into
Reactant in most latter two reactor is all contacted with the active catalyst higher for just regenerating, and can be dropped
About 5~10 DEG C of low bed layer mean temperature, the side reaction such as is hydrocracked, with existing work such that it is able to reduce
The CONTINUOUS REFORMER technology of industry is compared can increase product yield about 1%, and can reduce the carbon deposit on catalyst,
Extend the life-span of catalyst.Catalyst internal circulating load into every group of reactor can be adjusted as needed
Section, so as to optimize reaction and regeneration condition, improves catalyst service efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Following specific embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is a kind of schematic flow sheet of specific embodiment of hydro carbons continuous reforming process of the present invention.
Description of reference numerals
The reaction heating furnace of 1 reaction feed/product exchanger 2 first
The reaction heating furnace of 3 first reforming reactors (is anti-) 4 second
The reaction heating furnace of 5 second reforming reactors (two is anti-) 6 the 3rd
The reaction heating furnace of 7 tri-reforming devices (three is anti-) 8 the 4th
The anti-top hopper of 9 fourth reforming reactors (four is anti-) 10 1
The 11 2 anti-anti- top hoppers of top hopper 12 3
13 4 anti-top hoppers 14 1 instead buffer hopper
The 15 2 anti-buffering regenerators of hopper 16
17 regenerated catalysts are reprocessed and distribution system (RCTS)
18 reclaimable catalysts are reprocessed and distribution system (WCTS)
19 regenerated catalysts lifting blower fan 20 reclaimable catalyst lifting blower fan
Specific embodiment
Specific embodiment of the invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Specific embodiment described herein is merely to illustrate and explain the present invention, and is not limited to this hair
It is bright.
The present invention provides a kind of hydro carbons continuous reforming process, and the technique includes：Set at least three mutually flat
Capable reforming reactor and at least one catalyst regenerator；Reaction feed is relative to each reforming reactor
Conveying series connection carry out, i.e., reaction feed pass sequentially through each reforming reactor and with catalysis therein
Agent is reacted；Wherein, flowed to according to reaction feed, at least three reforming reactor is divided into the
One group of reactor and second group of reactor, first group of reactor are included in addition to last reforming reactor
All reforming reactors, second group of reactor is described last reforming reactor；Catalyst is
One group of reactor and second group of reactor are that parallel connection is carried out with the circulation conveying between regenerator, i.e., every group
Reacted reclaimable catalyst in reactor carries out cyclic regeneration in being all individually delivered to regenerator, and
Regenerated catalyst after regeneration is transported in every group of reactor by parallel connection and is reused for reaction；Catalyst is
One group of reactor is that counter flow in series is carried out with the conveying between regenerator, i.e., flowed to according to reaction feed,
Reclaimable catalyst in initial reactor in first group of reactor is delivered in regenerator to be carried out continuously
Regeneration, and the regenerated catalyst after regenerating is transported in the end reactor in first group of reactor and carries out
Reaction, and catalyst is countercurrently delivered in the initial reactor and successively successively by the end reactor
Reacted.
Hydro carbons continuous reforming process of the invention, the various process conditions employed in it, including original
Material oil, catalyst, the operating condition of reactor, the operating condition of regenerator for being used etc. are all abilities
Known to the those of ordinary skill of domain, there is no particular limitation to it for the present invention.
For example, described catalyst can contain primary activity component noble metal platinum (Pt) etc., co-catalysis
Aluminum oxide of agent component tin (Sn) and rhenium (Re) etc. and acid carrier etc. and other adjuvants, but not
It is limited to this.The operating condition of each reactor can be independently, but be not limited to：Reaction pressure
0.1~1.5MPa, preferably 0.2~1.0MPa；400~550 DEG C of reaction temperature (feedstock inlet temperature), it is excellent
Select 480-520 DEG C；Hydrogen-oil ratio (mol ratio) 0.1~10.0, preferably 1.0~5.0；Weight space velocity is 0.5~5,
Preferably 1.5~3.Described feedstock oil may be, but not limited to,：The straight-run naphtha of low octane rating,
Hydrotreated naphtha etc..
