CN105585410B - The method that naphtha catalytic cracking produces propylene - Google Patents
The method that naphtha catalytic cracking produces propylene Download PDFInfo
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Abstract
The present invention provides a kind of method that naphtha catalytic cracking produces propylene, and this method includes：In the presence of the first catalyst, the second catalyst and water, naphtha is subjected to catalytic pyrolysis, cleavage reaction product is obtained；First catalyst contains 2 60 weight % heat-resistant inorganic oxide and the 40 98 weight % zeolite of modified ZSM-5 5, and first catalyst is spheric granules and/or bar shaped particle；Second catalyst includes ordered structure carrier and is distributed in ordered structure carrier inner surface and/or the active component coating of outer surface；The molecular sieve is the molecular sieve with the one-dimensional ellipse pore passage structure of ten-ring.The method that the present invention is provided, can obtain more propylene products, the amount of obtained ethene, propylene and butylene is more than the 93 weight % of obtained pyrolysis product total amount, and productivity of propylene is high with the production of catalytic pyrolysis naphtha.
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, isopropylbenzene, propylene
Nitrile, acrylic acid etc..Current propylene is mainly derived from the ethylene cracker of petrochemical plant and the catalytic cracking unit of oil plant.With
Global propylene demand rapid growth, the yield of traditional processing technology is difficult to meet demand, therefore develops the technology of propylene enhancing
As an important development direction in petrochemical iy produced technology.
Conventional ethylene cracking is mainly by raw material of naphtha by steam heat producing ethylene by cracking and propylene, wherein heated
Cracking reaction mechanism limit, general propylene/ethylene ratio be 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 the process of a high energy consumption.Current 66-70% propylene
Produced with steam pyrolysis technology.
Catalytic pyrolysis is lower than the reaction temperature of steam thermal cracking about 50-200 DEG C, and energy consumption is relatively low.And catalytic pyrolysis
Reaction mechanism advantageously forms propylene molecules, therefore can realize naphtha production propene yield increase.
CN102372555A disclose it is a kind of be preparing light olefins through fluid catalytic cracking of naphtha method, with naphtha and water
For raw material, in the case where reaction temperature is 600-750 DEG C, weight space velocity is 0.1-2h-1, water is 0.1-8 with weight of oil ratio:1 condition
Under, raw material is in contact with fluid catalyst, and reaction generation ethene and propylene, wherein used catalyst are wrapped by weight percentage
Containing following components：A) 15.0-60.0% is selected from kaolin；B) 10.0-30.0% in silica or aluminum oxide at least one
Kind；C) 0.5-15.0% is selected from least one of phosphorus, rare earth or alkaline earth element oxide；D) 25.0-70.0%, which is selected from, is oriented to
Crystallite dimension prepared by agent method is 200-1000nm ZSM-5 zeolite.
A kind of method that CN101279881A discloses catalytic pyrolysis naphtha production ethene and propylene, with C4-C16 hydrocarbon
Naphtha is raw material, before being contacted after raw material hydrocarbon vaporization with catalyst, first with the gas mixing inert to reaction, wherein indifferent gas
The mol ratio of body and naphtha is more than 0 and less than or equal to 5.0:1, it is 580-750 DEG C, the reaction pressure in terms of gauge pressure in reaction temperature
Power is that, more than 0 and less than or equal to 0.5MPa, weight space velocity is 0.5-3 hours-1, water/naphtha weight ratio is 0-5:1 condition
Under, material mixed gas generate ethene and propylene with catalyst haptoreaction, and wherein used catalyst is selected from ZSM-5/ modenites
At least one of coexisting molecular sieve, ZSM-5/ beta zeolite coexistings molecular sieve or ZSM-5/Y zeolite coexisting molecular sieves.
CN1958731A discloses a kind of method of catalytic pyrolysis producing olefinic hydrocarbons, wherein will comprising naphtha, light diesel fuel and
The cracking petroleum hydrocarbon raw material of hydrogenation tail oil, by two filling different catalysts a and b of series connection up and down beds, enters
Row catalytic cracking reaction, obtains olefine in low carbon number.
Although above prior art results in propylene or light olefin, but the yield of propylene is still relatively low.
It is therefore desirable to be able to make naphtha catalytic cracking produce the higher method of propene yield.
The content of the invention
The invention aims to overcome prior art naphtha catalytic cracking produce propene yield it is low the problem of there is provided
A kind of method that naphtha catalytic cracking produces ethylene, propylene.
To achieve these goals, the present invention provides a kind of method that naphtha catalytic cracking produces propylene, and this method includes：
In the presence of the first catalyst, the second catalyst and water, naphtha is subjected to catalytic pyrolysis, cleavage reaction product is obtained；Wherein,
On the basis of the gross weight of first catalyst, first catalyst contain 2-60 weight % heat-resistant inorganic oxide and
40-98 weight % modified ZSM-5 zeolite, first catalyst is spheric granules and/or bar shaped particle；Second catalysis
Agent includes ordered structure carrier and is distributed in ordered structure carrier inner surface and/or the active component coating of outer surface；With described
On the basis of the gross weight of second catalyst, the content of the active component coating is 10-50 weight %；Applied with the active component
On the basis of the gross weight of layer, the active component coating contains 50-95 weight % molecular sieve and 5-50 weight % matrix；Institute
Molecular sieve is stated for the molecular sieve with the one-dimensional ellipse pore passage structure of ten-ring.
