CN104557400B - A kind of naphtha catalytic cracking produces the method for propylene - Google Patents
A kind of naphtha catalytic cracking produces the method for propylene Download PDFInfo
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- CN104557400B CN104557400B CN201310522779.9A CN201310522779A CN104557400B CN 104557400 B CN104557400 B CN 104557400B CN 201310522779 A CN201310522779 A CN 201310522779A CN 104557400 B CN104557400 B CN 104557400B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of method that naphtha catalytic cracking produces propylene, the method includes: Petroleum, under pretreatment condition, is contacted by (1) with pretreating agent, obtains the process oil that basic n content reduces；(2) in the presence of the first catalyst and water, the process oil that step (1) obtains is carried out the first catalytic pyrolysis, obtains product；(3) in the presence of the second catalyst and water, the product that step (2) obtains is carried out the second catalytic pyrolysis, obtains cleavage reaction product.The method that the present invention provides can improve naphtha catalytic cracking and produce the yield of propylene.
Description
Technical field
The present invention relates to a kind of method that naphtha catalytic cracking produces propylene.
Background technology
Propylene is one of most widely used basic organic chemical industry raw material, mainly for the production of polypropylene, different
Propyl benzene, acrylonitrile, acrylic acid etc..Propylene is mainly derived from ethylene cracker and the refining of petrochemical plant at present
The catalytic cracking unit of oil factory.Along with whole world propylene demand quickly increases, the yield of traditional processing technology is difficult
To meet demand, therefore develop that the technology of propylene enhancing has become in petrochemical iy produced technology one important
Exhibition direction.
Conventional ethylene cracking mainly passes through steam heat producing ethylene by cracking and propylene with Petroleum for raw material,
Wherein limited by heat scission reaction mechanism, general ethylene/propene than for maximum limit about 0.65, higher than this
Ratio, total olefin will decline.This process needs to consume substantial amounts of high-quality feed naphtha, is one
The process of individual high energy consumption.The propylene of 66-70% steam heat cracking technique produces at present.
Catalytic pyrolysis is lower than the reaction temperature that steam heat cracks about 50-200 DEG C, and energy consumption is relatively low.And urge
The reaction mechanism changing cracking advantageously forms propylene molecules, therefore can realize Petroleum and produce propene yield
Increase.
It is the method for preparing light olefins through fluid catalytic cracking of naphtha that CN102372555A discloses a kind of, with
Petroleum and water are raw material, and at reaction temperature is 600-750 DEG C, weight space velocity is 0.1-2h-1, water with
Weight of oil ratio is under conditions of for 0.1-8:1, and raw material contacts with fluid catalyst, and reaction generates ethylene
With propylene, wherein used catalyst comprises following components by weight percentage: a) 15.0-60.0% is selected from
Kaolin；B) at least one in silicon oxide or aluminium oxide of 10.0-30.0%；C) 0.5-15.0% choosing
At least one in phosphorus, rare earth or alkaline earth element oxide；D) 25.0-70.0% is selected from directed agents legal system
Standby crystallite dimension is the ZSM-5 zeolite of 200-1000nm.
CN101279881A discloses a kind of catalytic pyrolysis Petroleum and produces ethylene and the method for propylene, with
The Petroleum of C4-C16 hydrocarbon is raw material, before contact with catalyst after raw material hydrocarbon vaporization, first with to react in
Inert gas mixes, and wherein noble gas is more than 0 and to be less than or equal to the mol ratio of Petroleum
5.0:1, is 580-750 DEG C in reaction temperature, counts reaction pressure for more than 0 and be less than or equal to gauge pressure
0.5MPa, weight space velocity is 0.5-3 hour-1, under conditions of water/Petroleum weight ratio is 0-5:1, raw material
Gaseous mixture and catalyst haptoreaction generate ethylene and propylene, and wherein used catalyst is selected from ZSM-5/ silk
Geolyte coexisting molecular sieve, ZSM-5/ beta zeolite coexisting molecular sieve or ZSM-5/Y zeolite coexisting molecular sieve
In at least one.