Hydro carbons continuous reforming process of the invention, described reforming reactor is the affiliated technology in this area
Moving-burden bed reactor known to personnel；Moving-burden bed reactor can be 3~6 series connection, preferably 3~4
Platform is connected；Described regenerator is used to make to realize cyclic regeneration by the reclaimable catalyst of reaction inactivation, wraps
Include by burning, oxychlorination, the technique such as drying (or roasting) recover carbon content reclaimable catalyst high
Activity, the quantity of regenerator is preferably one, it is also possible to set again one it is standby.
A kind of specific embodiment of the invention, the hydro carbons continuous reforming process includes setting four
The individual reforming reactor being parallel to each other and a regenerator, i.e. the first reforming reactor 3, second are reformed anti-
Device 5, tri-reforming device 7, fourth reforming reactor 9 and regenerator 16 are answered, and the technique is also
Including setting regenerated catalyst reprocessing and distribution system RCTS17, reclaimable catalyst reprocessing and distributing
System WCTS18, reclaimable catalyst lifting blower fan 20 and regenerated catalyst lifting blower fan 19；It is described
First, second, and third reforming reactor is first group of reactor, and the fourth reforming reactor is second
Group reactor；Reaction feed sequentially passes through the first reforming reactor 3, the second reforming reactor the 5, the 3rd
Reforming reactor 7 and fourth reforming reactor 9；Regenerated catalyst lifts blower fan 19 with regenerated catalyst
RCTS17 is promoted to from regenerator 16；RCTS17 respectively with the third and fourth reforming reactor 7 and 9
It is connected；Blower fan 20 is lifted by treating in first and fourth reforming reactor 3 and 9 with reclaimable catalyst
Raw catalyst is promoted to WCTS18 respectively；WCTS18 is connected by 1 tremie pipe with regenerator 16
Connect；It is anti-that catalyst flows to the second reformation successively in first group of reactor by tri-reforming device 7
Answer the reforming reactor 3 of device 5 and first.
Hydro carbons continuous reforming process of the invention, the regenerated catalyst reprocessing and distribution system
RCTS 17 can carry out dust elutriation, reduction and reallocate to regenerated catalyst, then with parallel side-by-side
Mode be sent to respectively in each group reactor for chemical reaction process by tremie pipe.
Hydro carbons continuous reforming process of the invention, the reclaimable catalyst reprocessing and distribution system
WCTS 18 can be mixed to reclaimable catalyst, dust elutriation and locking transformation, then by blanking
Pipe is delivered to regenerator and is regenerated.
Hydro carbons continuous reforming process of the invention, those skilled in the art are it is appreciated that reaction
Charging can first be exchanged heat with product, then successively and alternately enter heating furnace and reaction below
Device, product to be left and arrive follow-up separator again after heat exchanger and separated.
Hydro carbons continuous reforming process of the invention, catalyst after regeneration from regenerator lifted to
, be respectively delivered to for catalyst by tremie pipe then to be chemically reacted in each group reactor by RCTS17.
The reclaimable catalyst for leaving each group reactor is lifted be delivered to WCTS18 respectively, then defeated by tremie pipe
Regenerator is delivered to be regenerated.
The present invention will be further illustrated by embodiment below, but therefore the present invention is not taken office
What is limited.
Embodiment
A kind of specific embodiment that 1 couple of present invention of the present embodiment combination accompanying drawing is provided is illustrated.Due to
What is carried out is prolonged commerical test, wherein described various process conditions allowed about ±
10% fluctuation.
