CN106221786A - A kind of method for transformation of Petroleum - Google Patents
A kind of method for transformation of Petroleum Download PDFInfo
- Publication number
- CN106221786A CN106221786A CN201510296090.8A CN201510296090A CN106221786A CN 106221786 A CN106221786 A CN 106221786A CN 201510296090 A CN201510296090 A CN 201510296090A CN 106221786 A CN106221786 A CN 106221786A
- Authority
- CN
- China
- Prior art keywords
- carbon number
- product
- reaction
- molecular sieve
- stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application discloses the method for transformation of a kind of Petroleum, naphtha catalytic cracking is combined with low-carbon alkanes steam pyrolysis, High-carbon alkane and higher olefins catalytic pyrolysis, preparing low-carbon olefins, light aromatics and high-knock rating gasoline.The method significantly improves the productivity of high value products, reduces the productivity of low value products；Simultaneously as major part reactant is converted in the catalytic pyrolysis that temperature is relatively low, energy consumption can be reduced generally.
Description
Technical field
The application relates to a kind of Petroleum conversion process, belongs to petrochemical industry.
Background technology
The chemical products such as Petroleum high-temperature vapor cracking ethylene preparation, propylene are that a huge petrochemical industry is produced
Industry.Have every year and count the Petroleum with hundred million tons for this process.Steam pyrolysis technology through for many years send out
Exhibition has reached high level, and its conversion ratio is high, and through primary first-order equation, the productivity of product is the most permissible
Reach higher level.Its shortcoming is poor selectivity, has substantial amounts of methane to generate in product, reaction temperature
Degree height, energy consumption is high.In view of this, people are developing producing olefin hydrocarbon by catalytic pyrolysis technology always in decades,
Cracking producing light olefins for Petroleum He other suitable feedstock.
The feature of catalytic pyrolysis is that reaction temperature is relatively low, and selectivity is high.But its conversion to lower carbon number hydrocarbons
Rate is low.At present, when the technology of report is with cycloalkyl and intermediate base Petroleum for raw material, its conversion per pass
The products collection efficiency produced, is not enough to compete with hydrothermal cracking.This is also that deep catalytic cracking technology develops
A lot of years, and fail so far to realize the most former of producing olefin hydrocarbon by catalytic pyrolysis of naphtha technology commercialization application
Cause.In addition using molecular sieve is the catalyst of active component, at reaction conditions, owing to high-temperature water steams
Gas makes framework of molecular sieve aluminum gradually deviate from, and catalyst activity is gradually reduced, thus causes reactant to convert
The technical barrier that rate declines the most does not solves.
Summary of the invention
An aspect according to the application, it is provided that the method for transformation of a kind of Petroleum, by by stone brain
Catalytic pyrolysis and the high-temperature vapor cracking technology of oil combine, preparing low-carbon olefins, aromatic hydrocarbons and Gaoxin
Alkane value gasoline.The method significantly improves the productivity of high value products, reduces the product of low value products
Rate；Simultaneously as major part reactant is converted, totally in the catalytic pyrolysis that temperature is relatively low
On can reduce energy consumption.
The method for transformation of described Petroleum, it is characterised in that at least comprise the following steps:
A) charging containing Petroleum is passed through the first reaction zone, 580 DEG C～the reaction temperature of 700 DEG C
Down with the catalyst haptoreaction containing molecular sieve, product is isolated to stream I and product I；
B) gained stream I in water vapour and step a) is passed through second reaction zone, at 780 DEG C～870 DEG C
Reaction temperature under carry out steam pyrolysis reaction, obtain product I II after reaction；
Described stream I includes the alkane that carbon number is 2～5；
Described product I include aromatic hydrocarbons that alkene that carbon number is 2～12, carbon number are 6～12 and
Carbon number is the alkane of 6～12；
Described product I II includes the virtue that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Hydrocarbon.
Obtain stream I and product I after the product of described first reaction zone is separated, remaining be
By-product I.By-product I mainly contains hydrogen and methane.
Product I II is obtained after the product of described second reaction zone is separated, remaining for by-product
III.By-product III mainly contains hydrogen and methane.
During in described product I, carbon number is the alkene of 2～12, mainly carbon number is 2～4
Low-carbon alkene.During in described product I, carbon number is the aromatic hydrocarbons of 6～12, mainly carbon number is
The aromatic hydrocarbons of 6～8.During in described product I, carbon number is the alkane of 6～12, mainly isoparaffin and
Cycloalkane containing side chain.Main Components in described product I is respectively provided with higher economic worth.Institute
State the low-carbon alkene that carbon number in product I is 2～4 and the aromatic hydrocarbons that carbon number is 6～8 can be as weight
The industrial chemicals wanted；Isoparaffin in described product I, the cycloalkane containing side chain, carbon number are
The aromatic hydrocarbons of 9～12 may be incorporated for producing high-knock rating gasoline.The present processes can make raw material stone brain
Oil reaction obtains more above-mentioned high value products.