CN1958731A discloses a kind of method that catalytic pyrolysis produces alkene, wherein will comprise Petroleum,
The cracking petroleum hydrocarbon raw material of light diesel fuel and hydrogenation tail oil, by two the filling different catalysts connected up and down
The beds of a and b, carries out catalytic cracking reaction, obtains olefine in low carbon number.
Although above prior art is obtained in that propylene or light olefin, but the yield of propylene is the most relatively low.
It is therefore desirable to be able to make naphtha catalytic cracking produce the higher method of propene yield.
Summary of the invention
The invention aims to overcome prior art naphtha catalytic cracking to produce low the asking of propene yield
Topic, it is provided that a kind of naphtha catalytic cracking produces the method for ethylene, propylene.
To achieve these goals, the present invention provides a kind of method that naphtha catalytic cracking produces propylene, should
Method includes: Petroleum, under pretreatment condition, is contacted by (1) with pretreating agent, obtains basic nitrogen and contains
The process oil that amount reduces；(2) in the presence of the first catalyst and water, the process that step (1) is obtained
Oil carries out the first catalytic pyrolysis, obtains product；(3) in the presence of the second catalyst and water, incite somebody to action
The product that step (2) obtains carries out the second catalytic pyrolysis, obtains cleavage reaction product；Wherein,
On the basis of the gross weight of described first catalyst, described first catalyst contains the heat-resisting of 2-60 weight %
Inorganic oxide and the modified ZSM-5 zeolite of 40-98 weight %, described first catalyst is spheroidal particle
And/or bar shaped granule；Described second catalyst includes ordered structure carrier and is distributed in ordered structure carrier
Surface and/or the active component coating of outer surface；On the basis of the gross weight of described second catalyst, described
The content of active component coating is 10-50 weight %；On the basis of the gross weight of described active component coating,
Described active component coating contains molecular sieve and the substrate of 5-50 weight % of 50-95 weight %；Described point
Son sieve is the molecular sieve with MWW structure.
The method provided by the present invention, can be produced with catalytic pyrolysis Petroleum and obtain more propylene product
Product.The method that the present invention provides, the amount of the ethylene obtained, propylene and butylene is that the pyrolysis product obtained is total
More than 90 weight % of amount, and Propylene Selectivity is more than 50%.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the method flow schematic diagram of a kind of naphtha catalytic cracking product propylene of the present invention.
Description of reference numerals
1 pretreatment tank 2 preheater 3 first reactor 4 heater
5 second reactor 6 condenser 7 knockout drum 8 first knockout towers
9 second knockout tower 10 the 3rd knockout towers
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, term ordered structure catalyst is used to refer to ordered structure carrier and be distributed in load
The catalyst of the active component coating of internal surface and/or outer surface；Ordered structure carrier is for having regular knot
The carrier of structure；Monolithic reactors is to have loaded ordered structure catalyst fixing as beds
Bed reactor.
The present invention provides a kind of method that naphtha catalytic cracking produces propylene, as it is shown in figure 1, the method bag
Include: Petroleum, under pretreatment condition, is contacted with pretreating agent by (1), obtain basic n content and reduce
Process oil；(2) in the presence of the first catalyst and water, the process oil that step (1) obtains is carried out
First catalytic pyrolysis, obtains product；(3) in the presence of the second catalyst and water, by step (2)
The product obtained carries out the second catalytic pyrolysis, obtains cleavage reaction product；Wherein, with described first
On the basis of the gross weight of catalyst, described first catalyst contains the heat-resistant inorganic oxide of 2-60 weight %
With the modified ZSM-5 zeolite of 40-98 weight %, described first catalyst is spheroidal particle and/or bar shaped
Granule；Described second catalyst include ordered structure carrier and be distributed in ordered structure carrier inner surface and/
Or the active component coating of outer surface；On the basis of the gross weight of described second catalyst, described activity group
The content of point coating is 10-50 weight %；On the basis of the gross weight of described active component coating, described
Active component coating contains molecular sieve and the substrate of 5-50 weight % of 50-95 weight %；Described molecular sieve
For having the molecular sieve of MWW structure.