The method provided by the present invention, can obtain more propylene products with the production of catalytic pyrolysis naphtha.In this hair
In bright preferred embodiment, the amount of obtained ethene, propylene and butylene be 93 weight % of obtained pyrolysis product total amount with
On, and productivity of propylene is high.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, refer to include ordered structure carrier using term ordered structure catalyst and be distributed in carrier inner surface
And/or the catalyst of the active component coating of outer surface；Ordered structure carrier is such as cellular set of the carrier with ordered structure
Body；Monolithic reactors are the fixed bed reactors for having loaded ordered structure catalyst as beds.
The present invention provides a kind of method that naphtha catalytic cracking produces propylene, and this method includes：In the first catalyst, second
In the presence of catalyst and water, naphtha is subjected to catalytic pyrolysis, cleavage reaction product is obtained；Wherein, with first catalyst
Gross weight on the basis of, heat-resistant inorganic oxide that first catalyst contains 2-60 weight % and 40-98 weight %'s changes
Property ZSM-5 zeolite, first catalyst be spheric granules and/or bar shaped particle；Second catalyst includes ordered structure
Carrier and it is distributed in ordered structure carrier inner surface and/or the active component coating of outer surface；With the total of second catalyst
On the basis of weight, the content of the active component coating is 10-50 weight %；Using the gross weight of the active component coating as base
Standard, the active component coating contains 50-95 weight % molecular sieve and 5-50 weight % matrix；The molecular sieve be with
The molecular sieve of the one-dimensional ellipse pore passage structure of ten-ring.
The purpose of the present invention can be effectively realized according to previously described versions of the present invention, on this basis, invention of the invention
People has found to produce the catalyst bed of propylene as naphtha catalytic cracking using the beaded catalyst and ordered structure catalyst of series connection
Layer, can be better achieved naphtha catalytic cracking production propylene.
Namely the first catalytic cracking reaction and second are carried out successively on first catalyst and second catalyst
Catalytic cracking reaction, can be better achieved naphtha catalytic cracking production propylene, improve the yield of propylene.
According to one kind of the present invention preferred embodiment, the catalytic pyrolysis is carried out as follows：
In the presence of the first catalyst and water, naphtha is subjected to the first catalytic pyrolysis, the first pyrolysis product oil is obtained；
In the presence of the second catalyst and water, the first pyrolysis product oil is subjected to the second catalytic pyrolysis, the cracking is obtained
Reaction product.
In preceding preferred embodiment, third is produced as naphtha catalytic cracking using the first catalyst and the second catalyst
The beds of alkene, carry out the first catalytic cracking reaction on the first catalyst and the second catalyst respectively and the second catalysis is split
Solution reaction.First catalyst is beaded catalyst and second catalyst is ordered structure catalyst, can be preferably
Realize that naphtha catalytic cracking produces propylene, improve the yield of propylene.
First catalytic pyrolysis and the second catalytic pyrolysis can be urged in same the first beds and second that are formed with
Carried out in the reactor of agent bed, can also each leisure be formed with the first reactor of the first beds and be formed with the
Carried out in the second reactor of two beds.
According to one kind of the present invention preferred embodiment, the temperature of the second catalytic pyrolysis is higher than the temperature of the first catalytic pyrolysis
80-200 DEG C of degree is preferably high 100-180 DEG C.It so can further improve the yield of propylene.
According to a kind of preferred embodiment of the present invention, the temperature of second catalytic pyrolysis is 600-700 DEG C, institute
The temperature for stating the first catalytic pyrolysis is 470-550 DEG C.It so can further improve the yield of propylene.
According to the method that provides of the present invention, the first catalytic pyrolysis is using spheric granules and/or bar shaped granuloplastic the
Carried out in the first reactor of one beds.Under preferable case, the reaction condition of first catalytic pyrolysis also includes：Pressure
Power is 0.02-1MPa, and oil/water charge-mass ratio is 1-5：1, oil charging weight (hourly) space velocity (WHSV) is 2-15h-1；Preferably, pressure is 0.1-
0.5MPa, oil/water charge-mass ratio is 1-2：1, oil charging weight (hourly) space velocity (WHSV) is 4-11h-1。
The method provided according to the present invention, the second catalytic pyrolysis is in the second catalyst using ordered structure catalyst formation
Carried out in the second reactor of bed.Under preferable case, the reaction condition of second catalytic pyrolysis includes：Pressure is 0.02-
1MPa, the first pyrolysis product oil/water charge-mass ratio is 0.2-8:1, the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) is 5-45h-1；
Preferably, pressure is 0.1-0.5MPa, and the first pyrolysis product oil/water charge-mass ratio is 0.9-5:1, the first pyrolysis product oil enters
It is 20-35h to expect weight (hourly) space velocity (WHSV) (relative to active component coating)-1.The present invention specific implementation in, due to normally only control into
Doses, under conditions of inlet amount determination, the amount of the first pyrolysis product oil is also determined, therefore in situation about being not particularly illustrated
Under, the first pyrolysis product oil/water charge-mass ratio is commonly referred to as entering for naphtha (or follow-up described processing oil)/water
Mass ratio is expected, when the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) refers to the charging weight of naphtha (or follow-up described processing oil)
Air speed.