As shown in figure 1, after reaction feed exchanges heat in reaction feed/product exchanger 1 with product
Sequentially pass through the first reaction heating furnace 2, the first reforming reactor 3, the second reaction heating furnace 4, the second weight
Whole reactor 5, the 3rd reaction heating furnace 6, tri-reforming device 7, the 4th reaction heating furnace 8 and
Four reforming reactors 9, product leave reactor 9 in reaction feed/product exchanger 1 with reaction
Then charging heat exchange is arrived follow-up separator and is separated again, wherein, first, second, and third reforms
Reactor is referred to as first group of reactor, and fourth reforming reactor is referred to as second group of reactor.Reaction mass exists
Pressure drop is produced in flow process, reactor operating pressure order from high to low is：First reforming reaction
Device 3, the second reforming reactor 5, tri-reforming device 7 and fourth reforming reactor 9.In regenerator
16 regeneration after catalyst by regenerated catalyst lifting blower fan 19 with nitrogen from regenerator 16 lifted to
RCTS17.Carry out the dust elutriation of catalyst first in RCTS17, then reusable heat hydrogen is to removing
Catalyst after dust is reduced, and is removed the nitrogen after dust and is sent to regenerated catalyst lifting blower fan
19 use as regenerated catalyst lifting nitrogen circulation.The pressure of RCTS17 higher than first group of reactor and
Second group of reactor, i.e., three anti-top hoppers 12, tri-reforming device 7, four anti-top hoppers 13
With fourth reforming reactor 9, the catalyst after reduction respectively enters each group by gravity by 2 tremie pipes
The top hopper 12 of reactor, 13, then enter corresponding reactor 7 by gravity, carried out in 9 chemical anti-
Should.The catalyst for finishing is reacted from reactor 9 to be lifted in two anti-buffering hoppers 15 with hydrogen, then
Entered in two anti-top hoppers 11 by tremie pipe by gravity, subsequently into being reacted in reactor 5.
The catalyst for finishing is reacted from reactor 5 to be lifted in two anti-buffering hoppers 14 with hydrogen, then by weight
Power is entered in an anti-top hopper 10 by tremie pipe, subsequently into being reacted in reactor 3.
In each group reactor it is used be all the high activity for just regenerating catalyst.Can be in the blanking
Catalyst flow control device is set on pipe or top hopper, to realize to entering in each group reactor again
The flow of raw catalyst is controlled or even dams.Lifting the nitrogen of blower fan 20 with reclaimable catalyst will treat
Raw catalyst is the first reforming reactor 3 from each group reactor respectively and fourth reforming reactor 9 lifted it is defeated
The top low-pressure area of WCTS18 is delivered to, the operating pressure of WCTS18 tops low-pressure area is less than the first weight
Whole reactor 3 and fourth reforming reactor 9, are lifted to the catalyst of WCTS from every group of reactor and conveyed
All it is independent, and it is controllable to lift conveying capacity, can as needed change carrying for reclaimable catalyst
Rise conveying capacity.In the top low-pressure area of WCTS18, catalyst is mixed first, then entered again
The dust elutriation of row catalyst, the nitrogen after removing dust is sent to reclaimable catalyst lifting blower fan 20 and makees
For reclaimable catalyst lifting nitrogen circulation is used, remove the catalyst after dust carries out locking transformation again,
Catalyst after boosting enters back into the bottom higher-pressure region of WCTS18, and the operating pressure of higher-pressure region is higher than regeneration
Device 16, the catalyst after boosting is delivered to regenerator 16 and is regenerated by tremie pipe, regenerator 16
Pressure be higher than RCTS17, the catalyst for leaving regenerator is promoted to RCTS, so far completes catalyst
Conveying circulation.
The present embodiment uses C6~C12Naphtha hydro carbons carries out cycloalkanes dehydrogenation, alkane ring in the hydrogen gas atmosphere
Fluidized dehydrogenation, isomerization and the reaction such as it is hydrocracked.Reaction feed (naphtha and hydrogen mixture) is through anti-
Should feed/product exchanger 1 exchange heat after, sequentially pass through the first reaction heating furnace 2, the first reforming reactor
3rd, the second reaction heating furnace 4, the second reforming reactor 5, the 3rd reaction heating furnace 6, tri-reforming are anti-
Device 7, the 4th reaction heating furnace 8 and fourth reforming reactor 9 are answered, it is anti-that product leaves fourth reforming
After answering device 9, exchanged heat with reaction feed in reaction feed/product exchanger 1, follow-up dividing then is arrived again
Separated from device.The inlet pressure of first reforming reactor 3 is about 0.56MPa (g), the second reformation instead
The inlet pressure of device 5 about 0.49MPa (g), the inlet pressure of tri-reforming device 7 is answered to be about
0.42MPa (g), the inlet pressure of fourth reforming reactor 9 are about 0.35MPa (g).