In the method that the present invention provides, the first catalyst and the second catalyst is used to split as Petroleum catalysis
Solve the beds producing propylene, on the first catalyst and the second catalyst, carry out the first catalysis respectively and split
Solve reaction and the second catalytic cracking reaction.Described first catalyst is beaded catalyst and described second catalysis
Agent is ordered structure catalyst, naphtha catalytic cracking can be better achieved and produce propylene, improve propylene
Yield.
In the present invention, described ordered structure catalyst includes ordered structure carrier and is distributed in ordered structure load
Internal surface and/or the active component coating of outer surface, wherein containing having MWW in active component coating
The molecular sieve of structure, can more effectively improve naphtha catalytic cracking and produce the productivity of propylene.It addition, will
Petroleum carries out pretreatment, can improve the yield of propylene further.It is probably pretreatment can help to subtract
The a small amount of impurity contained in few Petroleum, such as basic nitrogen etc., it helps reduce catalyst activity
Adverse effect.
The method provided according to the present invention, the first catalytic pyrolysis can use spheroidal particle and/or bar shaped
The reactor of granuloplastic first beds is carried out.Under preferable case, described first catalysis is split
The reaction condition solved includes: temperature is 450-550 DEG C, and pressure is 0.02-1MPa, processes oil/water charging
Mass ratio is 1-5:1, and processing oil charging weight (hourly) space velocity (WHSV) is 5-15h-1；Preferably, pressure is 0.05-1MPa,
Processing oil/water charge-mass ratio is 2-3:1, and processing oil charging weight (hourly) space velocity (WHSV) is 5-10h-1。
The method provided according to the present invention, the second catalytic pyrolysis can be formed using ordered structure catalyst
The second beds reactor in carry out.Under preferable case, the reaction of described second catalytic pyrolysis
Condition includes: temperature is 400-650 DEG C, and pressure is 0.02-1MPa, processes oil/water charge-mass ratio and is
0.2-8:1, processing oil charging weight (hourly) space velocity (WHSV) is 5-45h-1；Preferably, pressure is 0.05-0.5MPa, place
Reason oil/water charge-mass ratio is 1-5:1, and processing oil charging weight (hourly) space velocity (WHSV) is 10-40h-1。
In the present invention, it is provided that naphtha catalytic cracking produce propylene method can also include by inactivation urging
Agent uses air regenesis at 450-800 DEG C.The feed volume air speed of air can be 5-15h-1。
According to the present invention, before carrying out naphtha catalytic cracking product propylene, Petroleum can carry out pre-place
Reason, under preferable case, in step (1), described pretreatment condition includes: temperature is 20-80 DEG C, pressure
Power is 0.02-1MPa, and naphtha feed weight (hourly) space velocity (WHSV) is 0.5-5h-1；Preferable temperature is 25-60 DEG C.
According to the present invention, described pretreating agent can be to remove a small amount of impurity, such as basic nitrogen in Petroleum
Material.Under preferable case, in step (1), described pretreating agent is Hydrogen polystyrene cation
Exchanger resin.Preferably, described ion exchange resin can be highly acid, faintly acid, oxidation-reduction quality
Resin；Can also be commercially available, the such as trade mark be NKC-9 dry acid catalyst resin, CT-175, D005-II,
The Hydrogen macropore sulfuric acid resin of LSI-600, SXC-9.
In the present invention, described pretreating agent can use solvent to regenerate, described solvent can be ethanol,
One in acetone, methanol carries out described pretreatment can use dual system, i.e. uses arranged side by side pre-of two sets
Process, can be when a system carry out pretreatment, another system carries out regenerative process；Enter the most again
Two system switchings of row, can make described pretreatment realize being carried out continuously.