In the present invention, the first pyrolysis product oil is obtained preferably by by the progress gas-liquid separation of the first cleavage reaction product,
Wherein, the first pyrolysis product oil refers to more than C5 distillate.
With the method for the invention it is preferred to which this method also includes pre-treatment step：I.e. before catalytic pyrolysis is carried out, locating in advance
Under the conditions of reason, naphtha is contacted with pretreating agent, processing oil is obtained, the processing oil is subjected to the catalytic pyrolysis.By stone
Cerebrol is pre-processed, and can further improve the yield of propylene, it may be possible to which pretreatment can help to reduce in naphtha to contain
A small amount of impurity, such as basic nitrogen, help to reduce to the adverse effect of catalyst activity.
In the present invention there is provided naphtha catalytic cracking production propylene method can also include the catalyst of inactivation is existed
Air regenesis is used at 450-800 DEG C.The feed volume air speed of air can be 5-15h-1。
, according to the invention it is preferred in the case of, the pretreatment condition includes：Temperature is 20-80 DEG C, and pressure is 0.02-
1MPa, preferably 0.1-0.2MPa；Naphtha feed weight (hourly) space velocity (WHSV) is 0.5-5h-1；Preferable temperature is 25-60 DEG C.
, according to the invention it is preferred to which the condition of pretreatment causes naphtha neutral and alkali nitrogen content in below 1 μ g/g, it is preferably
0.4-0.6μg/g.It so can further improve the yield of propylene.If naphtha neutral and alkali nitrogen content is in foregoing preferred scope,
The pretreatment need not then be carried out.Catalytic pyrolysis is carried out using the naphtha of foregoing preferred basic n content, productivity of propylene is high.
According to the present invention, the pretreating agent can remove a small amount of impurity, the material of such as basic nitrogen in naphtha.It is excellent
In the case of choosing, the pretreating agent is ion exchange resin, and preferred ion exchanger resin is Hydrogen polystyrene cation exchange
Resin.It is highly preferred that the ion exchange resin can be highly acid, faintly acid, oxidation-reduction quality resin；Commercially available it can also obtain
, such as trade mark is NKC-9 dry acid catalyst resins, CT-175, D005-II, LSI-600, SXC-9 Hydrogen macropore sulfonic acid tree
Fat.
In the present invention, the pretreating agent can use solvent to be regenerated, and the solvent can be ethanol, acetone and first
One kind in alcohol, dual system can be used by carrying out the pretreatment, i.e., can be in a system using two sets of pretreatments arranged side by side
When being pre-processed, another system carries out pretreatment regenerative process；Carry out two systems switching again afterwards, can make described pre-
Processing realization is carried out continuously.
In the present invention, including ordered structure carrier and the activity for being distributed in ordered structure carrier inner surface and/or outer surface
The catalyst of component coating, forms ordered structure catalyst, wherein, containing in active component coating has the one-dimensional ellipse of ten-ring
The molecular sieve of type pore passage structure, can more effectively improve the yield that naphtha catalytic cracking produces propylene.
In accordance with the present invention it is preferred that, on the basis of the gross weight of second catalyst, the active component coating contains
Measure as 15-30 weight %.
According to the present invention, the ordered structure carrier can be used for providing beds in fixed bed reactors.The rule
Whole structure carrier can be the carrier block of monoblock, and inside is formed can be distributed catalysis on hollow pore passage structure, the inwall in duct
Agent coating, duct space may be used as the flowing space of fluid.Under preferable case, the ordered structure carrier, which is selected from, has two ends
The monolithic substrate of the parallel channels structure of opening.The ordered structure carrier can be the honeycomb that section has cellular perforate
The regular carrier of formula (abbreviation honeycomb substrate).
, according to the invention it is preferred in the case of, the hole density in the section of the ordered structure carrier for 6-140 holes/square li
Rice, preferably 20-100 holes/square centimeter；The sectional area in each hole is 0.4-10 square millimeters, preferably 2-7 square millimeters；
Percent opening is 50-80%.The shape in hole can for square (or wing square, i.e., the center of four edges in square hole
There is an inside wing of vertical edges position, and its length is the 1/5-2/5 of the square length of side), equilateral triangle, regular hexagon, circle and ripple
One kind in line shape.
, according to the invention it is preferred in the case of, the ordered structure carrier is selected from cordierite honeycomb carrier, mullite cellular set
At least one of body, cellular alumina carrier and metal alloy honeycomb substrate.
In accordance with the present invention it is preferred that, in second catalyst, on the basis of the gross weight of the active component coating,
The active component coating contains 80-95 weight % molecular sieve and 5-20 weight % matrix.