The reaction characteristics of catalytic pyrolysis is that reaction temperature is relatively low, selectivity good, but to carbon number is
The alkane conversion of 2～5 is low；The feature of steam pyrolysis is that reaction-ure conversion-age is high, but selectivity is relatively
Low, simultaneous reactions temperature is high, energy consumption is high.The application has combined both cleavage methods selectively
Come, respectively use two kinds of cleavage methods advantage aspect, make reactant first in the first reaction zone in relatively
Carrying out catalytic cracking reaction under low reaction temperature, major part material height is selectively generating product, will
The component of remaining applicable steam pyrolysis carries out steam pyrolysis in second reaction zone, and product is defeated
Go out or store.Wherein, carbon number is the alkane of 2～5, including ethane, propane, butane and pentane,
It is difficult to effectively convert in catalytic cracking reaction, and economic worth is the lowest simultaneously, but in steam pyrolysis
Reaction but can show conversion advantage, especially selectivity aspect.Isolate the anti-of the first reaction zone
Answering carbon number in product is the alkane of 2～5, carries out steam pyrolysis, and its product is mainly low carbene
Hydrocarbon and light aromatics, economic worth is much larger than the alkane that carbon number is 2～5.Simultaneously because first is anti-
The alkane total amount answering carbon number in district's product to be 2～5 is less, therefore second reaction zone steam
The energy consumption that cracking needs is the most little.In sum, for steam during the application changes prior art
The understanding of application aspect of cracking, only the most relatively low to economic worth, yield is few, be difficult to be catalyzed
The alkane component that carbon number is 2～5 converted carries out steam pyrolysis, increase only a small amount of energy consumption
In the case of, component the lowest for economic worth is largely converted into the product that economic worth is the highest, uses
It is more suitable for and low value component is converted into high value component by method more efficiently, the most significantly carry
High economic advantages.
In the application, " alkane " includes alkane and cycloalkane.
In the application, the low-carbon alkene of 2～4 " carbon number be " include ethylene, propylene, 1-butylene,
2-butylene, isobutene., 1,3-butadiene, referred to as low-carbon alkene.
In the application, the aromatic hydrocarbons of 6～8 " carbon number be ", it is called for short light aromatics or BTX, including benzene
(Benzene), toluene (Toluene) and dimethylbenzene (Xylene).
In the application, " Petroleum " includes full fraction naphtha and/or part fraction naphtha, typical case
Part fraction naphtha include the Petroleum (being abbreviated as IBP-150 DEG C), just of initial boiling point to 150 DEG C
Evaporate some the Petroleum (being abbreviated as IBP-180 DEG C) to 180 DEG C.
Another aspect according to the application, it is provided that the method for transformation of a kind of Petroleum, by by stone
Catalytic pyrolysis and the high-temperature vapor cracking technology of cerebrol combine, preparing low-carbon olefins and aromatic hydrocarbons.Should
Method significantly improves the productivity of high value products, reduces the productivity of low value products；Meanwhile, by
Converted in the catalytic pyrolysis that temperature is relatively low in major part reactant, energy can be reduced generally
Consumption.
The method for transformation of described Petroleum, it is characterised in that at least comprise the following steps:
A) charging containing Petroleum is passed through the first reaction zone, 580 DEG C～the reaction temperature of 700 DEG C
Lower with the catalyst haptoreaction containing molecular sieve, after reaction through isolated stream I, stream I I,
Product I I；
B) gained stream I in water vapour and step a) is passed through second reaction zone, at 780 DEG C～870 DEG C
Reaction temperature under carry out steam pyrolysis reaction, obtain product I II after reaction；
C) step a) gained logistics II is returned to described first reaction zone；
Described stream I includes the alkane that carbon number is 2～5；
Described stream I I includes the alkene that alkane that carbon number is 6～12, carbon number are 5～12；
Described product I I includes the virtue that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Hydrocarbon；
Described product I II includes the virtue that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Hydrocarbon.
The product of described first reaction zone is isolated to stream I, stream I I and product I I, remaining
Under for by-product II.By-product II mainly contains hydrogen, methane and the carbon number aromatic hydrocarbons more than 8.