In the present invention, obtain described first catalyst and can use commonly used in the art, prepare spherical
Granule and/or the method for bar shaped granule, such as bar shaped catalyst can be particle diameter 2-3mm, granule
The bar shaped granule of length 2-5mm.This is no longer going to repeat them.The most described first catalyst contain with
On the basis of the gross weight of this catalyst, the heat-resistant inorganic oxide of 2-60 weight %, 40-98 weight %
Modified ZSM-5 zeolite.Described heat-resistant inorganic oxide can be the material that this area is conventionally used as carrier,
Such as can be preferably aluminium oxide.Described modified ZSM-5 zeolite contains with described modified ZSM-5 zeolite
Gross weight on the basis of, the modifying element of 1-5 weight %.Described modifying element is selected from rare earth metal, IVB
At least one in race's metal, phosphorus, ferrum, zinc, stannum and vanadium.Wherein said rare earth metal can be selected from lanthanum
Being metal or yttrium, Group IVB metal can be preferably titanium or zirconium.
In the present invention, the preparation of described modified ZSM-5 zeolite can use the modification side that this area is conventional
Method is carried out, and this is no longer going to repeat them.
In the present invention, sial atomic molar ratio (Si/Al) of described modified ZSM-5 zeolite is 15-100:
1；It is preferably 50-100:1.
In the present invention, described second catalyst is ordered structure catalyst, including ordered structure carrier
And active component coating.
In accordance with the present invention it is preferred that, on the basis of the gross weight of described ordered structure catalyst, described work
The content of property component coating is 15-30 weight %.
According to the present invention, described ordered structure carrier may be used for providing in fixed bed reactors catalyst bed
Layer.This ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, duct
Inwall on can be distributed catalyst coat, space, duct can serve as the flowing space of fluid.Preferably feelings
Under condition, described ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.
Described ordered structure carrier can be the regular carrier of honeycomb fashion (the abbreviation honeycomb that cross section has cellular perforate
Carrier).
In the case of according to the invention it is preferred to, the hole density in the cross section of described ordered structure carrier is 6-140
Hole/square centimeter, the sectional area in each hole are 0.4-10 square millimeter.The shape in hole can be square
(or wing square, i.e. in square hole, the centre bit of four edges is equipped with the wing that vertical edges is inside, its
A length of square the length of side 1/5-2/5), equilateral triangle, regular hexagon, circular and corrugated in one
Kind.
In the case of according to the invention it is preferred to, described ordered structure carrier is selected from cordierite honeycomb carrier, not
Carry out at least one in stone honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
In the present invention, described active component coating contains molecular sieve and substrate, it is preferable that with described activity
On the basis of the gross weight of component coating, described active component coating contain 75-95 weight % molecular sieve and
The substrate of 5-25 weight %.
According to the present invention, described molecular sieve is MWW molecular sieve, has ten-ring or nine-atomic ring duct,
Channel openings diameter is in 0.45-0.56 nanometer.Structure type MWW refers to International Zeolite Association meeting (IZA)
The molecular sieve structure of name, for describing the Space expanding in duct in molecular sieve.Preferably, described
Molecular sieve is at least in MCM-22, MSM-49, ITQ-1, ITQ-2, SSZ-25 and PSH-3
Kind.
In the present invention, sial atomic molar ratio (Si/Al) of described molecular sieve can be 0.1-100:1；
It is preferably 30-80:1.
In the case of according to the invention it is preferred to, described substrate can be selected from aluminium oxide, silicon oxide, amorphous
At least one in sial, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide.Preferably,
Described substrate is silicon oxide.
In the present invention, obtain the preparation that described second catalyst can use the ordered structure catalyst of routine
Method, this is no longer going to repeat them.
In the case of according to the invention it is preferred to, described Petroleum is paraffinic base Petroleum, wherein olefin(e) centent
It is below 10 weight %；Preferably, described Petroleum contain according to the invention it is preferred in the case of, institute
State Petroleum and contain the alkene of 0.5-1.5 weight %, the alkane of 40-60 weight %, the ring of 20-40 weight %
Alkane and 10-20 weight % aromatic hydrocarbons.