According to the present invention, in second catalyst, the molecular sieve is with the one-dimensional ellipse pore passage structure of ten-ring
Molecular sieve, preferably channel openings diameter is at 0.45-0.56 nanometers.
According to the present invention, in second catalyst, preferably described molecular sieve is tied for the molecular sieve and/or MTT of TON structures
The molecular sieve of structure, wherein structure type TON, MTT refer to the molecular sieve structure of International Zeolite Association meeting (IZA) name, for retouching
State the Space expanding in duct in molecular sieve.The molecular sieve of the TON structures, including Theta-1 zeolites, ISI-1 zeolites,
KZ-2 zeolites, NU-10 zeolites, ZSM-22 zeolites and SSZ-32 zeolites etc., the molecular sieve of MTT structures include ZSM-23 zeolites, EU-
13 zeolites, ISI-4 zeolites and KZ-1 zeolites etc..
For the present invention, in second catalyst, preferably described molecular sieve is Theta-1 zeolites, ISI-1 zeolites, KZ-
2 zeolites, NU-10 zeolites, ZSM-22 zeolites, SSZ-32 zeolites, ZSM-23 zeolites, EU-13 zeolites, ISI-4 zeolites and KZ-1 boilings
At least one of stone.
, according to the invention it is preferred to the molecular sieve for TON structures molecular sieve and MTT structures molecular sieve mixture.
It is further preferred that the weight ratio of the molecular sieve of the TON structures and the molecular sieve of MTT structures is 0.1-10:1, more preferably 1-5:1.
According to the preferred embodiment of the present invention, the molecular sieve of the TON structures preferably includes Theta-1 zeolites, ISI-
One or more in 1 zeolite, KZ-2 zeolites, NU-10 zeolites, ZSM-22 zeolites and SSZ-32 zeolites.
According to the preferred embodiment of the present invention, the molecular sieves of the MTT structures include ZSM-23 zeolites, EU-13 zeolites,
One or more in ISI-4 zeolites and KZ-1 zeolites.
According to the present invention, in second catalyst, under preferable case, the matrix can selected from aluminum oxide, silica,
At least one of amorphous silica-alumina, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide.Preferably, the matrix is
One or more in silica, aluminum oxide and kaolin.
In the present invention, the preparation method of conventional ordered structure catalyst can be used by obtaining second catalyst,
This is no longer repeated one by one.
In the present invention, first catalyst contains 2-60 weight % heat-resistant inorganic oxide and 40-98 weight %
Modified ZSM-5 zeolite, the heat-resistant inorganic oxide can be conventionally used as the material of carrier for this area, for example, can be preferably
Aluminum oxide.
, according to the invention it is preferred in the case of, on the basis of the gross weight of the modified ZSM-5 zeolite, the modified ZSM-5
Zeolite contains 1-10 weight % modifying element, the modifying element be selected from rare earth metal, Group IVB metal, phosphorus, iron, zinc, tin and
At least one of vanadium.Wherein, the rare earth metal can be selected from lanthanide series metal or yttrium, Group IVB metal can be preferably titanium or
Zirconium.
In the present invention, preparing for the modified ZSM-5 zeolite can be carried out using the conventional method of modifying in this area, herein
No longer repeat one by one.
, according to the invention it is preferred in the case of, the sial atomic molar ratio of the modified ZSM-5 zeolite is 15-100：1；It is excellent
Elect 50-100 as:1.
In the present invention, obtain first catalyst can using commonly used in the art, prepare spheric granules and/or
The method of bar shaped particle, such as bar shaped catalyst can be particle diameter 2-3mm, particle length 2-5mm bar shaped particle.Herein
No longer repeat one by one.
, according to the invention it is preferred in the case of, the naphtha is paraffin based naphtha, wherein, olefin(e) centent is 10 weights
Measure below %；Under preferable case, the naphtha contains 0.5-1.5 weight % alkene, 40-60 weight % alkane, 20-40
Weight % cycloalkane and 10-20 weight % aromatic hydrocarbons.
According to the present invention, ethene and propylene are contained in obtained cleavage reaction product.Under preferable case, this method also includes
Obtained cleavage reaction product is subjected to separating treatment, the separating treatment includes：(a) cleavage reaction product is cooled down
And in knockout drum isolated liquid and gas；(b) by the gas phase in the first knockout tower isolated ethene and
More than C3 cuts；(c) by more than the C3 cuts in the isolated C3 cuts of the second knockout tower and more than C4 cuts, by 22-76
Weight % more than the C4 cuts are used as catalytic pyrolysis raw material (such as cut of 30~85 DEG C of boiling range)；(d) C3 cuts are existed
The 3rd isolated propylene of knockout tower and propane.
According to the present invention, in the separating treatment of progress, under preferable case, the gas phase is compressed before step (b)
To 1-4MPa；It is preferred that the gas phase is compressed into 2-3MPa.