Described carbon number be 2～4 low-carbon alkene, carbon number be 6～8 aromatic hydrocarbons be respectively provided with higher
Economic worth, all can be as important industrial chemicals, the present processes can make raw material Petroleum
Reaction obtains more above-mentioned high value products.
In the product of the first reaction zone catalytic pyrolysis, carbon number not less than 6 alkane and carbon former
The subnumber alkene not less than 5, it is also possible to be further converted to be worth higher low-carbon alkene and lightweight virtue
Hydrocarbon, but due to the carbon number in molecule more time, carry out steam pyrolysis reaction being generally selected property relatively
Low (relative to catalytic pyrolysis), is therefore not appropriate for steam pyrolysis.As it was previously stated, the application handle
Catalytic pyrolysis and steam pyrolysis combine, and use the advantage aspect of two kinds of cleavage methods respectively, make
First reactant carries out catalytic cracking reaction under relatively low reaction temperature in the first reaction zone, major part
Material height is selectively generating the product of high value, in remaining product, by applicable catalysis
The material of cracking is re-delivered to catalytic reactor freshening, and the material of applicable steam pyrolysis is carried out height
Temperature steam cracks, reactor product output or storage.In a kind of embodiment of the application, first
After the catalytic pyrolysis of reaction zone through separate, wherein carbon atom number be 2～5 alkane carry out steam pyrolysis
Outward, also alkane and the alkene that carbon number is 5～12 that carbon number is 6～12 are returned the first reaction
District proceeds catalytic pyrolysis, is converted into the higher low-carbon alkene of value and light aromatics.Therefore, originally
Application changes in prior art for freshening and the understanding of the application aspect of steam pyrolysis, has selection
Ground is only the lowest to economic worth, yield is few, be difficult to the alkane group that carbon number is 2～5 of catalyzed conversion
Part carries out steam pyrolysis, in the case of increase only a small amount of energy consumption, by group the lowest for economic worth
Part is largely converted into the product that economic worth is the highest；It is the most only 6～12 to carbon number
Alkane and the alkene that carbon number is 5～12 carry out catalytic pyrolysis freshening, low by applicable catalytic pyrolysis
Valuable product is further converted to be worth higher product.The technical scheme of the application, uses for not
Component with response characteristic carries out the technological means of Different treatments, with being more suitable for and more efficiently
Low value component is converted into high value component by method, and economic advantages are greatly improved generally.
Preferably, in described step a) the range of reaction temperature lower limit of the first reaction zone selected from 600 DEG C,
640 DEG C, 670 DEG C, the upper limit is selected from 720 DEG C, 700 DEG C, 680 DEG C, 670 DEG C.It is further preferred that
In described step a), the reaction temperature of the first reaction zone is 640 DEG C～680 DEG C.
Preferably, in the charging of described step a) the first reaction zone under the weight space velocity scope of Petroleum
Limit is selected from 0.5h-1、0.8h-1、1.0h-1、1.2h-1, the upper limit is selected from 2.5h-1、1.6h-1、1.4h-1、
1.2h-1、1.0h-1.It is further preferred that Petroleum in feeding in described step a) the first reaction zone
Weight space velocity be 0.5～2.5h-1。
The charging of described step a) the first reaction zone can contain water, described charging Zhong Shui and stone brain
The ratio range lower limit of the weight ratio water/Petroleum of oil is selected from 0,0.14,0.33,0.6,1, and the upper limit is selected
From 0.6,1,1.25,1.5.It is further preferred that the weight ratio water of water and Petroleum in described charging
/ Petroleum=0～1.5.It is further preferred that the weight ratio water/stone of water and Petroleum in described charging
Cerebrol=0～1.25.In catalytic pyrolysis process, water can be had to participate in, it is also possible in the case of anhydrous
Carry out catalytic pyrolysis.In catalytic cracking reaction, charging is without steam, and its advantage is, is not having
In the presence of having steam, molecular sieve would not lose activity because high temperature hydro-thermal takes off framework aluminum
Center, the life-span of catalyst will extend greatly.Additionally, energy consumption reduces, sewage reduces.As one
The individual mode that is preferably carried out, the charging of described step a) the first reaction zone is made up of Petroleum.
Preferably, described first reaction zone includes at least one fixed bed reactors.It is further preferred that
Described first reaction zone includes a fixed bed catalyst district, provides anti-by the way of external heat
Answer institute's calorific requirement.
