CN1223292A - Low-pressure combined bed two-stage catalytic reforming process - Google Patents
Low-pressure combined bed two-stage catalytic reforming process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000001833 catalytic reforming Methods 0.000 title claims description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- 238000002407 reforming Methods 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 17
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical compound [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims description 51
- 238000011069 regeneration method Methods 0.000 claims description 33
- 230000008929 regeneration Effects 0.000 claims description 32
- 125000004122 cyclic group Chemical group 0.000 claims description 25
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical group [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000012974 tin catalyst Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 238000007701 flash-distillation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 238000006057 reforming reaction Methods 0.000 abstract description 17
- 230000001172 regenerating effect Effects 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910002846 Pt–Sn Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100039339 Atrial natriuretic peptide receptor 1 Human genes 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 101000961044 Homo sapiens Atrial natriuretic peptide receptor 1 Proteins 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JSOQIZDOEIKRLY-UHFFFAOYSA-N n-propylnitrous amide Chemical compound CCCNN=O JSOQIZDOEIKRLY-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- -1 alkane cycloalkane aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 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
- 238000005070 sampling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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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
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention relates to a combined-bed two-stage catalystic reforming process. It is characterized by that under the condition of low pressure, the raw oil is contacted with platinum-rhenium catalyst in semi-regenerative reforming reaction stage formed from one fixed-bed reactor, then the obtained effluent after reaction is completely fed into the continuous regenerative reaction stage formed from 2-4 moving-bed reactors and one regenerator which are series-connected together, and further is contacted with the platinum-rhenium catalyst, and then the reaction product is undergone the processes of cooling and flash evaporation, and separation into hydrogen-enriched gas and reformate. Said catalyst can be continuously regenerated for circulating use, and said process has no need of separator and reducing valve between two reaction stages, its reaction pressure is less than than 0.95 MPa, and the operating cycle of the catalyst in the fixed-bed can be up to 12 months or longer.
Description
The invention belongs to a kind of catalytic reforming process, more particularly, is under low pressure by fixed-bed reactor and at least two low-pressure combined bed two-stage catalytic reforming process that moving-burden bed reactor constitutes.
Catalytic reforming process is to be raw material with low octane value gasoline or petroleum naphtha, in the presence of catalyzer, make it be converted into the stop bracket gasoline component, this component or process extracting can be produced highly purified petrochemical materials one benzene, toluene and dimethylbenzene light aromaticss such as (hereinafter to be referred as BTX), the while by-product is the hydrogen of cheapness in a large number, can make the hydrogen source of hydrogenation technique process.The reaction that raw material takes place in the presence of catalyzer comprises: the dehydrocyclization reaction of straight-chain paraffin isomerization reaction, hexa-atomic cycloalkanes dehydrogenation reaction, the isomerization reaction of five-ring dehydrating alkanes, alkane, hydrocracking reaction and green coke reaction, the coke laydown of generation is on the surface of catalyzer.The catalyzer that adopts in the catalytic reforming is the dual-function catalyst with metal function and acid function, wherein constitutes hydrogenation one dehydrogenation activity center by the metal constituent element; By carrier A l
2O
3On hydroxyl and the halogen (being generally chlorine) that adds constitute isocracking center one acid sites.
Existing thermo-negative reaction also has thermopositive reaction in the catforming process, based on thermo-negative reaction.For this reason, the reforming process flow process adopts reactors in series, is provided with process furnace between reactor, is used for streams is heated to temperature required.At present mainly contain three kinds at the reforming process of industrial widespread use: semi-regenerative reforming, cyclic reforming, continuous regenerative reforming.Semi-regenerative reforming and cyclic reforming technology all adopt fixed-bed reactor, and continuous regenerative reforming process using moving-burden bed reactor.
The characteristics of semi-regenerative reforming technology are: on-stream activity of such catalysts slowly descends, for keeping certain reformed oil octane value or aromatics yield just need constantly improve temperature of reaction, arrived last stage reaction, temperature of reaction is quite high, cause the reformed oil yield to descend, hydrogen purity and productive rate reduce; For guaranteeing certain production equipment running period, need higher reaction pressure and hydrogen oil molecule than (hereinafter to be referred as hydrogen-oil ratio).At present, the reaction conditions of typical in the world half generative reforming technology is: 480～540 ℃ of temperature of reaction, reaction pressure are 1.5～2.5MPa, and weight space velocity is 1～3 hour
-1, hydrogen-oil ratio is 5～8.
Cyclic reforming technology is to be equipped with a catalyst regeneration system in half generative reforming technology, can regenerate successively catalyzer in each reactor, catalyzer in each reactor can be regenerated separately at any time by switching in the reactive system, and will not stop work by full device.