In the present invention, it is preferable that the gas phase enters the first separation midsection, and more than C3 is obtained in the first knockout tower bottom of towe
Cut；More than C3 cuts feeding second is separated into midsection, C3 cuts are obtained in the second separation column overhead, in the second knockout tower tower
Bottom obtains more than C4 cuts, C3 cuts enter the 3rd knockout tower from bottom of towe 1/4 at, preferred 30-66 weight % in more than C4 cuts
It is used as catalytic pyrolysis raw material；Propylene is obtained in the tower top lateral line withdrawal function of the 3rd knockout tower.
, according to the invention it is preferred in the case of, the liquid phase is more than C5 cuts.
In the present invention, there can be a heating furnace between first catalytic pyrolysis and second catalytic pyrolysis by thing
Material heating, improves the temperature for the reactant for entering second catalytic pyrolysis.
In the present invention, it is related to pressure and is represented with gauge pressure.
The present invention will be described in detail by way of examples below.
In following examples, basic n content is measured by constant-current titration method.Gas-phase product property passes through gas-chromatography
Analysis method, is determined using the chromatographic apparatus of the model of Agilent company 6890.Yield and selectivity are calculated by below equation
Arrive：
Yield=(purpose product (such as (C2 =+C3 =) growing amount/reaction-ure feeding amount) × 100%
Selectivity=(purpose product such as (C2 =~C4 =) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The present embodiment is used for the method for illustrating that the naphtha catalytic cracking of the present invention produces propylene.
(1) pre-process.Under 60 DEG C, 0.1MPa, by naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing ring
The weight % of alkane 32, containing the weight % of aromatic hydrocarbons 11, containing the μ g/g of basic nitrogen 50) with weight (hourly) space velocity (WHSV) 1h-1With NKC-9 dry hydrogen catalyst resins
Contact, obtained processing basic nitrogen in oils content is 0.5 μ g/g.
(2) propylene is produced.After the processing oil and water that (1) is obtained are preheated through 250 DEG C, injection is equipped with the first catalyst granules
Carried out in fixed bed reactors after the first catalytic pyrolysis, reinject the regular reactor equipped with the second catalyst and carry out the second catalysis
Cracking.
Wherein, the ZRP-1 zeolites (sial atomic molar ratio is 50) that the La that the first catalyst contains 95 weight % is modified, 5
Weight % aluminum oxide, wherein, La content is 10 weight %.First catalyst is that particle diameter is that 2mm, length are 2mm's
Bar shaped catalyst；
Second catalyst is ordered structure catalyst, and ordered structure catalyst used includes cordierite honeycomb carrier (carrier
Hole density is 100 holes/square centimeter, and the sectional area in each hole is 7 square millimeters, and percent opening is 80%) and content is 20 weights
% active component coating is measured, (sial atomic molar ratio is for ZSM-22 zeolites in active component coating containing 90 weight %
30), 10 weight % matrix (aluminum oxide).
The reaction condition of first catalytic pyrolysis includes：Temperature is 470 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Speed is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of second catalytic pyrolysis includes：Temperature is 650 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The reaction product that second catalytic cracking reaction is obtained is passed through condenser condensation, and condensed product is passed through knockout drum
Isolated liquid and gas.Gas-phase product is further passed through to the first separation midsection, isolated ethene and more than C3 evaporate
Point.More than C3 cuts are further passed through into the second separation midsection to be separated, obtaining more than C4 in the second knockout tower bottom of towe evaporates
Point, obtain C3 cuts in the second separation column overhead.C3 cuts are further passed through the 3rd isolated propane of knockout tower and propylene.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Embodiment 2
The present embodiment is used for the method for illustrating that the naphtha catalytic cracking of the present invention produces propylene.
(1) pre-process.Under 30 DEG C, 0.2MPa, by naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing ring
The weight % of alkane 32, containing the weight % of aromatic hydrocarbons 11, containing the μ g/g of basic nitrogen 50) with weight (hourly) space velocity (WHSV) 5h-1With LSI-600 ion exchange resin
Contact, obtained processing basic nitrogen in oils content is 0.4 μ g/g.
(2) propylene is produced.After the processing oil and water that (1) is obtained are preheated through 250 DEG C, injection is equipped with the first catalyst granules
Carried out in fixed bed reactors after the first catalytic pyrolysis, it is that regular reactor carries out the second catalysis to reinject equipped with the second catalyst
Cracking.
Wherein, the ZSM-5 zeolite (sial atomic molar ratio is 75) that the Fe that the first catalyst contains 90 weight % is modified, 10
Weight % aluminum oxide, wherein, Fe content is 5 weight %.First catalyst is that particle diameter is that 2.5mm, length are 5mm's
Bar shaped catalyst；
Second catalyst is ordered structure catalyst, and ordered structure catalyst used includes cordierite honeycomb carrier (carrier
Hole density is 80 holes/square centimeter, and the sectional area in each hole is 5 square millimeters, and percent opening is 60%) and content is 15 weight %
Active component coating, the ZSM-23 zeolites (sial atomic molar ratio is 50) in active component coating containing 95 weight %, 5 weights
Measure % matrix (silica).
The reaction condition of first catalytic pyrolysis includes：Temperature is 550 DEG C, and pressure is 0.3MPa, and processing oil charging weighs space-time
Speed is 10.5hr-1, oil/water charge ratio is 1.