According to the present invention, containing ethylene and propylene in the cleavage reaction product that step (3) obtains.Preferably
In the case of, the method also includes that the cleavage reaction product by step (3) obtains carries out separating treatment, should
Separating treatment includes: described cleavage reaction product is carried out cooling down and separating in knockout drum by (i)
To liquid and gas；(ii) described gas phase isolated ethylene and more than C3 in the first knockout tower are evaporated
Point；(iii) described more than C3 fraction is evaporated at the second knockout tower isolated C3 fraction and more than C4
Point；(iv) by C3 fraction at the 3rd knockout tower isolated propylene and propane.
According to the present invention, in the separating treatment carried out, under preferable case, will before step (ii)
Described gas phase is compressed to 1-4MPa；Preferably described gas phase is compressed to 2-3MPa.
In the present invention, it is preferable that described gas phase enters the first knockout tower stage casing, at the bottom of the first knockout tower tower
Obtain more than C3 fraction；More than C3 fraction is sent into the second knockout tower stage casing, at the second knockout tower tower
Top obtains C3 fraction, is obtaining more than C4 fraction at the bottom of the second knockout tower tower, and C3 fraction enters the 3rd point
From tower away from the bottom of tower 1/4, in more than C4 fraction, preferred 30-66 weight % is as catalytic pyrolysis raw material；?
The tower top lateral line withdrawal function of the 3rd knockout tower obtains propylene.
In the present invention, described liquid phase is more than C5 fraction.The ethylene concentration that step (ii) obtains is 90-99
Weight %, the density of propylene that step (iv) obtains is 90-99 weight %, and propane concentration is 80-95 weight
%.
In the present invention, described first catalytic pyrolysis and described second catalytic pyrolysis can be that series sequence is entered
OK, it is also possible to being to carry out side by side, preferably series sequence is carried out.Correspondingly, can be according in the present invention
Series sequence carries out described first catalytic pyrolysis and described second catalytic pyrolysis.
In the present invention, one can be had to add between described first catalytic pyrolysis and described second catalytic pyrolysis
The temperature of the reaction of described second catalytic pyrolysis is raised by hot stove.
In the present invention, relate to pressure and all represent with gauge pressure.
The naphtha catalytic cracking provided the present invention below in conjunction with the flow chart shown in accompanying drawing 1 produces propylene
Method implementation process illustrates.
Petroleum is passed through pretreatment tank 1, contacts with the pretreating agent wherein loaded, obtain basic nitrogen and contain
The process oil that amount reduces.It is passed through the first reactor 3 together with being passed through after preheater 2 heats with water by process oil,
Contact with granule and/or the bar shaped catalyst of filling in the first reactor 3, carry out the first catalytic pyrolysis anti-
Should.The product that first catalytic cracking reaction obtains is passed through heater 4 and promotes temperature, and be passed through
Two reactors 5, contact with the ordered structure catalyst of filling in the second reactor 5, carry out the second catalysis
Cracking reaction.The product that second catalytic cracking reaction obtains being passed through condenser 6 condense, condensation is produced
Thing is passed through knockout drum 7 isolated liquid and gas.
Gas-phase product is passed through the first knockout tower 8 stage casing further, and isolated ethylene and more than C3 evaporate
Point.More than C3 fraction is passed through the second knockout tower 9 stage casing further separate, at the second knockout tower
Obtain more than C4 fraction at the bottom of tower, obtain C3 fraction at the second knockout tower tower top.By further for C3 fraction
It is passed through the 3rd knockout tower 10 isolated propane and propylene.
The pressure related in the present invention all represents with gauge pressure.
Hereinafter will be described the present invention by embodiment.
In following example, basic n content is recorded by constant-current titration method.Gas-phase product character is passed through
Chromatogram analysis method, uses the chromatographic apparatus of Agilent company 6890 model to measure.(C2 =+C3 =) receipts
Rate and (C2 =～C4 =) selectivity be calculated by below equation:
Yield=((C2 =+C3 =) growing amount/reaction-ure feeding amount) × 100%,
Selectivity=((C2 =～C4 =) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The method that the present embodiment produces propylene for the naphtha catalytic cracking that the present invention is described.
Method according to the flow implementation present invention shown in Fig. 1.
