CN105585410A - Method of catalytically pyrolyzing naphtha to produce propylene - Google Patents
Method of catalytically pyrolyzing naphtha to produce propylene Download PDFInfo
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Abstract
The invention provides a method of catalytically pyrolyzing naphtha to produce propylene. The method includes the step of catalytically pyrolyzing the naphtha in the presence of a first catalyst, a second catalyst and water to obtain a pyrolysis reaction product. The first catalyst includes, by weight, 2-60% of a heat-resistant inorganic oxide and 40-98% of modified ZSM-5 zeolite, wherein the first catalyst is spherical and/or bar-type granules. The second catalyst includes a structured carrier and an active component coating which is distributed on the inner surface and/or the outer surface of the structured carrier. The molecular sieve has a structure of ten-membered ring one-dimension elliptical-shaped pore channels. The method can be used for producing more propylene products by catalytically pyrolyzing the naphtha, the yield of ethylene, propylene and butylene account for more than 93% in total by weight of the total weight of the pyrolysis product, and the yield of propylene is high.
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, differentPropyl benzene, acrylonitrile, acrylic acid etc. Propylene is mainly derived from ethylene cracker and the refining of petrochemical plant at presentThe catalytic cracking unit of oil factory. Along with global propylene demand rapid growth, the output difficulty of traditional processing technologyTo satisfy the demands, the technology of therefore developing propylene enhancing has become important in petrochemical iy produced technologyExhibition direction.
Conventional cracking of ethylene is mainly to pass through steam heat producing ethylene by cracking and propylene taking naphtha as raw material,Limited by heat scission reaction mechanism, general propylene/ethylene ratio is for maximum limit is approximately 0.65, higher than thisRatio, total olefin productive rate will decline. The high-quality feed naphtha that this process need consumption is a large amount of is oneThe process of individual high energy consumption. The propylene of 66-70% is produced with steam heat cracking technique at present.
Catalytic pyrolysis is than the low about 50-200 DEG C of the reaction temperature of steam heat cracking, and energy consumption is lower. And urgeThe reaction mechanism of changing cracking is conducive to form propylene molecules, therefore can realize naphtha and produce propene yieldIncrease.
It is the method for preparing light olefins through fluid catalytic cracking of naphtha that CN102372555A discloses a kind of, withNaphtha and water are raw material, are at 600-750 DEG C in reaction temperature, and weight space velocity is 0.1-2h-1, water withWeight of oil is than under the condition for 0.1-8:1, and raw material contacts with fluid catalyst, and reaction generates etheneWith propylene, wherein used catalyst comprises following component by weight percentage: a) 15.0-60.0% is selected fromKaolin; B) 10.0-30.0% is selected from least one in silica or aluminium oxide; C) 0.5-15.0% choosingAt least one in phosphorus, rare earth or alkaline earth element oxide; D) 25.0-70.0% is selected from directed agents legal systemStandby crystallite dimension is the ZSM-5 zeolite of 200-1000nm.
CN101279881A discloses a kind of method of catalytic pyrolysis naphtha production ethene and propylene, withThe naphtha of C4-C16 hydrocarbon is raw material, before contacting with catalyst after raw material hydrocarbon vaporization, elder generation be reactingThe gas of inertia mixes, and wherein the mol ratio of inert gas and naphtha is for being greater than 0 and be less than or equal to5.0:1, is 580-750 DEG C in reaction temperature, in gauge pressure reaction pressure for being greater than 0 and be less than or equal to0.5MPa, weight space velocity is 0.5-3 hour-1, under the condition that water/naphtha weight ratio is 0-5:1, raw materialGaseous mixture and catalyst haptoreaction generate ethene and propylene, and wherein used catalyst is selected from ZSM-5/ silkGeolyte coexisting molecular sieve, ZSM-5/ beta zeolite coexisting molecular sieve or ZSM-5/Y zeolite coexisting molecular sieveIn at least one.
CN1958731A discloses a kind of catalytic pyrolysis and has produced the method for alkene, wherein will comprise naphtha,The cracking petroleum hydrocarbon raw material of light diesel fuel and hydrogenation tail oil, by two filling different catalysts of connecting up and downThe beds of a and b, carries out catalytic cracking reaction, obtains olefine in low carbon number.
Although above prior art can obtain propylene or light olefin, the yield of propylene is still lower.
Therefore, need to make naphtha catalytic cracking to produce the higher method of propene yield.
Summary of the invention
The object of the invention is to produce low the asking of propene yield in order to overcome prior art naphtha catalytic crackingTopic, provides a kind of naphtha catalytic cracking to produce the method for ethylene, propylene.