The reaction condition of second catalytic pyrolysis includes：Temperature is 700 DEG C, and pressure is 0.5MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 35hr-1, oil/water charge ratio is 0.9.
The reaction product that second catalytic cracking reaction is obtained is passed through condenser condensation, and condensed product is passed through knockout drum
Isolated liquid and gas.Gas-phase product is further passed through to the first separation midsection, isolated ethene and more than C3 evaporate
Point.More than C3 cuts are further passed through into the second separation midsection to be separated, obtaining more than C4 in the second knockout tower bottom of towe evaporates
Point, obtain C3 cuts in the second separation column overhead.C3 cuts are further passed through the 3rd isolated propane of knockout tower and propylene.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Embodiment 3
The present embodiment is used for the method for illustrating that the naphtha catalytic cracking of the present invention produces propylene.
(1) pre-process.Under 50 DEG C, 0.1MPa, by naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing ring
The weight % of alkane 32, containing the weight % of aromatic hydrocarbons 11, containing the μ g/g of basic nitrogen 50) with weight (hourly) space velocity (WHSV) 3h-1With CT-175 ion exchange resin
Contact, obtained processing basic nitrogen in oils content is 0.6 μ g/g.
(2) propylene is produced.After the processing oil and water that (1) is obtained are preheated through 250 DEG C, injection is equipped with the first catalyst granules
Carried out in fixed bed reactors after the first catalytic pyrolysis, reinject the regular reactor equipped with the second catalyst and carry out the second catalysis
Cracking.
Wherein, the ZSM-5 zeolite (sial atomic molar ratio is 100) that the P that the first catalyst contains 85 weight % is modified, 15
Weight % aluminum oxide, wherein, P content is 2 weight %.First catalyst is that particle diameter is the bar that 3mm, length are 5mm
Shape catalyst；
Second catalyst is ordered structure catalyst, and ordered structure catalyst used includes cordierite honeycomb carrier (carrier
Hole density is 20 holes/square centimeter, and the sectional area in each hole is 2 square millimeters, and percent opening is 75%) and content is 25 weight %
Active component coating, the NU-10 zeolites (sial atomic molar ratio is 80) in active component coating containing 80 amount %, 20 weights
(aluminum oxide+kaolin, weight ratio is 1 to amount % matrix:1).
The reaction condition of first catalytic pyrolysis includes：Temperature is 500 DEG C, and pressure is 0.5MPa, and processing oil charging weighs space-time
Speed is 4.6hr-1, oil/water charge ratio is 1.61.
The reaction condition of second catalytic pyrolysis includes：Temperature is 600 DEG C, and pressure is 0.2MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 20hr-1, oil/water charge ratio is 5.
The reaction product that second catalytic cracking reaction is obtained is passed through condenser condensation, and condensed product is passed through knockout drum
Isolated liquid and gas.Gas-phase product is further passed through to the first separation midsection, isolated ethene and more than C3 evaporate
Point.More than C3 cuts are further passed through into the second separation midsection to be separated, obtaining more than C4 in the second knockout tower bottom of towe evaporates
Point, obtain C3 cuts in the second separation column overhead.C3 cuts are further passed through the 3rd isolated propane of knockout tower and propylene.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, unlike, molecular sieve is by ZSM-22 zeolite (sial in catalyst
30) atomic molar ratio is replaces with ISI-4 zeolites (sial atomic molar ratio is 30), and the part by weight of the two is 1:1.
Embodiment 5
According to the method cracking naphtha of embodiment 3, unlike, (sial is former by NU-10 zeolites for molecular sieve in catalyst
80) sub- mol ratio is replaces with ZSM-23 zeolites (sial atomic molar ratio is 50), and the part by weight of the two is 2:1.
Embodiment 6
According to the method cracking naphtha of embodiment 3, unlike, molecular sieve is by SSZ-32 zeolite (sial in catalyst
30) atomic molar ratio is replaces with KZ-1 zeolites (sial atomic molar ratio is 50), and the part by weight of the two is 5:1.
Embodiment 7
According to the method for embodiment 1, unlike, ordered structure catalyst is first contacted, beaded catalyst is then contacted.I.e.
In step (2), first contact with the second catalyst (ordered structure catalyst) and carries out the first catalytic pyrolysis, then by reaction product and
The contact of first catalyst carries out the second catalytic pyrolysis.
The reaction condition of first catalytic pyrolysis includes：Temperature is 650 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Speed is 25hr-1, oil/water charge ratio is 1.
The reaction condition of second catalytic pyrolysis includes：Temperature is 470 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 6.3hr-1, oil/water charge ratio is 2.
Embodiment 8
Carried out according to the method for embodiment 1, unlike, directly carry out catalysis without the pre-treatment step and split
Solution.
Embodiment 9
Carried out according to the method for embodiment 1, unlike, the temperature of the first catalytic pyrolysis and the second catalytic pyrolysis is identical,
It is 470 DEG C.