(1) pretreatment.60 DEG C, under 0.1MPa, by Petroleum, (olefin-containing 1 weight %, containing alkane
Hydrocarbon 56 weight %, containing cycloalkane 32 weight %, containing aromatic hydrocarbons 11 weight %, basic n content is 57 μ g/g)
With weight (hourly) space velocity (WHSV) 1h-1With NKC-3 contacts ionic exchange resin, the process basic nitrogen in oils content obtained
It is 0.5 μ g/g.
(2) propylene is produced.The process oil (1) obtained and water, after 250 DEG C preheat, inject equipped with the
One catalyst be beds reactor in after, reinjecting equipped with the second catalyst is beds
Reactor.
Wherein, the first catalyst contains the ZSM-5 molecular sieve (ZRP-1 modified for La of content 95 weight %
Molecular sieve, Si/Al=50:1), content is the aluminium oxide of 5 weight %, and wherein, the content of La is 10% weight
Amount %, the first catalyst is bar shaped catalyst.Second catalyst is ordered structure catalyst, used regular
Structure catalyst includes that (carrier hole density is 62 holes/square centimeter to cordierite honeycomb carrier, each hole
Sectional area is 0.4 square millimeter, hole be shaped as square) and active component that content is 20 weight %
Coating, containing the MCM-22 molecular sieve (Si/Al=30:1) of 90 weight % in active component coating, 10
The substrate (aluminium oxide) of weight %.
The reaction condition of the first catalytic pyrolysis includes: temperature is 470 DEG C, and pressure is 0.1MPa, processes oil
Charging weight (hourly) space velocity (WHSV) is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of the second catalytic pyrolysis includes: temperature is 650 DEG C, and pressure is 0.1MPa, processes oil
Charging weight (hourly) space velocity (WHSV) (relative to the gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The product that second catalytic cracking reaction obtains being passed through condenser 6 condense, condensed product is passed through
Knockout drum 7 isolated liquid and gas.Gas-phase product is passed through further in the first knockout tower 8
Section, isolated ethylene and more than C3 fraction.More than C3 fraction is passed through further the second knockout tower 9
Stage casing separates, and is obtaining more than C4 fraction, obtain at the second knockout tower tower top at the bottom of the second knockout tower tower
To C3 fraction.C3 fraction is passed through further the 3rd knockout tower 10 isolated propane and propylene.
Calculate (C2 =+C3 =) yield and (C2 =～C4 =) selectivity, the results are shown in Table 1.
Embodiment 2
The method that the present embodiment produces propylene for the naphtha catalytic cracking that the present invention is described.
(1) pretreatment.30 DEG C, under 0.2MPa, by Petroleum, (olefin-containing 1 weight %, containing alkane
Hydrocarbon 56 weight %, containing cycloalkane 32 weight %, containing aromatic hydrocarbons 11 weight %, basic n content is 10 μ g/g)
With weight (hourly) space velocity (WHSV) 5h-1With LSI-600 contacts ionic exchange resin, the process basic nitrogen in oils content obtained
It is 0.4 μ g/g.
(2) propylene is produced.The process oil (1) obtained and water, after 250 DEG C preheat, inject equipped with the
One catalyst be beds reactor in after, reinjecting equipped with the second catalyst is beds
Reactor.
Wherein, the first catalyst contains the ZSM-5 molecular sieve modified for Fe of content 90 weight %
(Si/Al=75:1), content is the aluminium oxide of 10 weight %, and wherein, the content of Fe is 5 weight %,
First catalyst is bar shaped catalyst.Second catalyst is ordered structure catalyst.Ordered structure used is urged
Agent includes that (carrier hole density is 31 holes/square centimeter to cordierite honeycomb carrier, the sectional area in each hole
Be 1 square millimeter, hole be shaped as square) and active component coating that content is 15 weight %,
Active component coating contains the ITQ-1 molecular sieve (Si/Al=50:1) of 95 weight %, the base of 5 weight %
Matter (silicon oxide).
The reaction condition of the first catalytic pyrolysis includes: temperature is 500 DEG C, and pressure is 0.1MPa, processes oil
Charging weight (hourly) space velocity (WHSV) is 10.5hr-1, oil/water charge ratio is 1.