One according to the application is preferably carried out mode, it is provided that the first reaction in described method
The catalyst in district, this catalyst possesses the Petroleum one way reactivity worth of excellence, is more suitable for stone simultaneously
Alkene not less than 5 of cerebrol and carbon number and carbon number are not less than the body of 6 alkane simultaneous reactions
System, is also equipped with stronger steam stability.
Preferably, containing in the catalyst of molecular sieve in described step a), molecular sieve is Hydrogen ZSM-5
Molecular sieve.Described hydrogen type molecular sieve is exchanged by molecular sieve through ammonium ion, roasting obtains.
Preferably, containing in the catalyst of molecular sieve in described step a), molecular sieve is through group of the lanthanides unit
The molecular sieve that at least one and/or P elements modification in element obtains.It is further preferred that described modification
In molecular sieve, lanthanide series weight/mass percentage composition in modified molecular screen is in terms of oxide, the lowest
In 6%；P elements weight/mass percentage composition in modified molecular screen, with oxide P2O5Meter is the lowest
In 3%.It is further preferred that in described modified molecular screen, lanthanide series is in modified molecular screen
Weight/mass percentage composition, in terms of oxide, be not less than 9%；P elements matter in modified molecular screen
Amount percentage composition, with oxide P2O5Meter, is not less than 4%.
It is preferably carried out mode as one, described step a) contains in the catalyst of molecular sieve,
Molecular sieve is through lanthanum element and the molecular sieve of P elements modification；Wherein, lanthanum element is at modified molecular screen
In weight/mass percentage composition, with oxide La2O3Meter, is 6～12%；P elements is at modified molecular screen
In weight/mass percentage composition, with oxide P2O5Meter, is 3～10%.
It is preferably carried out mode as one, described step a) contains in the catalyst of molecular sieve,
Molecular sieve is through lanthanum element and the Hydrogen ZSM-5 molecular sieve of P elements modification；Wherein, lanthanum element
Weight/mass percentage composition in modified molecular screen, with oxide La2O3Meter, is 6～12%；P elements
Weight/mass percentage composition in modified molecular screen, with oxide P2O5Meter, is 3～10%.
Preferably, described step a) contain in the catalyst of molecular sieve, the sial mole of molecular sieve
Compare SiO2/Al2O3=20～200.
Preferably, in described step a) containing molecular sieve catalyst in catalyst by modified molecular screen
Form with aluminium oxide.It is further preferred that the weight/mass percentage composition that modified molecular screen is in the catalyst is not
Less than 60wt%.It is further preferred that the weight/mass percentage composition that modified molecular screen is in the catalyst is not
Less than 75wt%.
It is preferably carried out mode as one, described step c) enters water and the thing of second reaction zone
Weight ratio water/stream I I=0.3～0.5 of stream II；Second reaction zone temperature range 800 DEG C～850 DEG C；Water
It is 0.2 second～0.5 second with stream I I in the time of staying of second reaction zone.It is further preferred that the
Two reaction zone temperature scopes 820 DEG C～850 DEG C.
The beneficial effect that the application can produce includes:
1) method provided herein, the reaction temperature having catalytic pyrolysis concurrently is low, selectivity is high
Advantage, and steam pyrolysis is for the conversion advantage of the alkane for 2～5.
2) method provided herein, the productivity of high value products is higher, and energy consumption is lower simultaneously.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of embodiment of the application.
Fig. 2 is the schematic flow sheet of a kind of embodiment of the application.
Fig. 3 is catalyst CAT-2 in embodiment 7#Low-carbon (LC) in product during upper feeding anhydrous steam
Alkene is with the variation diagram in response time.
Fig. 4 is catalyst CAT-1 in embodiment 8#On product in low-carbon alkene with the response time
Variation diagram.
Fig. 5 is catalyst CAT-2 in embodiment 9#On product in low-carbon alkene with the response time
Variation diagram.
Fig. 6 is catalyst CAT-3 in embodiment 10#On product in low-carbon alkene with reaction time
Between variation diagram.
Detailed description of the invention
Below in conjunction with embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
If no special instructions, the raw material in embodiments herein and catalyst are all purchased by commercial sources
Buying, wherein ZSM-5 molecular sieve is bought from Catalyst Factory, Nankai Univ.The application uses in implementing
Petroleum component is as shown in table 1 below:
Table 1
Embodiments herein is analyzed method as follows:
Product is by online gas chromatographic analysis.Gas chromatogram is the 7890A of Agilent company, peace
The HP-5 capillary column detection of Jie Lun company.