Embodiment 10
Carried out according to the method for embodiment 1, unlike, the temperature of the first catalytic pyrolysis and the second catalytic pyrolysis is identical,
It is 650 DEG C.
Embodiment 11
Carried out according to the method for embodiment 1, unlike, the temperature of the first catalytic pyrolysis is 650 DEG C, the second catalytic pyrolysis
Temperature be 470 DEG C.
Comparative example 1
(1) pre-process.Under 60 DEG C, 0.1MPa, by naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing ring
The weight % of alkane 32, containing the weight % of aromatic hydrocarbons 11, containing the μ g/g of basic nitrogen 50) with weight (hourly) space velocity (WHSV) 1h-1Connect with NKC-9 dry acid catalyst resins
Touch, obtained processing basic nitrogen in oils content is 0.5 μ g/g.
(2) propylene is produced.After the processing oil and water that (1) is obtained are preheated through 250 DEG C, injection is equipped with the first catalyst granules
Carried out in fixed bed reactors after the first catalytic pyrolysis, reinject the regular reactor equipped with the second catalyst and carry out the second catalysis
Cracking.
Wherein, (sial atomic molar ratio is for ZRP-1 zeolites that the first catalyst contains the weight % of content 95 La is modified
50), content is 5 weight % aluminum oxide, wherein, La content is 10% weight.First catalyst be particle diameter be 2mm,
Length is 2mm bar shaped catalyst；
Second catalyst is ZSM-22 zeolites (sial atomic molar ratio is 30) and 82 weight % containing 18 weight %
The particle diameter of matrix (aluminum oxide) is the bar shaped catalyst that 2mm, length are 2mm.
The reaction condition of first catalytic pyrolysis includes：Temperature is 470 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Speed is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of second catalytic pyrolysis includes：Temperature is 650 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The reaction product that second catalytic cracking reaction is obtained is passed through condenser condensation, and condensed product is passed through knockout drum
Isolated liquid and gas.Gas-phase product is further passed through to the first separation midsection, isolated ethene and more than C3 evaporate
Point.More than C3 cuts are further passed through into the second separation midsection to be separated, obtaining more than C4 in the second knockout tower bottom of towe evaporates
Point, obtain C3 cuts in the second separation column overhead.C3 cuts are further passed through the 3rd isolated propane of knockout tower and propylene.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Comparative example 2
(1) pre-process.Under 60 DEG C, 0.1MPa, by naphtha (the weight % of olefin-containing 1, containing the weight % of alkane 56, containing ring
The weight % of alkane 32, containing the weight % of aromatic hydrocarbons 11, containing the μ g/g of basic nitrogen 50) with weight (hourly) space velocity (WHSV) 1h-1Connect with NKC-9 dry acid catalyst resins
Touch, obtained processing basic nitrogen in oils content is 0.5 μ g/g.
(2) propylene is produced.After the processing oil and water that (1) is obtained are preheated through 250 DEG C, injection is equipped with the first catalyst granules
Carried out in fixed bed reactors after the first catalytic pyrolysis, reinject the regular reactor equipped with the second catalyst and carry out the second catalysis
Cracking.
Wherein, (sial atomic molar ratio is for ZRP-1 zeolites that the first catalyst contains the weight % of content 95 La is modified
50), content is 5 weight % aluminum oxide, wherein, La content is 10 weight %.First catalyst be particle diameter be 2mm,
Length is 2mm bar shaped catalyst；
Second catalyst is ordered structure catalyst, and ordered structure catalyst used includes cordierite honeycomb carrier (carrier
Hole density is 100 holes/square centimeter, and the sectional area in each hole is 7 square millimeters, and percent opening is 80%) and content is 20 weights
The Beta zeolites (sial atomic molar ratio is 30) in % active component coating, active component coating containing 90 weight % are measured,
10 weight % matrix (aluminum oxide).
The reaction condition of first catalytic pyrolysis includes：Temperature is 470 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Speed is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of second catalytic pyrolysis includes：Temperature is 650 DEG C, and pressure is 0.1MPa, and processing oil charging weighs space-time
Fast (relative to gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The reaction product that second catalytic cracking reaction is obtained is passed through condenser condensation, and condensed product is passed through knockout drum
Isolated liquid and gas.Gas-phase product is further passed through to the first separation midsection, isolated ethene and more than C3 evaporate
Point.More than C3 cuts are further passed through into the second separation midsection to be separated, obtaining more than C4 in the second knockout tower bottom of towe evaporates
Point, obtain C3 cuts in the second separation column overhead.C3 cuts are further passed through the 3rd isolated propane of knockout tower and propylene.
Calculate (C2 =+C3 =) yield and (C2 =~C4 =) selectivity, the results are shown in Table 1.
Table 1
The method that the present invention is provided is can be seen that from the data result of table 1, naphtha catalytic cracking production propylene is being carried out
In, high ethene and propene yield can be obtained, and wherein propylene/ethylene ratio is more than 1, it is possible to achieve producing more propylene.