The reaction condition of the second catalytic pyrolysis includes: temperature is 700 DEG C, and pressure is 0.5MPa, processes oil
Charging weight (hourly) space velocity (WHSV) (relative to the gross weight of active component coating) is 35hr-1, oil/water charge ratio is 0.9.
The product that second catalytic cracking reaction obtains being passed through condenser 6 condense, condensed product is passed through
Knockout drum 7 isolated liquid and gas.Gas-phase product is passed through further in the first knockout tower 8
Section, isolated ethylene and more than C3 fraction.More than C3 fraction is passed through further the second knockout tower 9
Stage casing separates, and is obtaining more than C4 fraction, obtain at the second knockout tower tower top at the bottom of the second knockout tower tower
To C3 fraction.C3 fraction is passed through further the 3rd knockout tower 10 isolated propane and propylene.
Calculate (C2 =+C3 =) yield and (C2 =～C4 =) selectivity, the results are shown in Table 1.
Embodiment 3
The method that the present embodiment produces propylene for the naphtha catalytic cracking that the present invention is described.
(1) pretreatment.50 DEG C, under 0.1MPa, by Petroleum, (olefin-containing 1 weight %, containing alkane
Hydrocarbon 56 weight %, containing cycloalkane 32 weight %, containing aromatic hydrocarbons 11 weight %, basic n content is 30 μ g/g)
With weight (hourly) space velocity (WHSV) 3h-1With CT-175 contacts ionic exchange resin, the process basic nitrogen in oils content obtained
It is 0.6 μ g/g.
(2) propylene is produced.The process oil (1) obtained and water, after 250 DEG C preheat, inject equipped with the
One catalyst be beds reactor in after, reinjecting equipped with the second catalyst is beds
Reactor.
Wherein, the first catalyst contains the ZSM-5 molecular sieve modified for P of content 85 weight %
(Si/Al=100:1), content is the aluminium oxide of 15 weight %, and wherein, the content of P is 2 weight %,
First catalyst is bar shaped catalyst.Second catalyst is ordered structure catalyst, and ordered structure used is urged
Agent includes that (carrier hole density is 62 holes/square centimeter to cordierite honeycomb carrier, the sectional area in each hole
Be 0.4 square millimeter, hole be shaped as square) and active component coating that content is 25 weight %,
Active component coating contains the SSZ-25 molecular sieve (Si/Al=80:1) of 75 weight %, 25 weight %
Substrate (aluminium oxide+silicon oxide).
The reaction condition of the first catalytic pyrolysis includes: temperature is 550 DEG C, and pressure is 0.1MPa, processes oil
Charging weight (hourly) space velocity (WHSV) is 4.6hr-1, oil/water charge ratio is 1.61.
The reaction condition of the second catalytic pyrolysis includes: temperature is 600 DEG C, and pressure is 0.2MPa, processes oil
Charging weight (hourly) space velocity (WHSV) (relative to the gross weight of active component coating) is 20hr-1, oil/water charge ratio is 5.
The product that second catalytic cracking reaction obtains being passed through condenser 6 condense, condensed product is passed through
Knockout drum 7 isolated liquid and gas.Gas-phase product is passed through further in the first knockout tower 8
Section, isolated ethylene and more than C3 fraction.More than C3 fraction is passed through further the second knockout tower 9
Stage casing separates, and is obtaining more than C4 fraction, obtain at the second knockout tower tower top at the bottom of the second knockout tower tower
To C3 fraction.C3 fraction is passed through further the 3rd knockout tower 10 isolated propane and propylene.
Calculate (C2 =+C3 =) yield and (C2 =～C4 =) selectivity, the results are shown in Table 1.
Table 1
From the data result of table 1 it can be seen that the method for present invention offer, split carrying out Petroleum catalysis
Solve and produce in propylene, it is possible to obtain high ethylene and propene yield, and wherein propylene/ethylene ratio more than 1,
Producing more propylene can be realized.