The catalyst for being used contains noble metal platinum for Research Institute of Petro-Chemical Engineering (RIPP) exploitation
(Pt) and tin (Sn) and other adjuvants PS-VI continuous reforming catalysts.Leave regenerator 16
Catalyst carbon content after regeneration is approximately less than 0.2% (wt), and nitrogen is used by regenerated catalyst lifting blower fan 19
Gas is lifted to RCTS17 from regenerator 16.Carry out the dust elutriation of catalyst first in RCTS17,
Then the catalyst after removing dust is reduced with hot hydrogen in RCTS17, after removing dust
Nitrogen be sent to regenerated catalyst lifting blower fan 19 as regenerated catalyst lifting nitrogen circulation use.
The operating pressure of RCTS compares regenerator than tri-reforming device operating pressure 0.01~0.08MPa high
16 low 0.01~0.08MPa.Catalyst after reduction divides after leaving RCTS through 2 tremie pipes by gravity
Not Jin Ru reactor top hopper 12,13, then enter corresponding from reactor top hopper by gravity again
Reforming reactor 7, is chemically reacted in 9, reacted in reforming reactor 7 catalyst for finishing again according to
It is secondary to be delivered to reforming reactor 5,3.Used in each group reactor is all urging for the high activity that just regenerated
Agent.
Blower fan 20 is lifted with reclaimable catalyst by reclaimable catalyst nitrogen respectively from each group reactor
The lifting of reforming reactor 3,9 is delivered to WCTS18 tops low-pressure area, and the operating pressure of low-pressure area compares the
Low 0.01~the 0.08MPa of four reforming reactor 9, less than all of reactor.From every group of reactor to
The catalyst lifting conveying of WCTS is all independently carried out, and can as needed change each group reactor
Catalyst lifts conveying capacity, it is also possible to which the reclaimable catalyst in single group or multigroup reactor is individually carried
Conveying is risen, the circulation conveying of catalyst can be neatly carried out.In the low-pressure area of WCTS18 tops first
The mixing of catalyst is carried out, the dust elutriation of catalyst is then carried out again, removed the nitrogen after dust and send
Used as reclaimable catalyst lifting nitrogen circulation to reclaimable catalyst lifting blower fan 20.Remove dust it
Catalyst afterwards carries out locking transformation again, and the catalyst after boosting enters back into the bottom high pressure of WCTS18
Area, the operating pressure about 0.01~0.08MPa higher than regenerator 16 of bottom higher-pressure region.Higher-pressure region is treated
Raw catalyst is delivered to regenerator 16 and is regenerated by tremie pipe, and the operating pressure of regenerator is about 0.65
MPa (g), the catalyst after regeneration is lifted be delivered to RCTS17 again, completes the circulation of catalyst.
Reaction mass is reacted in the reactor can all make carbon deposit on catalyst surface, leave reactor
, than entering the high of reactor, for the process of series connection conveying, carbon deposited catalyst will for coke content on catalyst
Go successively to reactor below, therefore, its coke content can also be accumulated constantly, in the backward catalyst
Coke content is higher, and activity is also constantly reduced, and existing CONTINUOUS REFORMER is exactly to use this series connection mode of movement,
Its catalyst is circulated and causes the catalyst activity in downstream reactor less than the reactor of upstream, catalyst
Activity can not give full play to.The circulation that continuous reforming process of the invention is combined using catalyst connection in series-parallel
The mode of conveying so that be all " fresh " catalyst for just regenerating into every group of catalyst of reactor,
The average coke content of reactor is low, and the effect of catalyst can more be not fully exerted.Into most latter two reaction
Reactant in device is all contacted with the active catalyst higher for just regenerating, and can reduce bed averagely warm
About 5~10 DEG C of degree, the side reaction such as is hydrocracked, with existing industrialized continuous weight such that it is able to reduce
Adjusting technique is compared can increase product yield about 1%, and can reduce the carbon deposit on catalyst, extend catalyst
Life-span.Catalyst internal circulating load into every group of reactor can be adjusted as needed, so as to optimize
Reaction and regeneration condition, improve catalyst service efficiency.
Table 1 listed in the present embodiment and according to (catalyst connection in series-parallel circulation conveying) of the invention and press respectively
Three groups of check experiments of hydro carbons CONTINUOUS REFORMER are carried out according to prior art (conveying of catalyst following current series circulation)
Result of the test.