In the cyclic regeneration reforming process, the reactive system back is ad hoc a catalyst regenerator, and under the CONTINUOUS REFORMER normal operating condition, catalyzer flows between reactor and revivifier, the reclaimable catalyst that reacted is delivered in the revivifier and is regenerated, and the catalyzer after the regeneration is back to reactor.Promptly be in high reactivity, highly selective state all the time at reacting middle catalyst, hydrogen-oil ratio and reaction pressure reduce greatly than half regenerative technology.
Enter the nineties, the refinery is faced with many new problem and requirements: 1, along with the enforcement of stricter environmental protection standard, the unleaded operating severity that will force refinery to improve reformer of gasoline is to produce more stop bracket gasoline component; 2,, also constantly increasing as the reformer treatment capacity of BTX main source along with the increase of market to stop bracket gasoline and light aromatics demand; 3, the refinery hydrogenation technique impels the further expansion of reformation scale to the increase of hydrogen demand.Therefore, be maximum performance activity of such catalysts and selectivity, improve the efficient (being the yield of reformed oil, aromatic hydrocarbons and hydrogen) of catforming process, need constantly to reduce reaction pressure and hydrogen-oil ratio.
USP3,992,465 have proposed two-stage reforming technology for the first time, and this technology is half regeneration reaction section that is made of three fixed-bed reactor for first section, and second section is by a moving-burden bed reactor and the cyclic regeneration conversion zone that revivifier constitutes.Isolate aromatic hydrocarbons (toluene, ethylbenzene, dimethylbenzene) and carbon six cuts from the effusive reformed oil of moving-burden bed reactor through fractionating system, the raffinate (non-aromatics) that obtains behind the carbon six cuts process aromatic hydrocarbons extracting unit is back to moving-burden bed reactor and further carries out aromatization, to produce the more benzene of high yield.The more independent semi-regenerative reforming technology of the hydrogen-oil ratio of this technology and reaction pressure has obvious decline.
Afterwards, France Inst Francais Du Petrole has proposed Dualforming technology, technical process and USP3 in " IFP Solutions for Revamping Catalytic ReformingUnits; 1996 NPRA, AM-96-50 ", 992,465 broadly similars, but cancelled the part that raffinate carbon six alkane return moving-burden bed reactor, simplified technology, reaction pressure is 1.57MPa, and installing running period is 12 months.
American UOP company has also reported similar technology in " Conversion of for Fixed-Bed Reformers to UOP CCRPlatforming Technology; 1989 NPRA, AM-89-47 ", reaction pressure is 1.19MPa, hydrogen-oil ratio is 4.6, and installing running period is 12 months.
Inst Francais Du Petrole has developed Dualforming Plus technology on the basis of Dualforming technology, add a separator after first section fixed bed reaction district, and first section reaction effluent is divided into hydrogen-rich carbon four by separator or carbon (is C below four
4 -) gas phase and carbon five or carbon (is C more than five
5 +) liquid phase, wherein 85% rich hydrogen C
4 -Gas phase is delivered to first section fixed bed reaction district by a recycle compressor; Remaining rich hydrogen C
4 -Gas phase is reduced to required pressure and C through reducing valve
5 +Liquid-phase mixing is delivered to the moving bed reaction district of back.The fixed-bed reactor reaction pressure of front is 2.01MPa, and the continuous generating moving-bed reaction pressure of back is reduced to 0.52MPa, and be 12 months first period fixed-bed reactor running period.
USP5,354,451, USP5,211,838 all is similar two-stage reforming technology, and proposes first section and can adopt two fixed-bed reactor, and two moving-burden bed reactors of second section employing are provided with cooling separator and reducing valve simultaneously between fixed-bed reactor and moving-burden bed reactor.USP5,221,463 separators of having cancelled between the two-stage reforming technology have only kept reducing valve.Guarantee that the front fixed-bed reactor react under elevated pressures, and the moving-burden bed reactor of back is in lower pressure, the minimum differntial pressure of two-stage process is 0.35MPa.The effluent of first section fixed bed separates the moving-burden bed reactor that all enters the back without separator.
USP5,190,638th, another kind of two-stage reforming technology, first section is the cyclic regeneration reforming process, adopts a moving-burden bed reactor; Second section is semi-regenerative reforming technology, adopts three fixed-bed reactor.
USP5,190,639th, form two-stage reforming technology with containing after the two cover half-regeneration reformer parallel connections of three fixed-bed reactor to combine with the cyclic regeneration reforming process of a moving-burden bed reactor.