In embodiments herein, " productivity " computational methods are as follows:
Productivity=target product growing amount/naphtha feed amount × 100%
In embodiments herein, " selectivity of (ethylene+propylene+butylene) " computational methods are as follows:
The selectivity of (ethylene+propylene+butylene)=(ethylene+propylene+butylene)/(hydrogen+carbon atom
Number is the hydro carbons of 1～4) × 100%
In embodiments herein, productivity and selectivity are all based on weight and calculate.
Embodiment 1 catalyst CAT-1#Preparation
Modified molecular screen Z-1
#
Preparation
Infusion process is used to prepare modified molecular screen, particularly as follows: by silica alumina ratio SiO2/Al2O3(mol ratio)
The Hydrogen ZSM-5 molecular sieve 84g of=30 impregnated in the La (NO that 100ml concentration is 0.74mol/L3)3
In solution, then at 120 DEG C of drying, 550 DEG C of roastings, the most again by the solid impregnating after roasting in 100g
Concentration is in the phosphoric acid solution of 4wt%, and then at 120 DEG C of drying, 550 DEG C of roastings, the modification obtained divides
Son sieve is designated as sample Z-1#.Sample Z-1#In: La2O3Weight/mass percentage composition be 12%, P2O5's
Weight/mass percentage composition is 4%.
Catalyst CAT-1
#
Preparation
Take 75g sample Z-1#With 25 grams of aluminium oxide mixing, add the stirring of 30ml 3% dust technology and mediate,
Then extruded moulding, then at 120 DEG C of drying, 650 DEG C of roastings, obtains preformed catalyst, is designated as catalysis
Agent CAT-1#.Catalyst CAT-1#Middle sample Z-1#Weight/mass percentage composition be 75%, aluminium oxide
Weight/mass percentage composition is 25%.
Embodiment 2 catalyst CAT-2#Preparation
Modified molecular screen Z-2
#
Preparation
By silica alumina ratio SiO2/Al2O3The Hydrogen ZSM-5 molecular sieve 84g of (mol ratio)=50 impregnated in
100ml concentration is the La (N0 of 0.74mol/L3)3In solution, then at 120 DEG C of drying, 550 DEG C of roastings
Burn, the most again by the solid impregnating after roasting in the phosphoric acid solution that 100g concentration is 4wt%, then at
120 DEG C of drying, 550 DEG C of roastings, the modified molecular screen obtained is designated as sample Z-2#.Sample Z-2#In:
La2O3Weight/mass percentage composition be 12%, P2O5Weight/mass percentage composition be 4%.
Catalyst CAT-2
#
Preparation
Take 80g sample Z-2#Mix with 20g aluminium oxide, add the stirring of 40ml 3% dust technology and mediate,
Then extruded moulding, then at 120 DEG C of drying, 650 DEG C of roastings, obtains preformed catalyst, is designated as catalysis
Agent CAT-2#.Catalyst CAT-2#Middle sample Z-2#Weight/mass percentage composition be 80%, aluminium oxide
Weight/mass percentage composition is 20%.
Embodiment 3 catalyst CAT-3#Preparation
Modified molecular screen Z-3
#
Preparation
By silica alumina ratio 5iO2/Al2O3The Hydrogen ZSM-5 molecular sieve 87g dipping of (mol ratio)=100
In the La (NO that 100ml concentration is 0.56mol/L3)3In solution, then at 120 DEG C of drying, 550 DEG C
Roasting, the most again by the solid impregnating after roasting in the phosphoric acid solution that 100g concentration is 4wt%, then
In 120 DEG C of drying, 550 DEG C of roastings, the modified molecular screen obtained is designated as sample Z-3#.Sample Z-3#
In: La2O3Weight/mass percentage composition be 9%, P2O5Weight/mass percentage composition be 4%.
Catalyst CAT-3
#
Preparation
Take 80g sample Z-3#With 20 grams of aluminium oxide mixing, add the stirring of 80ml 3% dust technology and mediate,
Then extruded moulding, then at 120 DEG C of drying, 650 DEG C of roastings, obtains preformed catalyst, is designated as catalysis
Agent CAT-3#.Catalyst CAT-3#Middle sample Z-3#Weight/mass percentage composition be 80%, aluminium oxide
Weight/mass percentage composition is 20%.