Continuous reforming process of the present invention and existing industrialized company from the results shown in Table 1
Continuous reforming process is compared and had the following advantages：
1st, continuous reforming process of the present invention is all into the catalyst of the 3rd, fourth reforming reactor
The fresh catalyst without carbon deposit for just regenerating, active highest reacts severity conditions (anti-in identical
Product is answered to reach identical RON values), compared with existing industrialized CONTINUOUS REFORMER, each reaction
The inlet temperature of device declines 3~5 DEG C.
2nd, identical reaction severity conditions under, continuous reforming process of the present invention than it is existing
Industrialized continuous reforming process average reaction temperature declines so that the average carbon deposit rate reduction on catalyst
30~40%, C5 +Liquid yield increases by 0.7~1.1%, and hydrogen yield increases by 2.1~4.7%.
For the catalytic reforming unit that a set for the treatment of capacity is 1,000,000 tons/year, using of the present invention
Continuous reforming process with using compared with existing continuous reforming process, annual increasing gasoline yield 0.7~1.1 ten thousand ton,
Increase about 2100~33,000,000 yuan of income, increase production 720~1700 tons of hydrogen, increase income about 720~1700
Wan Yuan.
In above-mentioned comparative example, continuous reforming process of the present invention and existing industrial continuous reforming process
Operating mode uses identical air speed and identical catalyst filling ratio, i.e., continuous reforming process of the present invention
Operating mode does not optimize.If optimizing reaction condition (such as catalyst of continuous reforming process of the present invention
Filling ratio etc.), then can reduce catalyst filling amount or further improve liquid yield, increase the benefit.
Table 1
Claims (8)
1. a kind of hydro carbons continuous reforming process, the technique includes：At least three weights being parallel to each other are set
Whole reactor and at least one catalyst regenerator；It is characterized in that：
Reaction feed is carried out relative to the conveying series connection of each reforming reactor, i.e., reaction feed is successively
Reacted by each reforming reactor and with catalyst therein；Wherein, flowed to according to reaction feed,
At least three reforming reactor is divided into first group of reactor and second group of reactor, first group of reaction
Device includes all reforming reactors in addition to last reforming reactor, and second group of reactor is described
Last reforming reactor；
Catalyst is simultaneously with the circulation conveying between regenerator in first group of reactor and second group of reactor
What connection was carried out, i.e., the reacted reclaimable catalyst in every group reactor is all individually delivered in regenerator
Cyclic regeneration is carried out, and the regenerated catalyst after regenerating is transported in every group of reactor by parallel connection and is reused for
Reaction；
Catalyst is that counter flow in series is carried out with the conveying between regenerator in first group of reactor, i.e., according to
Reaction feed is flowed to, and the reclaimable catalyst in the initial reactor in first group of reactor is delivered into regeneration
Cyclic regeneration is carried out in device, and the regenerated catalyst after regenerating is transported to the end in first group of reactor
Reacted in reactor, and catalyst is countercurrently delivered to the starting instead successively by the end reactor
Answer in device and reacted successively.
2. hydro carbons continuous reforming process according to claim 1, the technique also includes：Independently control
From every group of reactor to the conveying capacity of the reclaimable catalyst of regenerator and/or conveying opportunity, and independently control
Make the conveying capacity from regenerator to every group of regenerated catalyst of reactor and/or conveying opportunity.
3., according to the hydro carbons continuous reforming process of claim 1 or 2, the technique also includes：Setting is treated
Raw catalyst reprocessing and distribution system WCTS, the reclaimable catalyst in every group of reactor is with parallel side-by-side
Mode it is elevated be delivered to the WCTS, mixed in WCTS, dust elutriation and locking become
Journey is pressed through, is then transferred to be regenerated in regenerator；And regenerated catalyst reprocessing is set and is divided
Match system RCTS, regenerated catalyst is promoted to the RCTS from regenerator carries out dust elutriation, reduction
And redistribution process, then it is respectively delivered in each group reactor from RCTS in the way of parallel side-by-side
For chemical reaction process.