The two-stage reforming technology of CN87104743A invention is to improve C
5 +Yield and hydrogen yield are purpose, and first section is adopted two fixed-bed reactor, and second section is adopted a moving-burden bed reactor.First section reacted effluent all enters second section moving bed reaction district, replenishes new hydrogen at this simultaneously.This technological reaction pressure is 1.0MPa, and the hydrogen-oil ratio in first section fixed bed reaction district is 3, and moving bed reaction district hydrogen-oil ratio is 6.Be 690～840 hours the running period of fixed bed catalyst.
In sum, the main technique form of two-stage reforming technology of the prior art is that half generative reforming conversion zone adopts two to three fixed-bed reactor, and cyclic regeneration reforming reaction section adopts one to two moving-burden bed reactor, and reaction pressure is 1.19～1.57MPa.Or be to improve the yield of reformed oil and hydrogen and the running period that increases catalyzer in the fixed-bed reactor, behind half generative reforming conversion zone, increase separator and/or reducing valve, guarantee that half generative reforming conversion zone is in elevated pressures, and cyclic regeneration reforming reaction section is in lower pressure.
The objective of the invention is to provide on the basis of existing technology the low-pressure combined bed two-stage catalytic reforming process of a kind of low hydrogen/gasoline ratio (3.0～4.5), low reaction pressure (1.0MPa is following).
Technology provided by the invention is: stock oil is contacted with catalyzer in the half generative reforming conversion zone that is made of fixed-bed reactor, reacted effluent all enters in the cyclic regeneration conversion zone that is made of two to four moving-burden bed reactors and the series connection of revivifier and further contacts cooling, separating obtained product with catalyzer.
Technology provided by the invention is so concrete enforcement: stock oil enters first section half generative reforming conversion zone, and this Duan Youyi process furnace and a fixed-bed reactor series connection constitute; The effluent that comes out from first section half generative reforming conversion zone all enters second section cyclic regeneration reforming reaction section, and this section is made of two to four moving-burden bed reactors and a revivifier series connection, and a process furnace is arranged before each moving-burden bed reactor; The product that comes out from second section cyclic regeneration reforming reaction section is divided into gas-liquid two-phase after cooling, flash distillation: recycle after a hydrogen-rich gas part is boosted, another part removes downstream unit as one of product, liquid phase stream is delivered to the downstream fractionating system, removes the product jar as reformed oil after stable; Catalyzer in second section moving-bed recycles after revivifier regeneration.
Stock oil used in the present invention is one or more the mixture among the catalytic cracking heavy naphtha that is selected from behind coking naphtha behind virgin naphtha, the hydrogenation, visbreaking petroleum naphtha, the hydrogenation; Before stock oil enters combined low-pressure bed technological reaction, all need make with extra care in the raw materials pretreatment system, to remove impurities in raw materials, the especially sulphur in the raw material, nitrogen, arsenic and heavy metal.
Except that the temperature of reaction of fixed bed and moving-burden bed reactor is respectively 460～510 ℃ and 500～540 ℃, all the other processing condition are identical in two sections, for: reaction pressure 0.3～0.9MPa, hydrogen-oil ratio 3.0～4.5, weight hourly space velocity is 1～4 hour
-1
Catalyzer in the fixed-bed reactor is the difunctional platinum-rhenium catalyst with high reactivity, highly selective and good stability, the method preparation that preferred platinum-rhenium catalyst provides according to CN1147536A, (with the butt aluminum oxide is benchmark to its composition, heavy %) is: platinum 0.10～1.00, rhenium 0.10～3.00, titanium 0.01～0.15, chlorine 0.50～3.00, surplus be γ-Al
2O
3Carrier.The Intake Quantity of platinum-rhenium catalyst accounts for 10～20 heavy % of catalyzer general reserve in the reaction system.
Catalyzer in several moving-burden bed reactors is the difunctional platinum-tin catalyst of high reactivity, highly selective, the method preparation that preferred platinum-tin catalyst provides according to CN1150169A, (with the butt aluminum oxide is benchmark to its composition, heavy %) is: platinum 0.10～1.00, tin 0.10～1.00, titanium 0.01～0.20, chlorine 0.50～2.50, carrier are γ-Al
2O
3The Intake Quantity of catalyzer accounts for 80～90 heavy % of general reserve in the reaction system.
Below in conjunction with accompanying drawing technology provided by the present invention is given further instruction.
Accompanying drawing 1 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and two moving-beds.
First section of this technological process is the half generative reforming conversion zone that is made of process furnace [11] and fixed-bed reactor [13], and fixed-bed reactor are equipped with difunctional platinum-rhenium catalyst in [13]; Second section is by process furnace [15], [19], and the cyclic regeneration reforming reaction section that moving-burden bed reactor [17], [22] and revivifier [23] constitute is equipped with difunctional platinum-tin catalyst in moving-burden bed reactor [17], [22].