Embodiment 4～6 catalyst CAT-2#The reaction of upper Petroleum
Reaction process is as it is shown in figure 1, be first passed through naphtha fed (IBP-180 DEG C) and water vapour
First reaction zone, the first reaction zone is filling 10g catalyst CAT-2#Fixed bed reactors, instead
Answering and react at temperature 670 DEG C, the product obtained after the first reaction zone reaction is isolated to
Stream I, product I and by-product I.Wherein stream I includes the alkane that carbon number is 2～5, product
I includes that aromatic hydrocarbons that alkene that carbon number is 2～12, carbon number are 6～12 and carbon number are 6～12
Alkane, remaining for by-product I.Stream I and water vapour are passed through the steam of second reaction zone
In cracking reactor, carrying out steam pyrolysis reaction, second reaction zone is tube furnace reactor, obtains
Product I II and the product I that obtains of the fixed bed reactors of the first reaction zone in chemical products mixing.
Product I II that wherein second reaction zone obtains includes low-carbon alkene, the carbon atom that carbon number is 2～4
Number is the aromatic hydrocarbons of 6～8, remaining for by-product III.
Reaction condition and productivity are shown in Table 2.
Table 2 catalyst CAT-2#The reaction condition of upper Petroleum (IBP-180 DEG C) and productivity
Notea: in table, productivity is weight percent productivity.
Noteb: BTX refers to light aromatics, including benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene).
From table 2, data understand, and under 670 DEG C of reaction temperatures, Petroleum is through a catalytic pyrolysis
In reaction and product, carbon number 2～5 alkane carries out steam pyrolysis freshening.Finalization chemical product is (low
Carbon olefin+BTX) and total product of high-knock rating gasoline (isolating remaining fluid product after BTX)
Rate is up to 87～88%.
Upper first reaction zone of embodiment 7 catalyst CAT-2# not containing water vapor reacts
Reaction process is with embodiment 4, and simply the first reaction zone does not adds steam, reacting flow chart such as figure
Shown in 1.The Petroleum (IBP-180 DEG C) reaction result under the conditions of 670 DEG C is listed in table 3.
Table 3 catalyst CAT-2#Upper Petroleum is without the reaction condition of water and productivity
Notea: in table, productivity is weight percent productivity.
Noteb: BTX refers to light aromatics, including benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene).
During it can be seen that the catalytic cracking reaction of the first reaction zone is without steam, selectivity is
Declining, methane production has risen, but the product of " low-carbon alkene+BTX " in catalytic pyrolysis product
Rate has risen, and during this is because do not have steam, the activity of catalyst is higher, reactant
Conversion ratio raising causes.Owing to the selectivity of catalytic cracking reaction declines, target product is caused always to produce
Rate declines, but still up to 80%.
In catalytic reaction products, low-carbon alkene is shown in Fig. 3 with the change in response time.
Embodiment 8～10 carries out using the Petroleum reaction of catalytic pyrolysis freshening in different catalysts
Its flow process as in figure 2 it is shown, be first passed through by naphtha fed (IBP-150 DEG C) and water vapour
One reaction zone.The first reaction zone in embodiment 8, embodiment 9 and embodiment 10 loads 10g respectively
The catalyst CAT-1 of preparation in embodiment 1,2 and 3#, catalyst CAT-2#With catalyst CAT-3#
Fixed bed reactors, be fixed bed reactors.The product obtained after first reaction zone reaction
It is isolated to stream I, stream I I, product I I and by-product II.Wherein stream I includes carbon atom
Number is the alkane of 2～5；Stream I I includes that alkane that carbon number is 6～12 and carbon number are
The alkene of 5～12；Product I I includes that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Aromatic hydrocarbons；Remaining for by-product II.The fixed bed reactors that stream I I returns the first reaction zone continue
Continue and carry out catalytic cracking reaction.By anti-for steam pyrolysis that stream I and water vapour are passed through second reaction zone
Answering in device, carry out steam pyrolysis reaction, second reaction zone is tube furnace reactor, the product obtained
Product I I that the fixed bed reactors of III and the first reaction zone obtain is all as chemical products.Wherein
Product I II that two reaction zones obtain includes that low-carbon alkene that carbon number is 2～4 and carbon number are 6～8
Aromatic hydrocarbons, remaining for by-product III.
The sky of Petroleum in the weight ratio of reaction temperature, water and Petroleum (IBP-150 DEG C), charging
Speed is shown in Table 4, and remaining condition is with embodiment 4.Petroleum (IBP-150 DEG C) is in different catalysts
Reaction result is listed in table 4.
Reaction condition in table 4 embodiment 8～10 different catalysts and productivity
Notea: in table, productivity is weight percent productivity.
Noteb: BTX refers to light aromatics, including benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene).
Notec: C6～12Alkane refers to the alkane that carbon number is 6～12.
Petroleum through the catalytic cracking reaction of the first reaction zone, the steam pyrolysis freshening of stream I and
The catalysis freshening of logistics 2, in different catalysts, the gross production rate of chemical products can reach 83～85%.