4. hydro carbons continuous reforming process according to claim 1, the technique includes, sets four mutually
Parallel reforming reactor and a regenerator, i.e. the first reforming reactor (3), the second reforming reactor
(5), tri-reforming device (7), fourth reforming reactor (9) and regenerator (16), and should
Technique also includes that set regenerated catalyst reprocessing and distribution system RCTS (17), reclaimable catalyst locates again
Reason and distribution system WCTS (18), reclaimable catalyst lift blower fan (20) and regenerated catalyst is carried
Rise blower fan (19)；First, second, and third reforming reactor is first group of reactor, described the
Four reforming reactors are second group of reactor；Reaction feed sequentially passes through the first reforming reactor (3),
Two reforming reactors (5), tri-reforming device (7) and fourth reforming reactor (9)；Regeneration is urged
Agent regenerated catalyst lifts blower fan (19) and is promoted to RCTS (17) from regenerator (16)；RCTS
(17) it is connected with the third and fourth reforming reactor (7 and 9) respectively；Lifted with reclaimable catalyst
Respectively be promoted to reclaimable catalyst in first and fourth reforming reactor (3 and 9) by blower fan (20)
WCTS(18)；WCTS (18) is connected by 1 tremie pipe with regenerator (16)；Catalyst
The second reforming reactor (5) is flowed to by tri-reforming device (7) successively in first group of reactor
With the first reforming reactor (3).
5. hydro carbons continuous reforming process according to claim 4, wherein, regenerated catalyst is by from regeneration
Device (16) is promoted to RCTS (17) and carries out dust elutriation, reduction and redistribution process, then with flat
Row mode arranged side by side from RCTS (17) each group reactor is respectively delivered to by tremie pipe in for chemistry
Course of reaction；During from RCTS (17) to the conveying capacity of every group of regenerated catalyst of reactor and/or conveying
Machine is individually controllable.
6. hydro carbons continuous reforming process according to claim 4, wherein, first and fourth reforming reaction
Reclaimable catalyst in device (3 and 9) is elevated in the way of parallel side-by-side to be delivered to WCTS (18),
Mixed in the WCTS (18), dust elutriation and locking transformation process, it is then defeated by tremie pipe
Regenerator (16) is delivered to be regenerated；From every group of reactor to the reclaimable catalyst of WCTS (18)
Lifting conveying capacity and/or conveying opportunity are individually controllable.
7. hydro carbons continuous reforming process according to claim 4, wherein, the operation of RCTS (17)
Pressure is less than the operating pressure of regenerator (16), such that it is able to catalyst is lifted to RCTS from regenerator
(17)；The position of RCTS (17) bottom is higher than the position on each group reactor top, RCTS (17) simultaneously
Operating pressure of the operating pressure higher than tri-reforming device (7) and fourth reforming reactor (9),
Allow that catalyst is flowed into every group of reactor from RCTS (17).
8. hydro carbons continuous reforming process according to claim 4, wherein, WCTS (18) bottom
Higher than the position on regenerator (16) top, WCTS (18) is divided into two pressure areas, in transformation for position
Upper zone before is low-pressure area, and pressure is less than the first reforming reactor (3) and fourth reforming reactor
(9), reclaimable catalyst can be carried from the first reforming reactor (3) and fourth reforming reactor (9)
It is raised to the low-pressure area；Lower region after transformation is higher-pressure region, and pressure is higher than regenerator (16), is treated
Raw catalyst can be flowed into regenerator (16) from the higher-pressure region.
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| CN204111688U (en) * | 2014-08-21 | 2015-01-21 | 中国石化工程建设有限公司 | Hydro carbons continuous reformer (four) |
| CN104293377A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Reforming reaction device |
| CN204111687U (en) * | 2014-08-21 | 2015-01-21 | 中国石化工程建设有限公司 | Hydro carbons continuous reformer (one) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293377A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Reforming reaction device |
| CN204111688U (en) * | 2014-08-21 | 2015-01-21 | 中国石化工程建设有限公司 | Hydro carbons continuous reformer (four) |
| CN204111687U (en) * | 2014-08-21 | 2015-01-21 | 中国石化工程建设有限公司 | Hydro carbons continuous reformer (one) |
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