Claims (14)
1. the method that naphtha catalytic cracking produces propylene, the method includes:
(1) under pretreatment condition, Petroleum is contacted with pretreating agent, obtain the process oil that basic n content reduces；
(2) in the presence of the first catalyst and water, the process oil that step (1) obtains is carried out the first catalytic pyrolysis, obtains product；
(3) in the presence of the second catalyst and water, the product that step (2) obtains is carried out the second catalytic pyrolysis, obtains cleavage reaction product；
Wherein, on the basis of the gross weight of described first catalyst, described first catalyst contains heat-resistant inorganic oxide and the modified ZSM-5 zeolite of 40-98 weight % of 2-60 weight %, and described first catalyst is spheroidal particle and/or bar shaped granule；Described second catalyst includes ordered structure carrier and is distributed in ordered structure carrier inner surface and/or the active component coating of outer surface；On the basis of the gross weight of described second catalyst, the content of described active component coating is 10-50 weight %；On the basis of the gross weight of described active component coating, described active component coating contains molecular sieve and the substrate of 5-50 weight % of 50-95 weight %；Described molecular sieve is the molecular sieve with MWW structure.
Method the most according to claim 1, wherein, the reaction condition of described first catalytic pyrolysis includes: temperature is 450-550 DEG C, and pressure is 0.02-1MPa, and processing oil/water charge-mass ratio is 1-5:1, and processing oil charging weight (hourly) space velocity (WHSV) is 5-15 h-1。
Method the most according to claim 1, wherein, the reaction condition of described second catalytic pyrolysis includes: temperature is 400-650 DEG C, and pressure is 0.02-1 MPa, and processing oil/water charge-mass ratio is 0.2-8:1, and processing oil charging weight (hourly) space velocity (WHSV) is 5-45h-1。
Method the most according to claim 1, wherein, in step (1), described pretreatment condition includes: temperature is 20-80 DEG C, and pressure is 0.02-1MPa, and naphtha feed weight (hourly) space velocity (WHSV) is 0.5-5h-1。
Method the most according to claim 1, wherein, in step (1), described pretreating agent is Hydrogen styrene type cation exchange resin.
Method the most according to claim 1, wherein, described molecular sieve is at least one in MCM-22, MSM-49, ITQ-1, ITQ-2, SSZ-25 and PSH-3.
Method the most according to claim 1, wherein, described ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.
Method the most according to claim 7, wherein, the hole density in the cross section of described ordered structure carrier be 6-140 hole/square centimeter, the sectional area in each hole be 0.4-10 square millimeter.
Method the most according to claim 1, wherein, at least one in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate of described ordered structure carrier.
Method the most according to claim 1, wherein, on the basis of the gross weight of described modified ZSM-5 zeolite, described modified ZSM-5 zeolite contains the modifying element of 1-10 weight %, at least one in rare earth metal, Group IVB metal, phosphorus, ferrum, zinc, stannum and vanadium of described modifying element.
11. methods according to claim 1, wherein, the sial atomic molar of described modified ZSM-5 zeolite is than for 15-100:1.
12. methods according to claim 1, wherein, described Petroleum is paraffinic base Petroleum, and wherein olefin(e) centent is below 10 weight %.
13. according to the method described in any one in claim 1-12, and wherein, the method also includes that the cleavage reaction product by step (3) obtains carries out separating treatment, and this separating treatment includes:
(i) carry out cooling down and isolated liquid and gas in knockout drum by described cleavage reaction product；
(ii) by described gas phase isolated ethylene and more than C3 fraction in the first knockout tower；
(iii) by described more than C3 fraction at the second knockout tower isolated C3 fraction and more than C4 fraction；
(iv) by C3 fraction at the 3rd knockout tower isolated propylene and propane.
14. methods according to claim 13, wherein, are compressed to 1-4MPa by described gas phase before step (ii).
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| 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 |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition |
| CN103316707A (en) * | 2012-03-20 | 2013-09-25 | 中国石油化工股份有限公司 | Catalyst and method for catalytic cracking of petroleum hydrocarbons |
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| 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 |
| CN102451742A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method for honeycomb supported catalyst containing coating of molecular sieve composition |
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