Stock oil after refining through pipeline [1] with enter process furnace [11] after circulating hydrogen from pipeline [2] mixes, be heated to desired reaction temperature at this, enter fixed-bed reactor [13] through pipeline [12] and react.So far, reformer feed has been finished first section reforming reaction in the combined low-pressure bed catalytic reforming process.
All enter second section from first section effluent, the effluent of fixed-bed reactor [13] enters process furnace [15] through pipeline [14], enters moving-burden bed reactor [17] by pipeline [16] after being heated to required temperature of reaction.The effluent that comes out from reactor [17] enters process furnace [19] from pipeline [18], is heated to desired reaction temperature and enters moving-burden bed reactor [22] through pipeline [20].So far, the reforming reaction in second section moving-burden bed reactor finishes.
Deliver to cold exchange device [7] from the effusive product of reactor [22] through pipeline [25], cooled product enters separator [5] through pipeline [6].In separator [5], logistics is divided into gas-liquid two-phase through flash distillation: the top is a hydrogen-rich gas, wherein a part after pipeline [4] enters recycle compressor [3] compression, through pipeline [2] with go first section after refining stock oil from pipeline [1] mixes; Another part hydrogen-rich gas as hydrogen product after pipeline [8] enters supercharger [10], dehydrogenation gas purification system or directly remove downstream unit, the logistics of separator bottom liquid phases is delivered to the downstream fractionating system through pipeline [9], removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
Be provided with a revivifier [23] in moving-burden bed reactor [17], [22] back, used platinum-tin catalyst in second section moving-bed is carried out cyclic regeneration.After the reaction beginning, the carbon deposit reclaimable catalyst that moving-burden bed reactor [22] bottom emits enters regeneration in the revivifier [23] by catalyzer lift line [26], catalyzer after the regeneration is delivered in the reactor [17] through pipeline [24], original catalyzer is by catalyzer lift line [21] dereaction device [22] in the reactor [17], catalyzer is cyclic regeneration so continuously, makes the catalyzer in reactor [17], [22] remain high activity and selectivity.
Accompanying drawing 2 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and three moving-beds.
First section of this technological process is the half generative reforming conversion zone that is made of process furnace [11] and fixed-bed reactor [13], and fixed-bed reactor are equipped with difunctional platinum-rhenium catalyst in [13]; Second section is by process furnace [15], [19], [28], and the cyclic regeneration reforming reaction section that moving-burden bed reactor [17], [22], [31] and revivifier [23] constitute is equipped with difunctional platinum-tin catalyst in moving-burden bed reactor [17], [22], [31].
Stock oil after refining through pipeline [1] with enter process furnace [11] after circulating hydrogen from pipeline [2] mixes, be heated to desired reaction temperature at this, enter fixed-bed reactor [13] through pipeline [12] and react.So far, reformer feed has been finished first section reforming reaction in the combined low-pressure bed catalytic reforming process.
All enter second section from first section effluent, the effluent of fixed-bed reactor [13] enters process furnace [15] through pipeline [14], enters moving-burden bed reactor [17] by pipeline [16] after being heated to required temperature of reaction.The logistics of coming out from reactor [17] enters process furnace [19] from pipeline [18], is heated to desired reaction temperature and enters moving-burden bed reactor [22] through pipeline [20].The logistics of coming out from reactor [22] enters process furnace [28] from pipeline [27], is heated to desired reaction temperature and enters moving-burden bed reactor [31] through pipeline [29].So far, the reforming reaction in second section moving-burden bed reactor finishes.
Deliver to cold exchange device [7] from the effusive product of reactor [31] through pipeline [32], cooled product enters separator [5] through pipeline [6].In separator [5], logistics is divided into gas-liquid two-phase through flash distillation: the top is a hydrogen-rich gas, wherein a part after pipeline [4] enters recycle compressor [3] compression, through pipeline [2] with go first section after refining stock oil from pipeline [1] mixes; Another part hydrogen-rich gas as hydrogen product after pipeline [8] enters supercharger [10], dehydrogenation gas purification system or directly remove downstream unit, the logistics of separator bottom liquid phases is delivered to the downstream fractionating system through pipeline [9], removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
Be provided with a revivifier [23] in moving-burden bed reactor [17], [22], [31] back, used platinum-tin catalyst in second section moving-bed is carried out cyclic regeneration.After the reaction beginning, the carbon deposit reclaimable catalyst that moving-burden bed reactor [31] bottom emits enters regeneration in the revivifier [23] by catalyzer lift line [33], catalyzer after the regeneration is delivered in the reactor [17] through pipeline [24], original catalyzer is by catalyzer lift line [21] dereaction device [22] in the reactor [17], original catalyzer is by catalyzer lift line [30] dereaction device [31] in the reactor [22], catalyzer is cyclic regeneration so continuously, makes the catalyzer in reactor [17], [22], [31] remain high activity and selectivity.