To achieve these goals, the invention provides a kind of method of naphtha catalytic cracking product propylene, shouldMethod comprises: under the first catalyst, the second catalyst and water exist, naphtha is carried out to catalytic pyrolysis,Obtain cleavage reaction product; Wherein, taking the gross weight of described the first catalyst as benchmark, described first urgesThe modified ZSM-5 zeolite of the heat-resistant inorganic oxide that agent contains 2-60 % by weight and 40-98 % by weight,Described the first catalyst is spheric granules and/or bar shaped particle; Described the second catalyst comprises that ordered structure carriesBody and the active component coating that is distributed in ordered structure carrier inner surface and/or outer surface; Urge with described secondThe gross weight of agent is benchmark, and the content of described active component coating is 10-50 % by weight; With described workThe gross weight of property component coating is benchmark, the molecular sieve that described active component coating contains 50-95 % by weightMatrix with 5-50 % by weight; Described molecular sieve is the molecule with ten-ring one dimension ellipse duct structureSieve.
By method provided by the invention, can produce the more propylene product of acquisition by catalytic pyrolysis naphthaProduct. In the preferred embodiment of the present invention, the amount of ethene, propylene and the butylene obtaining is splitting of obtainingMore than 93 % by weight of hydrolysis products total amount, and productivity of propylene is high.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
In the present invention, use term ordered structure catalyst to refer to and comprise that ordered structure carrier carries with being distributed inThe catalyst of the active component coating of body inner surface and/or outer surface; Ordered structure carrier is for having regular knotSuch as honeycomb substrate of the carrier of structure; Monolithic reactors is for having loaded ordered structure catalyst as catalysisThe fixed bed reactors of agent bed.
The invention provides a kind of method that naphtha catalytic cracking produces propylene, the method comprises: urge firstAgent, the second catalyst and water carry out catalytic pyrolysis by naphtha under existing, and obtain cleavage reaction product;Wherein, taking the gross weight of described the first catalyst as benchmark, described the first catalyst contains 2-60 % by weightHeat-resistant inorganic oxide and the modified ZSM-5 zeolite of 40-98 % by weight, described the first catalyst is ballShape particle and/or bar shaped particle; Described the second catalyst comprises ordered structure carrier and is distributed in ordered structureThe active component coating of carrier inner surface and/or outer surface; Taking the gross weight of described the second catalyst as baseStandard, the content of described active component coating is 10-50 % by weight; With the gross weight of described active component coatingAmount is benchmark, the base of the molecular sieve that described active component coating contains 50-95 % by weight and 5-50 % by weightMatter; Described molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure.
Can effectively realize object of the present invention according to aforementioned schemes of the present invention, on this basis, thisBright inventor find adopt series connection beaded catalyst and ordered structure catalyst as naphtha catalysisThe beds of propylene is produced in cracking, can realize better naphtha catalytic cracking and produce propylene.
Also on described the first catalyst and described the second catalyst, carry out successively the first catalytic pyrolysis anti-Should with the second catalytic cracking reaction, can realize better naphtha catalytic cracking produce propylene, improve propyleneYield.
According to one of the present invention preferred embodiment, described catalytic pyrolysis carries out as follows:
Under the first catalyst and water existence, naphtha is carried out to the first catalytic pyrolysis, obtain the first crackingProduct oil;
Under the second catalyst and water existence, the first pyrolysis product oil is carried out to the second catalytic pyrolysis, obtainDescribed cleavage reaction product.
In aforementioned preferred embodiment, adopt the first catalyst and the second catalyst as naphtha catalysisThe beds that propylene is produced in cracking carries out the first catalysis respectively on the first catalyst and the second catalystCracking reaction and the second catalytic cracking reaction. Described the first catalyst is that beaded catalyst and described second is urgedAgent is ordered structure catalyst, can realize better naphtha catalytic cracking and produce propylene, improves propyleneYield.
Described the first catalytic pyrolysis and the second catalytic pyrolysis can be at same first beds that is formed withWith in the reactor of the second beds, carry out, also can each leisure be formed with the first bedsThe first reactor and being formed with in the second reactor of the second beds carries out.
According to one of the present invention preferred embodiment, the temperature of the second catalytic pyrolysis is higher than the first catalysisThe temperature 80-200 DEG C of cracking, preferred high 100-180 DEG C. So can further improve the productive rate of propylene.
The preferred embodiment of one according to the present invention, the temperature of described the second catalytic pyrolysis is600-700 DEG C, the temperature of described the first catalytic pyrolysis is 470-550 DEG C. So can further improve thirdThe productive rate of alkene.