Claims (16)
1. a kind of method that naphtha catalytic cracking produces propylene, this method includes：
In the presence of the first catalyst, the second catalyst and water, naphtha is subjected to catalytic pyrolysis, cleavage reaction product is obtained；
Wherein, the catalytic pyrolysis is carried out as follows：
In the presence of the first catalyst and water, naphtha is subjected to the first catalytic pyrolysis, the first pyrolysis product oil is obtained；
In the presence of the second catalyst and water, the first pyrolysis product oil is subjected to the second catalytic pyrolysis, the cracking reaction is obtained
Product；
On the basis of the gross weight of first catalyst, first catalyst contains 2-60 weight % heat resistant inorganic oxidation
The modified ZSM-5 zeolite of thing and 40-98 weight %, first catalyst is spheric granules and/or bar shaped particle；
Second catalyst includes ordered structure carrier and is distributed in the activity of ordered structure carrier inner surface and/or outer surface
Component coating；On the basis of the gross weight of second catalyst, the content of the active component coating is 10-50 weight %；
On the basis of the gross weight of the active component coating, the active component coating contains 50-95 weight % molecular sieve and 5-
50 weight % matrix；The molecular sieve is the molecular sieve with the one-dimensional ellipse pore passage structure of ten-ring, and the molecular sieve is
The molecular sieve of TON structures and/or the molecular sieve of MTT structures.
2. according to the method described in claim 1, wherein, the temperature of the second catalytic pyrolysis is higher than the temperature of the first catalytic pyrolysis
80-200℃。
3. according to the method described in claim 1, wherein, the temperature of the second catalytic pyrolysis is higher than the temperature of the first catalytic pyrolysis
100-180℃。
4. the method according to any one in claim 1-3, wherein, the temperature of second catalytic pyrolysis is 600-
700 DEG C, the temperature of first catalytic pyrolysis is 470-550 DEG C.
5. the method according to any one in claim 1-3, wherein,
The reaction condition of first catalytic pyrolysis includes：Pressure is 0.02-1MPa, and oil/water charge-mass ratio is 1-5：1, oil
Charging weight (hourly) space velocity (WHSV) is 2-15h-1；
The reaction condition of second catalytic pyrolysis includes：Pressure is 0.02-1MPa, and oil/water charge-mass ratio is 0.2-8:1,
Oil charging weight (hourly) space velocity (WHSV) is 5-45h-1。
6. the method according to any one in claim 1-3, wherein,
The reaction condition of first catalytic pyrolysis includes：Pressure is 0.1-0.5MPa, and oil/water charge-mass ratio is 1-2：1, oil
Charging weight (hourly) space velocity (WHSV) is 4-11h-1；
The reaction condition of second catalytic pyrolysis includes：Pressure is 0.1-0.5MPa, the first pyrolysis product oil/water feedstock quality
Than for 0.9-5:1, the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) is 20-35h-1。
7. the method according to any one in claim 1-3, wherein, this method also includes：Before catalytic pyrolysis is carried out,
Under pretreatment condition, naphtha is contacted with pretreating agent, processing oil is obtained, the processing oil is carried out into the catalysis splits
Solution.
8. method according to claim 7, wherein, the pretreating agent is ion exchange resin, the pretreatment condition
Including：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。
9. according to the method described in claim 1, wherein, the molecular sieve for TON structures molecular sieve and MTT structures molecule
The mixture of sieve；The molecular sieve of the TON structures include Theta-1 zeolites, ISI-1 zeolites, KZ-2 zeolites, NU-10 zeolites,
One or more in ZSM-22 zeolites and SSZ-32 zeolites；The molecular sieve of the MTT structures includes ZSM-23 zeolites, EU-13
One or more in zeolite, ISI-4 zeolites and KZ-1 zeolites.
10. method according to claim 9, wherein, the weight of the molecular sieve of the TON structures and the molecular sieve of MTT structures
Amount is than being 0.1-10:1.
11. method according to claim 9, wherein, the weight of the molecular sieve of the TON structures and the molecular sieve of MTT structures
Amount is than being 1-5:1.
12. according to the method described in claim 1, wherein, the ordered structure carrier be selected from both ends open parallel hole
The monolithic substrate of road structure.
13. the method according to claim 1 or 12, wherein, the hole density in the section of the ordered structure carrier is 6-140
Hole/square centimeter, the sectional area in each hole are 0.4-10 square millimeters, and percent opening is 50-80%.
14. the method according to claim 1 or 12, wherein, the ordered structure carrier is selected from cordierite honeycomb carrier, not
Come at least one of stone honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
15. according to the method described in claim 1, wherein, it is described to change on the basis of the gross weight of the modified ZSM-5 zeolite
Property ZSM-5 zeolite contain 1-10 weight % modifying element, the modifying element be selected from rare earth metal, Group IVB metal, phosphorus, iron,
At least one of zinc, tin and vanadium, wherein, the sial atomic molar ratio of the modified ZSM-5 zeolite is 15-100：1.
16. according to the method described in claim 1, wherein, the naphtha be paraffin based naphtha, wherein, olefin(e) centent is
Below 10 weight %.
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| CN1958731A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for producing olefin through catalytic cracking |
| 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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| CN1958731A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for producing olefin through catalytic cracking |
| 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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