Fig. 4, Fig. 5 and Fig. 6 are in embodiment 8, embodiment 9 and embodiment 10 respectively, once urge
In change product, low-carbon alkene is with the variation diagram in response time.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. the method for transformation of a Petroleum, it is characterised in that at least comprise the following steps:
A) charging containing Petroleum is passed through the first reaction zone, 580 DEG C～the reaction temperature of 700 DEG C
Down with the catalyst haptoreaction containing molecular sieve, product is isolated to stream I and product I；
B) gained stream I in water vapour and step a) is passed through second reaction zone, at 780 DEG C～870 DEG C
Reaction temperature under carry out steam pyrolysis reaction, obtain product I II after reaction；
Described stream I includes the alkane that carbon number is 2～5；
Described product I include aromatic hydrocarbons that alkene that carbon number is 2～12, carbon number are 6～12 and
Carbon number is the alkane of 6～12；
Described product I II includes the virtue that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Hydrocarbon.
2. the method for transformation of a Petroleum, it is characterised in that at least comprise the following steps:
A) charging containing Petroleum is passed through the first reaction zone, 580 DEG C～the reaction temperature of 700 DEG C
Down with the catalyst haptoreaction containing molecular sieve, product is isolated to stream I, stream I I
With product I I；
B) gained stream I in water vapour and step a) is passed through second reaction zone, at 780 DEG C～870 DEG C
Reaction temperature under carry out steam pyrolysis reaction, obtain product I II after reaction；
C) step a) gained logistics II is returned to described first reaction zone；
Described stream I includes the alkane that carbon number is 2～5；
Described stream I I includes the alkene that alkane that carbon number is 6～12, carbon number are 5～12；
Described product I I includes the aromatic hydrocarbons that low-carbon alkene that carbon number is 2～4, carbon number are 6～8；
Described product I II includes the virtue that low-carbon alkene that carbon number is 2～4, carbon number are 6～8
Hydrocarbon.
Method the most according to claim 1 and 2, it is characterised in that in described step a)
The reaction temperature of one reaction zone is 640 DEG C～680 DEG C.
Method the most according to claim 1 and 2, it is characterised in that described step a) first
In reaction zone feeds, the weight space velocity of Petroleum is 0.5h-1～2.5h-1。
Method the most according to claim 1 and 2, it is characterised in that described step a) enters
Possibly together with water vapour in material, steam and the weight ratio water's steam/Petroleum of Petroleum in described charging
=0～1.5.
Method the most according to claim 1 and 2, it is characterised in that contain in described step a)
Having in the catalyst of molecular sieve, molecular sieve is Hydrogen ZSM-5 molecular sieve.
Method the most according to claim 1 and 2, it is characterised in that contain in described step a)
Having in the catalyst of molecular sieve, molecular sieve is at least one in lanthanide series and/or P elements modification
The molecular sieve obtained.
Method the most according to claim 1 and 2, it is characterised in that contain in described step a)
Having in the catalyst of molecular sieve, molecular sieve is through lanthanum element and the molecular sieve of P elements modification；Wherein,
Lanthanum element weight/mass percentage composition in modified molecular screen, with oxide La2O3Meter, is 6～12%；
P elements weight/mass percentage composition in modified molecular screen, with oxide P2O5Meter, is 3～10%.
Method the most according to claim 1 and 2, it is characterised in that contain in described step a)
Have in the catalyst of molecular sieve, the silica alumina ratio SiO of molecular sieve2/Al2O3=20～200.