According to method provided by the invention, the first catalytic pyrolysis is adopting spheric granules and/or bar shaped particleIn the first reactor of the first beds forming, carry out. Under preferable case, described the first catalysis is splitThe reaction condition of separating also comprises: pressure is 0.02-1MPa, and oil/water charging mass ratio is 1-5:1, and oil entersMaterial weight (hourly) space velocity (WHSV) is 2-15h-1; Preferably, pressure is 0.1-0.5MPa, and oil/water charging mass ratio is 1-2:1, oily charging weight (hourly) space velocity (WHSV) is 4-11h-1。
According to method provided by the invention, the second catalytic pyrolysis adopt that ordered structure catalyst forms theIn the second reactor of two beds, carry out. Under preferable case, the reaction of described the second catalytic pyrolysisCondition comprises: pressure is 0.02-1MPa, and the first pyrolysis product oil/water charging mass ratio is 0.2-8:1, theOne pyrolysis product oil charging weight (hourly) space velocity (WHSV) is 5-45h-1; Preferably, pressure is 0.1-0.5MPa, and first splitsHydrolysis products oil/water charging mass ratio is 0.9-5:1, the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) (with respect toActive component coating) be 20-35h-1. In specific embodiment of the invention, owing to generally only controlling chargingAmount, under the definite condition of inlet amount, the amount of the first pyrolysis product oil is also determined, therefore not specialIn situation about illustrating, described the first pyrolysis product oil/water charging mass ratio be commonly referred to as naphtha (or afterContinuous described processing oil) the charging mass ratio of/water, the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) refers to stoneThe charging weight (hourly) space velocity (WHSV) of cerebrol (or follow-up described processing oil).
In the present invention, the first pyrolysis product oil is preferably by the first cleavage reaction product is carried out to gas-liquid and dividesFrom obtaining, wherein, the first pyrolysis product oil refers to distillate more than C5.
The method according to this invention, preferably the method also comprises pre-treatment step: carrying out catalytic pyrolysisBefore, under pretreatment condition, naphtha is contacted with pretreating agent, obtain processing oil, by described processingOil carries out described catalytic pyrolysis. Naphtha is carried out to pretreatment, can further improve the yield of propylene,May be that pretreatment can help to reduce a small amount of impurity containing in naphtha, such as basic nitrogen etc., helpIn the adverse effect reducing catalyst activity.
In the present invention, the method that the naphtha catalytic cracking providing produces propylene can also comprise urging inactivationAgent is used air regenesis at 450-800 DEG C. The feed volume air speed of air can be 5-15h-1。
According to the present invention, under preferable case, described pretreatment condition comprises: temperature is 20-80 DEG C, pressesPower is 0.02-1MPa, is preferably 0.1-0.2MPa; Naphtha feed weight (hourly) space velocity (WHSV) is 0.5-5h-1; PreferablyTemperature is 25-60 DEG C.
According to the present invention, the condition of preferred pretreatment makes naphtha neutral and alkali nitrogen content below 1 μ g/g,Be preferably 0.4-0.6 μ g/g. So can further improve the productive rate of propylene. If naphtha neutral and alkali nitrogen containsAmount is in aforementioned preferable range, without carrying out described pretreatment. Use aforementioned preferred basic n contentNaphtha carries out catalytic pyrolysis, and productivity of propylene is high.
According to the present invention, described pretreating agent can be to remove a small amount of impurity, for example basic nitrogen in naphthaMaterial. Under preferable case, described pretreating agent is ion exchange resin, and preferred ion exchanger resin isHydrogen styrene type cation exchange resin. More preferably, described ion exchange resin can be highly acid,Faintly acid, oxidation-reduction quality resin; Also can be commercially available, for example trade mark is the catalysis of NKC-9 dry hydrogenThe Hydrogen macropore sulfuric acid resin of resin, CT-175, D005-II, LSI-600, SXC-9.
In the present invention, described pretreating agent can use solvent to regenerate, described solvent can be ethanol,One in acetone and methyl alcohol, carries out described pretreatment and can adopt dual system, uses two covers arranged side by sidePretreatment, can be in the time that a system be carried out pretreatment, and another system is carried out pretreatment regenerative process;Carry out again afterwards two systems and switch, can make described pretreatment realize and carry out continuously.
In the present invention, comprise ordered structure carrier and be distributed in ordered structure carrier inner surface and/or appearanceThe catalyst of the active component coating of face, forms ordered structure catalyst, wherein, and in active component coatingContain the molecular sieve with ten-ring one dimension ellipse duct structure, can more effectively improve naphtha and urgeChange cracking and produce the productive rate of propylene.
According to the present invention, preferably, taking the gross weight of described the second catalyst as benchmark, described active groupThe content of point coating is 15-30 % by weight.
According to the present invention, described ordered structure carrier can be for providing catalyst bed in fixed bed reactorsLayer. This ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, ductInwall on the catalyst coat that can distribute, space, duct can be as the flowing space of fluid. Preferably feelingsUnder condition, described ordered structure carrier is selected from the monolithic substrate of the parallel pore passage structure with both ends open.Described ordered structure carrier can be that the regular carrier of honeycomb fashion that cross section has cellular perforate (is called for short honeycombCarrier).
According to the present invention, under preferable case, the hole density in the cross section of described ordered structure carrier is 6-140Hole/square centimeter, is preferably 20-100 hole/square centimeter; The sectional area in each hole is 0.4-10 square of milliRice, is preferably 2-7 square millimeter; Percent opening is 50-80%. The shape in hole can be square (or the wingWing square, in square hole, the centre bit of four edges is equipped with the inside wing of perpendicular edge, and its length isThe 1/5-2/5 of the square length of side), equilateral triangle, regular hexagon, circle and corrugated in one.
According to the present invention, under preferable case, described ordered structure carrier is selected from cordierite honeycomb carrier, notCarry out at least one in stone honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
According to the present invention, preferably, in described the second catalyst, with the gross weight of described active component coatingAmount is benchmark, the base of the molecular sieve that described active component coating contains 80-95 % by weight and 5-20 % by weightMatter.
According to the present invention, in described the second catalyst, described molecular sieve is for having ten-ring one dimension ellipseThe molecular sieve of pore passage structure, preferably duct opening diameter is in 0.45-0.56 nanometer.
According to the present invention, in described the second catalyst, preferred described molecular sieve is the molecule of TON structureThe molecular sieve of sieve and/or MTT structure, wherein structure type TON, MTT refer to international zeolite associatingThe molecular sieve structure of meeting (IZA) name, for describing the space topological structure in molecular sieve duct. DescribedThe molecular sieve of TON structure, comprises that Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 boilStone, ZSM-22 zeolite and SSZ-32 zeolite etc., the molecular sieve of MTT structure comprise ZSM-23 zeolite,EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite etc.
For the present invention, in described the second catalyst, preferred described molecular sieve is Theta-1 zeolite, ISI-1Zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite, SSZ-32 zeolite, ZSM-23 zeolite,At least one in EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite.
According to the present invention, the molecular sieve that preferred described molecular sieve is TON structure and the molecule of MTT structureThe mixture of sieve. More preferably, the weight of the molecular sieve of the molecular sieve of described TON structure and MTT structureThan being 0.1-10:1, more preferably 1-5:1.
According to the preferred embodiment of the present invention, the molecular sieve of described TON structure, preferably includes Theta-1In zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeoliteOne or more.
According to the preferred embodiment of the present invention, the molecular sieve of described MTT structure comprises that ZSM-23 boilsOne or more in stone, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite.
According to the present invention, in described the second catalyst, under preferable case, described matrix can be selected from oxidationIn aluminium, silica, amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxideAt least one. Preferably, described matrix is one or more in silica, aluminium oxide and kaolin.
In the present invention, obtain described the second catalyst and can adopt the preparation of conventional ordered structure catalystMethod, this is no longer going to repeat them.
In the present invention, heat-resistant inorganic oxide and 40-98 that described the first catalyst contains 2-60 % by weightThe modified ZSM-5 zeolite of % by weight, described heat-resistant inorganic oxide can be conventionally used as carrier for this areaMaterial, for example can be preferably aluminium oxide.
According to the present invention, under preferable case, taking the gross weight of described modified ZSM-5 zeolite as benchmark,The modifying element that described modified ZSM-5 zeolite contains 1-10 % by weight, described modifying element is selected from rare earthAt least one in metal, IVB family metal, phosphorus, iron, zinc, tin and vanadium. Wherein, described rare earth goldGenus can be selected from lanthanide series metal or yttrium, and IVB family metal can be preferably titanium or zirconium.
In the present invention, the preparation of described modified ZSM-5 zeolite can adopt the modification side of this area routineMethod is carried out, and this is no longer going to repeat them.
According to the present invention, under preferable case, the sial atomic molar ratio of described modified ZSM-5 zeolite is15-100:1; Be preferably 50-100:1.
In the present invention, obtain described the first catalyst and can adopt this area routine to use, prepare sphericalThe method of particle and/or bar shaped particle, for example bar shaped catalyst can be particle diameter 2-3mm, particleThe bar shaped particle of length 2-5mm. This is no longer going to repeat them.
According to the present invention, under preferable case, described naphtha is paraffinic base naphtha, and wherein, alkene containsAmount is below 10 % by weight; Under preferable case, alkene that described naphtha contains 0.5-1.5 % by weight,The alkane of 40-60 % by weight, the cycloalkane of 20-40 % by weight and 10-20 % by weight aromatic hydrocarbons.
According to the present invention, in the cleavage reaction product obtaining, contain ethene and propylene. Under preferable case, shouldMethod also comprises carries out separating treatment by the cleavage reaction product obtaining, and this separating treatment comprises: (a) willDescribed cleavage reaction product carries out cooling and separates and obtain liquid and gas in knockout drum; (b) willDescribed gas phase separates and obtains ethene and the above cut of C3 in the first knockout tower; (c) by more than described C3Cut separates and obtains C3 cut and the above cut of C4 at the second knockout tower, described in 22-76 % by weightThe above cut of C4 for example, as catalytic pyrolysis raw material the cut of 30～85 DEG C (boiling range); (d) C3 is heated up in a steamerDivide at the 3rd knockout tower and separate and obtain propylene and propane.
According to the present invention, in the separating treatment of carrying out, under preferable case, before will in step (b)Described gas phase is compressed to 1-4MPa; Preferably described gas phase is compressed to 2-3MPa.
In the present invention, preferably, described gas phase enters the first knockout tower stage casing, at the bottom of the first knockout tower towerObtain the above cut of C3; Above C3 cut is sent into the second knockout tower stage casing, at the second knockout tower towerTop obtains C3 cut, obtains the above cut of C4 at the bottom of the second knockout tower tower, and C3 cut enters the 3rd point1/4 place at the bottom of from tower from tower, in the above cut of C4, preferred 30-66 % by weight is as catalytic pyrolysis raw material; ?The tower top lateral line withdrawal function of the 3rd knockout tower obtains propylene.
According to the present invention, under preferable case, described liquid phase is the above cut of C5.
In the present invention, can between described the first catalytic pyrolysis and described the second catalytic pyrolysis, there is one to addHot stove, by heating material, improves the temperature of the reactant that enters described the second catalytic pyrolysis.
In the present invention, relate to pressure and all represent with gauge pressure.
Below will describe the present invention by embodiment.
In following examples, basic n content records by constant-current titration method. Gas-phase product character is passed throughGas chromatography analysis method, adopts the chromatographic apparatus of Agilent company 6890 models to measure. Yield and choosingSelecting property calculates by following formula:
Yield=(object product is (as (C2 ＝+C3 ＝) growing amount/reaction-ure feeding amount) × 100%
Selectively=(object product is as (C2 ＝～C4 ＝) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The present embodiment produces the method for propylene for naphtha catalytic cracking of the present invention is described.
(1) pretreatment. Under 60 DEG C, 0.1MPa, by naphtha (containing alkene 1 % by weight, containing alkaneHydrocarbon 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, containing basic nitrogen 50 μ g/g) withWeight (hourly) space velocity (WHSV) 1h-1Contact the processing basic nitrogen in oils content obtaining with NKC-9 dry hydrogen catalyst resinBe 0.5 μ g/g.
(2) produce propylene. The processing oil that (1) is obtained and water are after 250 DEG C of preheatings, and injection is equipped with theIn the fixed bed reactors of one catalyst granules, carry out, after the first catalytic pyrolysis, reinjecting the second catalysis being housedThe regular reactor of agent carries out the second catalytic pyrolysis.
(sial atom rubs the ZRP-1 zeolite of the La modification that wherein, the first catalyst contains 95 % by weightYou are than being 50), the aluminium oxide of 5 % by weight, wherein, the content of La is 10 % by weight. The first catalystFor particle diameter is the bar shaped catalyst that 2mm, length are 2mm;
The second catalyst is ordered structure catalyst, and ordered structure catalyst used comprises that cordierite honeycomb carries(carrier hole density is 100 hole/square centimeters to body, and the sectional area in each hole is 7 square millimeters, percent openingBe 80%) and content be the active component coating of 20 % by weight, in active component coating, contain 90 weightThe ZSM-22 zeolite (sial atomic molar ratio is 30) of %, the matrix (aluminium oxide) of 10 % by weight.
The reaction condition of the first catalytic pyrolysis comprises: temperature is 470 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 650 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The product that the second catalytic cracking reaction is obtained passes into condenser condenses, and condensed product passes into gasLiquid knockout drum separates and obtains liquid and gas. Gas-phase product is further passed into the first knockout tower stage casing, pointFrom obtaining the above cut of ethene and C3. Above C3 cut is further passed into the second knockout tower stage casing to be enteredRow separates, and obtains the above cut of C4 at the bottom of the second knockout tower tower, obtains C3 at the second knockout tower tower topCut. C3 cut is further passed into the 3rd knockout tower separation and obtain propane and propylene.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Embodiment 2
The present embodiment produces the method for propylene for naphtha catalytic cracking of the present invention is described.
(1) pretreatment. Under 30 DEG C, 0.2MPa, by naphtha (containing alkene 1 % by weight, containing alkaneHydrocarbon 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, containing basic nitrogen 50 μ g/g) withWeight (hourly) space velocity (WHSV) 5h-1Contact with LSI-600 ion exchange resin, the processing basic nitrogen in oils content obtaining is0.4μg/g。
(2) produce propylene. The processing oil that (1) is obtained and water are after 250 DEG C of preheatings, and injection is equipped with theIn the fixed bed reactors of one catalyst granules, carry out, after the first catalytic pyrolysis, reinjecting the second catalysis being housedAgent is that regular reactor carries out the second catalytic pyrolysis.
(sial atom rubs the ZSM-5 zeolite of the Fe modification that wherein, the first catalyst contains 90 % by weightYou are than being 75), the aluminium oxide of 10 % by weight, wherein, the content of Fe is 5 % by weight. The first catalystFor particle diameter is the bar shaped catalyst that 2.5mm, length are 5mm;
The second catalyst is ordered structure catalyst, and ordered structure catalyst used comprises that cordierite honeycomb carries(carrier hole density is 80 hole/square centimeters to body, and the sectional area in each hole is 5 square millimeters, percent openingBe 60%) and content be the active component coating of 15 % by weight, in active component coating, contain 95 weightThe ZSM-23 zeolite (sial atomic molar ratio is 50) of %, the matrix (silica) of 5 % by weight.
The reaction condition of the first catalytic pyrolysis comprises: temperature is 550 DEG C, and pressure is 0.3MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 10.5hr-1, oil/water charge ratio is 1.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 700 DEG C, and pressure is 0.5MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 35hr-1, oil/water charge ratio is 0.9.
The product that the second catalytic cracking reaction is obtained passes into condenser condenses, and condensed product passes into gasLiquid knockout drum separates and obtains liquid and gas. Gas-phase product is further passed into the first knockout tower stage casing, pointFrom obtaining the above cut of ethene and C3. Above C3 cut is further passed into the second knockout tower stage casing to be enteredRow separates, and obtains the above cut of C4 at the bottom of the second knockout tower tower, obtains C3 at the second knockout tower tower topCut. C3 cut is further passed into the 3rd knockout tower separation and obtain propane and propylene.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Embodiment 3
The present embodiment produces the method for propylene for naphtha catalytic cracking of the present invention is described.
(1) pretreatment. Under 50 DEG C, 0.1MPa, by naphtha (containing alkene 1 % by weight, containing alkaneHydrocarbon 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, containing basic nitrogen 50 μ g/g) withWeight (hourly) space velocity (WHSV) 3h-1Contact with CT-175 ion exchange resin, the processing basic nitrogen in oils content obtaining is0.6μg/g。
(2) produce propylene. The processing oil that (1) is obtained and water are after 250 DEG C of preheatings, and injection is equipped with theIn the fixed bed reactors of one catalyst granules, carry out, after the first catalytic pyrolysis, reinjecting the second catalysis being housedThe regular reactor of agent carries out the second catalytic pyrolysis.
(sial atom rubs the ZSM-5 zeolite of the P modification that wherein, the first catalyst contains 85 % by weightYou are than being 100), the aluminium oxide of 15 % by weight, wherein, the content of P is 2 % by weight. The first catalystFor particle diameter is the bar shaped catalyst that 3mm, length are 5mm;
The second catalyst is ordered structure catalyst, and ordered structure catalyst used comprises that cordierite honeycomb carries(carrier hole density is 20 hole/square centimeters to body, and the sectional area in each hole is 2 square millimeters, percent openingBe 75%) and content be the active component coating of 25 % by weight, in active component coating, contain 80 amount %NU-10 zeolite (sial atomic molar ratio is 80), the matrix of 20 % by weight (aluminium oxide+kaolin,Weight ratio is 1:1).
The reaction condition of the first catalytic pyrolysis comprises: temperature is 500 DEG C, and pressure is 0.5MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 4.6hr-1, oil/water charge ratio is 1.61.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 600 DEG C, and pressure is 0.2MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 20hr-1, oil/water charge ratio is 5.
The product that the second catalytic cracking reaction is obtained passes into condenser condenses, and condensed product passes into gasLiquid knockout drum separates and obtains liquid and gas. Gas-phase product is further passed into the first knockout tower stage casing, pointFrom obtaining the above cut of ethene and C3. Above C3 cut is further passed into the second knockout tower stage casing to be enteredRow separates, and obtains the above cut of C4 at the bottom of the second knockout tower tower, obtains C3 at the second knockout tower tower topCut. C3 cut is further passed into the 3rd knockout tower separation and obtain propane and propylene.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, different, in catalyst, molecular sieve is by ZSM-22Zeolite (sial atomic molar ratio is 30) and ISI-4 zeolite (sial atomic molar ratio is 30) replace,And the part by weight of the two is 1:1.
Embodiment 5
According to the method cracking naphtha of embodiment 3, different, in catalyst, molecular sieve is by NU-10Zeolite (sial atomic molar ratio is 80) and ZSM-23 zeolite (sial atomic molar ratio is 50) generationReplace, and the part by weight of the two is 2:1.
Embodiment 6
According to the method cracking naphtha of embodiment 3, different, in catalyst, molecular sieve is by SSZ-32Zeolite (sial atomic molar ratio is 30) and KZ-1 zeolite (sial atomic molar ratio is 50) replace,And the part by weight of the two is 5:1.
Embodiment 7
According to the method for embodiment 1, different, first contact ordered structure catalyst, then contactGrain catalyst. Be in step (2), first contact and carry out with the second catalyst (ordered structure catalyst)The first catalytic pyrolysis, then contacts product to carry out the second catalytic pyrolysis with the first catalyst.
The reaction condition of the first catalytic pyrolysis comprises: temperature is 650 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 25hr-1, oil/water charge ratio is 1.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 470 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 6.3hr-1, oil/water charge ratio is 2.
Embodiment 8
Carry out according to the method for embodiment 1, different, do not carry out described pre-treatment step and directly enterRow catalytic pyrolysis.
Embodiment 9
Carry out according to the method for embodiment 1, different, the first catalytic pyrolysis and the second catalytic pyrolysisTemperature is identical, is 470 DEG C.
Embodiment 10
Carry out according to the method for embodiment 1, different, the first catalytic pyrolysis and the second catalytic pyrolysisTemperature is identical, is 650 DEG C.
Embodiment 11
Carry out according to the method for embodiment 1, different, the temperature of the first catalytic pyrolysis is 650 DEG C,The temperature of the second catalytic pyrolysis is 470 DEG C.
Comparative example 1
(1) pretreatment. Under 60 DEG C, 0.1MPa, by naphtha (containing alkene 1 % by weight, containing alkaneHydrocarbon 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, containing basic nitrogen 50 μ g/g) withWeight (hourly) space velocity (WHSV) 1h-1Contact with NKC-9 dry acid catalyst resin, the processing basic nitrogen in oils content obtaining is0.5μg/g。
(2) produce propylene. The processing oil that (1) is obtained and water are after 250 DEG C of preheatings, and injection is equipped with theIn the fixed bed reactors of one catalyst granules, carry out, after the first catalytic pyrolysis, reinjecting the second catalysis being housedThe regular reactor of agent carries out the second catalytic pyrolysis.
(sial is former for the ZRP-1 zeolite of the La modification that wherein, the first catalyst contains content 95 % by weightSub-mol ratio is 50), content is the aluminium oxide of 5 % by weight, wherein, the content of La is 10% weight.The first catalyst is that particle diameter is the bar shaped catalyst that 2mm, length are 2mm;
The second catalyst is the ZSM-22 zeolite (sial atomic molar ratio is 30) that contains 18 % by weightWith the particle diameter of the matrix (aluminium oxide) of 82 % by weight be the bar shaped catalysis that 2mm, length are 2mmAgent.
The reaction condition of the first catalytic pyrolysis comprises: temperature is 470 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 650 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The product that the second catalytic cracking reaction is obtained passes into condenser condenses, and condensed product passes into gasLiquid knockout drum separates and obtains liquid and gas. Gas-phase product is further passed into the first knockout tower stage casing, pointFrom obtaining the above cut of ethene and C3. Above C3 cut is further passed into the second knockout tower stage casing to be enteredRow separates, and obtains the above cut of C4 at the bottom of the second knockout tower tower, obtains C3 at the second knockout tower tower topCut. C3 cut is further passed into the 3rd knockout tower separation and obtain propane and propylene.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Comparative example 2
(1) pretreatment. Under 60 DEG C, 0.1MPa, by naphtha (containing alkene 1 % by weight, containing alkaneHydrocarbon 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, containing basic nitrogen 50 μ g/g) withWeight (hourly) space velocity (WHSV) 1h-1Contact with NKC-9 dry acid catalyst resin, the processing basic nitrogen in oils content obtaining is0.5μg/g。
(2) produce propylene. The processing oil that (1) is obtained and water are after 250 DEG C of preheatings, and injection is equipped with theIn the fixed bed reactors of one catalyst granules, carry out, after the first catalytic pyrolysis, reinjecting the second catalysis being housedThe regular reactor of agent carries out the second catalytic pyrolysis.
(sial is former for the ZRP-1 zeolite of the La modification that wherein, the first catalyst contains content 95 % by weightSub-mol ratio is 50), content is the aluminium oxide of 5 % by weight, wherein, the content of La is 10 % by weight.The first catalyst is that particle diameter is the bar shaped catalyst that 2mm, length are 2mm;
The second catalyst is ordered structure catalyst, and ordered structure catalyst used comprises that cordierite honeycomb carries(carrier hole density is 100 hole/square centimeters to body, and the sectional area in each hole is 7 square millimeters, percent openingBe 80%) and content be the active component coating of 20 % by weight, in active component coating, contain 90 weightThe Beta zeolite (sial atomic molar ratio is 30) of %, the matrix (aluminium oxide) of 10 % by weight.
The reaction condition of the first catalytic pyrolysis comprises: temperature is 470 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) is 6.3hr-1, oil/water charge ratio is 2.
The reaction condition of the second catalytic pyrolysis comprises: temperature is 650 DEG C, and pressure is 0.1MPa, processes oilCharging weight (hourly) space velocity (WHSV) (with respect to the gross weight of active component coating) is 25hr-1, oil/water charge ratio is 1.
The product that the second catalytic cracking reaction is obtained passes into condenser condenses, and condensed product passes into gasLiquid knockout drum separates and obtains liquid and gas. Gas-phase product is further passed into the first knockout tower stage casing, pointFrom obtaining the above cut of ethene and C3. Above C3 cut is further passed into the second knockout tower stage casing to be enteredRow separates, and obtains the above cut of C4 at the bottom of the second knockout tower tower, obtains C3 at the second knockout tower tower topCut. C3 cut is further passed into the 3rd knockout tower separation and obtain propane and propylene.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Table 1
Can find out that from the data result of table 1 method provided by the invention is split carrying out naphtha catalysisSeparate and produce in propylene, can obtain high ethene and propene yield, and wherein propylene/ethylene ratio is greater than 1,Can realize producing more propylene.
Claims (14)
1. naphtha catalytic cracking produces a method for propylene, and the method comprises:
Under the first catalyst, the second catalyst and water exist, naphtha is carried out to catalytic pyrolysis, obtainCleavage reaction product;
Wherein, taking the gross weight of described the first catalyst as benchmark, described the first catalyst contains 2-60The modified ZSM-5 zeolite of the heat-resistant inorganic oxide of % by weight and 40-98 % by weight, described the first catalysisAgent is spheric granules and/or bar shaped particle;
Described the second catalyst comprise ordered structure carrier and be distributed in ordered structure carrier inner surface and/orThe active component coating of outer surface; Taking the gross weight of described the second catalyst as benchmark, described active componentThe content of coating is 10-50 % by weight; Taking the gross weight of described active component coating as benchmark, described workThe molecular sieve that property component coating contains 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve isThere is the molecular sieve of ten-ring one dimension ellipse duct structure.
2. method according to claim 1, wherein, described catalytic pyrolysis carries out as follows:
Under the first catalyst and water existence, naphtha is carried out to the first catalytic pyrolysis, obtain the first crackingProduct oil;
Under the second catalyst and water existence, the first pyrolysis product oil is carried out to the second catalytic pyrolysis, obtainDescribed cleavage reaction product.
3. method according to claim 2, wherein, the temperature of the second catalytic pyrolysis is higher than firstThe temperature 80-200 DEG C of catalytic pyrolysis, preferred high 100-180 DEG C.
4. according to the method in claim 2 or 3, wherein, the temperature of described the second catalytic pyrolysisFor 600-700 DEG C, the temperature of described the first catalytic pyrolysis is 470-550 DEG C.
5. according to the method described in any one in claim 2-4, wherein,
The reaction condition of described the first catalytic pyrolysis comprises: pressure is 0.02-1MPa, oil/water charging qualityThan being 1-5:1, oily charging weight (hourly) space velocity (WHSV) is 2-15h-1; Preferably, pressure is 0.1-0.5MPa, oil/Water charging mass ratio is 1-2:1, and oily charging weight (hourly) space velocity (WHSV) is 4-11h-1；
The reaction condition of described the second catalytic pyrolysis comprises: pressure is 0.02-1MPa, oil/water charging qualityThan being 0.2-8:1, oily charging weight (hourly) space velocity (WHSV) is 5-45h-1; Preferably, pressure is 0.1-0.5MPa, firstPyrolysis product oil/water charging mass ratio is 0.9-5:1, and the first pyrolysis product oil charging weight (hourly) space velocity (WHSV) is20-35h-1。
6. according to the method described in any one in claim 1-5, wherein, the method also comprises:Carrying out before catalytic pyrolysis, under pretreatment condition, naphtha is contacted with pretreating agent, processedOil, carries out described catalytic pyrolysis by described processing oil.
7. according to the method described in any one in claim 6, wherein, described pretreating agent be fromSub-exchange resin, described pretreatment condition comprises: temperature is 20-80 DEG C, pressure is 0.02-1MPa,Naphtha feed weight (hourly) space velocity (WHSV) is 0.5-5h-1。
8. according to the method described in any one in claim 1-7, wherein, described molecular sieve is TONThe molecular sieve of the molecular sieve of structure and/or MTT structure.
9. method according to claim 8, wherein, described molecular sieve is the molecule of TON structureThe mixture of the molecular sieve of sieve and MTT structure; Preferably, the molecular sieve of described TON structure and MTTThe weight ratio of the molecular sieve of structure is 0.1-10:1, more preferably 1-5:1; The molecule of described TON structureSieve comprise Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite andOne or more in SSZ-32 zeolite; The molecular sieve of described MTT structure comprise ZSM-23 zeolite,One or more in EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite.
10. according to the method described in any one in claim 1-9, wherein, described ordered structure carriesBody is selected from the monolithic substrate of the parallel pore passage structure with both ends open.
11. methods according to claim 10, wherein, the cross section of described ordered structure carrierHole density is that the sectional area in 6-140 hole/square centimeter, each hole is 0.4-10 square millimeter, and percent opening is50-80％。
12. according to the method described in any one in claim 1-11, wherein, and described ordered structureCarrier is selected from cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeybeeAt least one in nest carrier.
13. according to the method described in any one in claim 1-2, wherein, and with described modified ZSM-5The gross weight of zeolite is benchmark, the modifying element that described modified ZSM-5 zeolite contains 1-10 % by weight,Described modifying element is selected from least one in rare earth metal, IVB family metal, phosphorus, iron, zinc, tin and vanadiumKind, wherein, the sial atomic molar of described modified ZSM-5 zeolite is than being 15-100:1.
14. according to the method described in any one in claim 1-13, and wherein, described naphtha isParaffinic base naphtha, wherein, olefin(e) centent is below 10 % by weight.
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