Accompanying drawing 3 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and four moving-beds.
First section of this technological process is the half generative reforming conversion zone that is made of process furnace [11] and fixed-bed reactor [13], and fixed-bed reactor are equipped with difunctional platinum-rhenium catalyst in [13]; Second section is by process furnace [15], [19], [28], [34], the cyclic regeneration reforming reaction section that moving-burden bed reactor [17], [22], [31], [36] and revivifier [23] constitute is equipped with difunctional platinum-tin catalyst in moving-burden bed reactor [17], [22], [31], [36].
Stock oil after refining through pipeline [1] with enter process furnace [11] after circulating hydrogen from pipeline [2] mixes, be heated to desired reaction temperature at this, enter fixed-bed reactor [13] through pipeline [12] and react.So far, reformer feed has been finished first section reforming reaction in the combined low-pressure bed catalytic reforming process.
All enter second section from first section effluent, the effluent of fixed-bed reactor [13] enters process furnace [15] through pipeline [14], enters moving-burden bed reactor [17] by pipeline [16] after being heated to required temperature of reaction.The logistics of coming out from reactor [17] enters process furnace [19] from pipeline [18], is heated to desired reaction temperature and enters moving-burden bed reactor [22] through pipeline [20].The logistics of coming out from reactor [22] enters process furnace [28] from pipeline [27], is heated to desired reaction temperature and enters moving-burden bed reactor [31] through pipeline [29].The logistics of coming out from reactor [31] enters process furnace [34] from pipeline [32], is heated to desired reaction temperature and enters moving-burden bed reactor [36] through pipeline [35].So far, the reforming reaction in second section moving-burden bed reactor finishes.
Deliver to cold exchange device [7] from the effusive product of reactor [36] through pipeline [37], cooled product enters separator [5] through pipeline [6].In separator [5], logistics is divided into gas-liquid two-phase through flash distillation: the top is a hydrogen-rich gas, wherein a part after pipeline [4] enters recycle compressor [3] compression, through pipeline [2] with go first section after refining stock oil from pipeline [1] mixes; Another part hydrogen-rich gas as hydrogen product after pipeline [8] enters supercharger [10], dehydrogenation gas purification system or directly remove downstream unit, the logistics of separator bottom liquid phases is delivered to the downstream fractionating system through pipeline [9], removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
Be provided with a revivifier [23] in moving-burden bed reactor [17], [22], [31], [36] back, used platinum-tin catalyst in second section moving-bed is carried out cyclic regeneration.After the reaction beginning, the carbon deposit reclaimable catalyst that moving-burden bed reactor [36] bottom emits enters regeneration in the revivifier [23] by catalyzer lift line [38], catalyzer after the regeneration is delivered in the reactor [17] through pipeline [24], original catalyzer is by catalyzer lift line [21] dereaction device [22] in the reactor [17], original catalyzer is by catalyzer lift line [30] dereaction device [31] in the reactor [22], original catalyzer is by catalyzer lift line [39] dereaction device [36] in the reactor [31], catalyzer is cyclic regeneration so continuously, makes reactor [17], [22], [31], [36] catalyzer in remains high activity and selectivity.
The invention has the advantages that: reaction pressure is lower than 0.95MPa, and separator or reducing valve are not set between the two-stage process, and the effluent of fixed-bed reactor all enters the moving bed reaction section without separating; The load of revivifier be can reduce simultaneously, the treatment capacity of existing apparatus and the severity of reaction improved.
Accompanying drawing 1 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and two moving-beds.
Accompanying drawing 2 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and three moving-beds.
Accompanying drawing 3 illustrates the flow process of the low-pressure combined bed two-stage catalytic reforming process that is made of a fixed bed and four moving-beds.
Each numbering is described as follows in the accompanying drawing: [13] are fixed-bed reactor, [17], [22], [31], [31], [36] are moving-burden bed reactor, [11], [15], [19], [28], [34] are process furnace, [23] be revivifier, [7] be cold exchange device, [5] are separator, and [10] are supercharger, [3] be recycle compressor, all the other numberings are pipeline.Heavy line in the accompanying drawing is represented the reactant flow pipeline, and fine line is represented the hydrogen-rich gas pipeline, and dotted line is represented the catalyzer lift line.
The following examples will give further instruction to technology provided by the invention, but not thereby limiting the invention.
It (is Low Pressure Combined BedReforming that embodiment adopts reforming process for combined low-pressure bed, hereinafter to be referred as LPCBR), carry out on the adiabatic reformation pilot plant of four pipes, fixed-bed reactor use platinum-rhenium catalyst, and moving-burden bed reactor all uses platinum-tin catalyst; Comparative Examples adopts continuous regenerative reforming technology (being Continuous Catalytic Reforming, C R), and the CCR technological test adopts three or four moving-burden bed reactor series connection, and catalyzer all adopts platinum-tin catalyst.Reforming raw oil is a petroleum naphtha, and its main character sees Table 1.The reaction conditions of embodiment, Comparative Examples and test-results see Table 2 with table 3, the octane value in the table is the not clean research octane number (RON) of leading, i.e. RONC.
In the LPCBR technology that constitutes by a fixed bed and three moving-beds, stock oil A after the pre-hydrotreatment enters first section, this section is by a process furnace and the half generative reforming conversion zone that the fixed-bed reactor series connection constitutes, all enter second section from first section effluent, this second section is by three moving-burden bed reactors and the cyclic regeneration reforming reaction section that the revivifier series connection constitutes, and a process furnace is arranged before each moving-burden bed reactor.
Reaction conditions is: reaction pressure 0.7MPa, hydrogen-oil ratio 3.6, weight hourly space velocity 2.0 hours
-1The fixed-bed reactor above-mentioned platinum-rhenium catalyst of packing into, Intake Quantity account for 16.4 heavy % of reaction system general reserve, 480 ℃ of temperature of reaction; The moving-burden bed reactor above-mentioned platinum-tin catalyst of packing into, Intake Quantity account for 83.6 heavy % of reaction system general reserve, 525 ℃ of temperature of reaction.
The product that comes out from second section cyclic regeneration reforming reaction section is divided into gas-liquid two-phase after cooling, flash distillation: recycle after a hydrogen-rich gas part is boosted, emptying after another part metering sampling analysis, liquid phase stream is as the reformed oil product, and test-results sees Table 2.
Similar to Example 1, stock oil is A, and in the LPCBR technology that is made of a fixed bed and three moving-beds, reaction conditions is: reaction pressure 0.30MPa, hydrogen-oil ratio 3.9, weight hourly space velocity 2.0 hours
-1The temperature of reaction of fixed bed and moving-burden bed reactor is respectively 480 ℃ and 519 ℃, and the Intake Quantity of two-stage catalytic agent is with embodiment 1, and test-results sees Table 2.
Comparative Examples 1
In the CCR technology that is made of three moving-burden bed reactor series connection, stock oil is A, and reaction conditions is: reaction pressure 0.70MPa, hydrogen-oil ratio 4.5, weight hourly space velocity 1.6 hours
-1, 525 ℃ of temperature of reaction.Test-results sees Table 2.Data show in the table 2, compare with Comparative Examples 1, and under identical reaction pressure and temperature of reaction, the weight hourly space velocity of embodiment 1 reaches 2.0 hours
-1Be that treatment capacity has improved 25%.
Comparative Examples 2
In the CCR technology that is made of three moving-burden bed reactor series connection, stock oil is A, and reaction conditions is: reaction pressure 0.70MPa, hydrogen-oil ratio 3.8, weight hourly space velocity 2.0 hours
-1, 535 ℃ of temperature of reaction.Test-results sees Table 2.Data show in the table 2, and in CCR technology, the treatment capacity of Comparative Examples 2 has improved 25% than Comparative Examples 1, and for obtaining the result identical with Comparative Examples 1, temperature of reaction reaches 535 ℃.And in LPCBR technology, embodiment 1 had increased fixed-bed reactor before CCR technology, and the moving-bed weight hourly space velocity also rises to 2.0 hours
-1, for guaranteeing the test-results of Comparative Examples 1, temperature of reaction only needs 525 ℃.On the other hand,, the CCR technological transformation of three moving-beds is reduced more than 15% for LPCBR technology can make the coking amount of movable bed catalyst, reduced the load of existing revivifier from the coking situation of moving-burden bed reactor platinum-tin catalyst.As seen, be LPCBR technology with the CCR technological transformation that has three moving-beds now, can improve the treatment capacity and the reaction severity of device.The reaction pressure of LPCBR technology is 0.30MPa among the embodiment 2, compare with embodiment 1, under the situation that obtains identical reformed oil octane value, the yield of reformed oil has improved 2.6 percentage points, aromatics yield has improved 4.2 percentage points, and the temperature of reaction of moving-burden bed reactor has reduced by 6 ℃.Simultaneously with this understanding, the expection of fixed bed reactor catalyst still can reach 12 months running period.
In the LPCBR technology that constitutes by a fixed bed and four moving-beds, stock oil B after the pre-hydrotreatment enters first section, this section is by a process furnace and the half generative reforming conversion zone that the fixed-bed reactor series connection constitutes, all enter second section from first section effluent, this second section is by four moving-burden bed reactors and the cyclic regeneration reforming reaction section that the revivifier series connection constitutes, and a process furnace is arranged before each moving-burden bed reactor.
Reaction conditions is: reaction pressure 0.88MPa, hydrogen-oil ratio 4.5, weight hourly space velocity 1.16 hours
-1The fixed-bed reactor above-mentioned platinum-rhenium catalyst of packing into, Intake Quantity account for 15.0 heavy % of reaction system general reserve, 480 ℃ of temperature of reaction; The moving-burden bed reactor above-mentioned platinum-tin catalyst of packing into, Intake Quantity account for 85.0 heavy % of reaction system general reserve, 515.1 ℃ of temperature of reaction.Test-results sees Table 3.
Comparative Examples 3
In the CCR technology that is made of four moving-burden bed reactor series connection, stock oil is B, and reaction conditions is: reaction pressure 0.88MPa, hydrogen-oil ratio 4.5, weight hourly space velocity 1.16 hours
-1, 522.0 ℃ of temperature of reaction, test-results sees Table 3.Data show in the table 3, under identical reaction depth (identical product RONC) and treatment capacity, after the CCR technological transformation of existing four moving-beds become LPCBR technology among the embodiment 3, moving-bed partial reaction temperature has reduced by 6.9 ℃, the reformed oil yield has improved 0.2 percentage point, and the coking amount in the moving-burden bed reactor has descended 23%, greatly reduces the load of revivifier, for precondition is provided the work-ing life that increases device inlet amount (promptly improving treatment capacity) and catalyzer.
Table 1
| Stock oil | ????A | ????B |
| Density (20 ℃), kg/cm 3Boiling range (ASTM-D86); ℃ initial boiling point 50% end point of distillation group composition, heavy % alkane cycloalkane aromatic hydrocarbons | ????727.2 ????88 ????109 ????149 ????55.5 ????41.3 ????3.2 | ????727.4 ????86 ????109 ????151 ????58.6 ????37.8 ????3.6 |
Table 2
| | Embodiment | 1 | | Comparative Examples 1 | Comparative Examples 2 |
| The catalyst agent ratio of packing in technological reaction condition fixed bed/moving-bed, the m% reaction pressure, MPa hydrogen-oil ratio weight hourly space velocity, hour -1The fixed bed reaction temperature, ℃ moving bed reaction temperature, ℃ test-results generates oily yield, heavy % hydrogen yield, heavy % generates oily octane value (RONC) aromatics yield, heavy % expects running period, month platinum-tin catalyst carbon deposit, heavy % | LPCBR Pt-Re/Pt-Sn 16.4/83.6 0.70 3.6 2.0 480 525 84.6 4.2 101.0 64.1 24/ continuous benchmark-15.3 | LPCBR Pt-Re/Pt-Sn 16.4/83.6 0.30 3.9 2.0 480 519 87.2 4.3 101.2 68.3 12/ continuously- | CCR Pt-Sn-0.70 4.5 1.6-525 84.2 4.2 101.2 63.4 continuously- | CCR Pt-Sn-0.70 3.8 2.0-535 84.5 4.2 101.2 63.8 continuous benchmark |
Table 3
| The | Embodiment | 3 | Comparative Examples 3 |
| The catalyst agent ratio of packing in technological reaction condition fixed bed/moving-bed, the m% reaction pressure, MPa hydrogen-oil ratio weight hourly space velocity, hour -1The fixed bed reaction temperature, ℃ moving bed reaction temperature, ℃ test-results generates oily yield, heavy % generates oily octane value (RONC) hydrogen yield, heavy % expects running period, month platinum-tin catalyst carbon deposit, heavy % | LPCBR Pt-Re/Pt-Sn 15.0/85.0 0.88 4.5 1.16 480 515.1 83.1 101.8 3.3 30/ continuous benchmark-23 | CCR Pt-Sn-0.88 4.5 1.16-522.0 82.9 102.0 3.4 continuous benchmark |
Claims (10)
1, a kind of combined bed two-stage catalytic reforming process, it is characterized in that under low pressure making stock oil in the half generative reforming conversion zone that constitutes by fixed-bed reactor, to contact with catalyzer, reacted effluent all enters in the cyclic regeneration conversion zone that is made of two to four moving-burden bed reactors and the series connection of revivifier and further contacts cooling, separating obtained product with catalyzer.
2,, it is characterized in that described stock oil is one or more the mixture among the catalytic cracking heavy naphtha that is selected from behind coking naphtha behind virgin naphtha, the hydrogenation, visbreaking petroleum naphtha, the hydrogenation according to the technology of claim 1.
3, according to the technology of claim 1, it is characterized in that reaction pressure is 0.3～0.9MPa in two sections, hydrogen oil molecule ratio is 3.0～4.5, weight hourly space velocity is 1～4 hour
-1
4,, it is characterized in that the temperature of reaction of fixed bed and moving-burden bed reactor is respectively 460～510 ℃ and 500～540 ℃ according to the technology of claim 1.
5, according to the technology of claim 1, it is characterized in that the catalyzer in the described fixed-bed reactor is platinum-rhenium catalyst, the Intake Quantity of platinum-rhenium catalyst accounts for 10～20 heavy % of catalyzer general reserve in the reaction system.
6,, it is characterized in that before the described fixed-bed reactor a placed in-line with it process furnace being arranged according to the technology of claim 1.
7, according to the technology of claim 1, it is characterized in that the catalyzer in the described moving-burden bed reactor is a platinum-tin catalyst, the Intake Quantity of platinum-tin catalyst accounts for 80～90 heavy % of reaction system general reserve.
8,, it is characterized in that before described each moving-burden bed reactor a placed in-line with it process furnace being arranged all according to the technology of claim 1.
9, according to the technology of claim 1, it is characterized in that after cooling, flash distillation, being divided into gas-liquid two-phase: recycle after a hydrogen-rich gas part is boosted from the product that last moving-burden bed reactor comes out, another part removes downstream unit, liquid phase stream is delivered to the downstream fractionating system, removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
10,, it is characterized in that recycling after catalyzer in the described moving-bed is regenerated in revivifier according to the technology of claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117280.6A CN1111584C (en) | 1998-08-14 | 1998-08-14 | Low-pressure combined bed two-stage catalytic reforming process |
| DE19938036A DE19938036A1 (en) | 1998-08-14 | 1999-08-12 | Low pressure combined bed two stage catalytic reforming process |
| IT1999MI001818A ITMI991818A1 (en) | 1998-08-14 | 1999-08-12 | LOW PRESSURE CATALYTIC REFORMING PROCESS WITH COMBINATION OF TWO-ZONE REACTOR |
| JP11230146A JP2000063852A (en) | 1998-08-14 | 1999-08-16 | Low pressure combined bed two-zone catalytic reforming process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117280.6A CN1111584C (en) | 1998-08-14 | 1998-08-14 | Low-pressure combined bed two-stage catalytic reforming process |
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| CN1223292A true CN1223292A (en) | 1999-07-21 |
| CN1111584C CN1111584C (en) | 2003-06-18 |
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| CN98117280.6A Expired - Lifetime CN1111584C (en) | 1998-08-14 | 1998-08-14 | Low-pressure combined bed two-stage catalytic reforming process |
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| Country | Link |
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| JP (1) | JP2000063852A (en) |
| CN (1) | CN1111584C (en) |
| DE (1) | DE19938036A1 (en) |
| IT (1) | ITMI991818A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333051C (en) * | 2004-06-29 | 2007-08-22 | 中国石油化工股份有限公司 | Parallel-flow catalytic reforming processing method for multiple movable bed reactors |
| CN105621357A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Methane-reforming and hydrogen-production method |
| CN108611119A (en) * | 2016-12-12 | 2018-10-02 | 河北新启元能源技术开发股份有限公司 | Naphtha catalytic reforming unit and its catalytic reforming process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597519B (en) * | 2008-06-04 | 2013-02-06 | 北京金伟晖工程技术有限公司 | System and method for reforming naphtha productive aromatic hydrocarbon |
-
1998
- 1998-08-14 CN CN98117280.6A patent/CN1111584C/en not_active Expired - Lifetime
-
1999
- 1999-08-12 DE DE19938036A patent/DE19938036A1/en not_active Withdrawn
- 1999-08-12 IT IT1999MI001818A patent/ITMI991818A1/en unknown
- 1999-08-16 JP JP11230146A patent/JP2000063852A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333051C (en) * | 2004-06-29 | 2007-08-22 | 中国石油化工股份有限公司 | Parallel-flow catalytic reforming processing method for multiple movable bed reactors |
| CN105621357A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Methane-reforming and hydrogen-production method |
| CN105621357B (en) * | 2014-10-27 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of methane reforming hydrogen production process |
| CN108611119A (en) * | 2016-12-12 | 2018-10-02 | 河北新启元能源技术开发股份有限公司 | Naphtha catalytic reforming unit and its catalytic reforming process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111584C (en) | 2003-06-18 |
| JP2000063852A (en) | 2000-02-29 |
| ITMI991818A0 (en) | 1999-08-12 |
| DE19938036A1 (en) | 2000-04-27 |
| ITMI991818A1 (en) | 2001-02-12 |
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