Method the most according to claim 1 and 2, it is characterised in that in described step b)
Enter the water vapour of second reaction zone and weight ratio water/stream I I=0.2～0.5 of stream I I；Second reaction
District's temperature range 800 DEG C～850 DEG C；Water and stream I I are 0.2 second in the time of staying of second reaction zone
～0.5 second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510296090.8A CN106221786B (en) | 2015-06-02 | 2015-06-02 | Naphtha conversion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510296090.8A CN106221786B (en) | 2015-06-02 | 2015-06-02 | Naphtha conversion method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106221786A true CN106221786A (en) | 2016-12-14 |
| CN106221786B CN106221786B (en) | 2021-03-02 |
Family
ID=57528696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510296090.8A Active CN106221786B (en) | 2015-06-02 | 2015-06-02 | Naphtha conversion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106221786B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021019326A1 (en) | 2019-07-31 | 2021-02-04 | Sabic Global Technologies B.V. | Naphtha catalytic cracking process |
| WO2021019344A1 (en) | 2019-07-31 | 2021-02-04 | Sabic Global Technologies B.V. | Naphtha catalytic cracking process |
| CN115869988A (en) * | 2022-12-02 | 2023-03-31 | 厦门大学 | Catalyst for preparing low-carbon olefins by catalytic cracking of naphtha and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457833A (en) * | 1981-08-27 | 1984-07-03 | Ashland Oil, Inc. | Process and catalyst for the conversion of carbo-metallic containing oils |
| CN1651363A (en) * | 2004-01-14 | 2005-08-10 | 凯洛格·布朗及鲁特有限公司 | Integrated catalytic cracking and steam pyrolysis process for olefins |
| CN101279287A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis |
| CN102372555A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing light olefins through fluid catalytic cracking of naphtha |
| CN102371172A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing alkene through catalytic cracking |
| CN103374395A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and ethylene by taking naphtha as raw material |
-
2015
- 2015-06-02 CN CN201510296090.8A patent/CN106221786B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457833A (en) * | 1981-08-27 | 1984-07-03 | Ashland Oil, Inc. | Process and catalyst for the conversion of carbo-metallic containing oils |
| CN1651363A (en) * | 2004-01-14 | 2005-08-10 | 凯洛格·布朗及鲁特有限公司 | Integrated catalytic cracking and steam pyrolysis process for olefins |
| CN101279287A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis |
| CN102372555A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing light olefins through fluid catalytic cracking of naphtha |
| CN102371172A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing alkene through catalytic cracking |
| CN103374395A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and ethylene by taking naphtha as raw material |
Non-Patent Citations (2)
| Title |
|---|
| 张勇: "《烯烃技术进展》", 31 October 2008 * |
| 黄风林: "《石油天然气化工工艺》", 30 September 2011 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021019326A1 (en) | 2019-07-31 | 2021-02-04 | Sabic Global Technologies B.V. | Naphtha catalytic cracking process |
| WO2021019344A1 (en) | 2019-07-31 | 2021-02-04 | Sabic Global Technologies B.V. | Naphtha catalytic cracking process |
| CN115869988A (en) * | 2022-12-02 | 2023-03-31 | 厦门大学 | Catalyst for preparing low-carbon olefins by catalytic cracking of naphtha and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106221786B (en) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10894752B2 (en) | Catalyst and method for aromatization of C3-C4 gases, light hydrocarbon fractions and aliphatic alcohols, as well as mixtures thereof | |
| WO2016192041A1 (en) | Process for converting naphtha | |
| JP5881856B2 (en) | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use | |
| CN104250186B (en) | A kind of preparation method of low-carbon alkene | |
| CN103980082B (en) | A kind of method of preparing propylene from methanol | |
| Rossetti et al. | Ethylene production from diluted bioethanol solutions | |
| CN105622306A (en) | Method for producing aromatic hydrocarbon with oxygen-containing compound as raw material | |
| JP6408611B2 (en) | Process for producing p-xylene and propylene from methanol and / or dimethyl ether | |
| CN106221786A (en) | A kind of method for transformation of Petroleum | |
| CN103058814B (en) | Method for producing aromatic hydrocarbon and olefin from liquefied gas | |
| CN102285851B (en) | Method for increasing yields of ethylene and propylene | |
| JP6408612B2 (en) | A method for producing p-xylene with high selectivity and co-producing propylene | |
| CN103121891B (en) | Method for producing low-carbon olefin | |
| CN107602321A (en) | A kind of fluidized-bed process method of benzene and methanol alkylation production paraxylene | |
| CN104557377B (en) | The method of oxygenatedchemicals and naphtha coupled reaction production ethylene and propylene | |
| CN102286292B (en) | Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate | |
| CN109569703A (en) | Catalyst and preparation method and application by naphtha and methanol production gasoline component | |
| CN102285854B (en) | Method for increasing yields of propylene, ethylene and butadiene | |
| CN102285857B (en) | Method for increasing yields of propylene and ethylene | |
| CN107794080B (en) | The method for modifying of F- T synthesis naphtha | |
| KR101795851B1 (en) | Method for producing aromatics from light hydrocarbons using oxygen using carbon dioxide | |
| Magomedova et al. | Effect of feedstock and gas atmosphere composition on selectivity and distribution of hydrocarbon groups in gasoline synthesis from oxygenates | |
| CN104250190B (en) | A kind of preparation method of propylene | |
| CN109608301A (en) | A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene | |
| CN103316707A (en) | Catalyst and method for catalytic cracking of petroleum hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |