CN102649677A - Method for preparing aromatic hydrocarbon by aromatizing C4 hydrocarbon - Google Patents
Method for preparing aromatic hydrocarbon by aromatizing C4 hydrocarbon Download PDFInfo
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Abstract
The invention relates to a method for preparing aromatic hydrocarbon by aromatizing C4 hydrocarbon. According to the method, the technical problem of easy inactivity of a catalyst due to carbon deposition in the prior art is mainly solved. According to the method disclosed by the invention, with the C4 hydrocarbon as a raw material and under the conditions that the reaction temperature is 300-600DEG C, the reaction pressure is 0.1-1MPa and the weight space velocity is 0.1-20hour<-1>, the C4 hydrocarbon as the raw material and the catalyst are contacted to perform an aromatization reaction to generate the aromatic hydrocarbon in a fixed bed reactor, wherein the catalyst is mesoporous ZSM-11 zeolite of which the silicon-aluminum mol ratio of SiO2 to Al2O3 is 40-200 and the grain size is less than and equal to 500 nanometers. According to the method disclosed by the invention, the problem is better solved; and the method can be used for the industrial production of the preparation of the aromatic hydrocarbon by aromatizing the C4 hydrocarbon.
Description
Technical field
The present invention relates to the method that a kind of mixed c 4 aromizing prepares aromatic hydrocarbons.
Background technology
Light aromatic hydrocarbons benzene, toluene and YLENE (BTX) are widely used in synthon, synthetic resins, viton and various fine chemicals.Toluene and YLENE are still produced the important mediation component of stop bracket gasoline.The main source of aromatic hydrocarbons is from CR, pressure gasoline and coke by-products, to separate to obtain in the world.Carbon four hydrocarbon that the steam cracking device of refinery and various CCU by-product are a large amount of.In recent years, along with the minimizing day by day of petroleum resources, with abundant cheap lighter hydrocarbons resource, the research that changes the benzene,toluene,xylene (BTX) of high added value into had become current important research project and hot issue.
As far back as the forties in last century, just light-hydrocarbon aromatized technology has been carried out research and discovery abroad.Exploitation, especially the MFI type zeolite (being ZSM-5) of Mobil company mesopore zeolite have characteristics such as good shape selective catalysis performance, thermostability and catalyst life length after getting into the seventies in last century, and light-hydrocarbon aromatized technology just is achieved.Uop Inc. of the BP company in 1984 and the U.S. has developed jointly Cyclar technology [R.E Anderson; J.A.Johnson, J.R.Mowry.Processing of LPG to Aromatics and Hydrogen.The AICHE Spring National Meeting, Houston; Tex; Mar.24-28,1985], this technology is with C
3～C
4Hydrocarbon or LPG liquefied petroleum gas are raw material, adopt the modified zsm-5 zeolite catalyzer of BP company invention and the simulation moving-bed regeneration techniques of Uop Inc..Aromatics yield reaches 55～66% (to fresh feeds).Build up a cover scale in the refinery of Grange-mouth Scottand BP company the end of the year 1989 is 1.5 * 10
4The industrial demonstration unit in ton/year adopts the continuous catalyst regenerating technology that LPG liquefied petroleum gas is converted into aromatic hydrocarbons and by-product hydrogen [oil and gas chemical industry, 2005,34 (3): 165-167].The ZSM-5 sieve catalyst [US6124515] of this process application gallium modification, raw material and beds generation aromatization.Ga/HZSM-5 sieve catalyst aromatization activity is high, and physical strength is good, has stronger anti-coking performance and anti-hydrothermal deactivation ability, and continuous operation still kept high activity and selectivity in several days, satisfied the requirement of moving bed reaction and regeneration condition technology.This process using moving-bed though catalyzer can cyclic regeneration, adopts the moving-bed cost of investment high.
Disclosed some aromatization of low carbon hydrocarbon Catalysts and its preparation methods in the following patent documentation:
US 4150062 (1979) has disclosed a kind of zeolite with carbon two～C 4 olefin production high-octane rating aromatic type gasoline, is through metal ion-modified ZSM-5, ZSM-11, ZSM-12, ZSM-35 or ZSM-38 zeolite.Introduced the aromatization effect of a kind of potassium modified ZSM-5 in fixed-bed reactor in the embodiment in detail.Wherein, in order to reduce the carbon distribution deactivation rate of catalyzer, this patent adopts water as co-fed (water/olefin molar ratio is 0.5～15).
US 0192539A1 (2004) has disclosed a kind of synthetic silicon-germanium-aluminium zeolite; When synthetic, directly introduce germanium atom and get into zeolite framework; This zeolite molecular sieve gets the finished product molecular sieve-4 A through dip loading platinum; The ZSM-5 platinum get molecular sieve B, ZSM-5 and germanium oxide mechanically mixing again platinum get molecular sieve C, be raw material with propane, through estimating the back discovery; Molecular sieve-4 A has higher BTX selectivity (BTX content reaches 56-57wt% in the product), and its selectivity almost remained unchanged at 150 hours.
US 7186872B2 (2007) has disclosed and a kind ofly directly gallium has been introduced zeolite framework; The Pt/Ga-ZSM-5 zeolite molecular sieve of platinum then; The Pt/ZSM-5 molecular sieve relatively (is raw material with propane) of the Pt/Ga/ZSM-5 zeolite molecular sieve of load gallium, platinum and a platinum successively coexists on the zeolite molecular sieve; The Pt/Ga-ZSM-5 zeolite molecular sieve shows higher BTX selectivity (72 hours, the BTX selectivity is 50wt%).
CN 101088614A (2007) has disclosed a kind of aromatized eutectic superfine zeolite grain catalyst; Ultrafine particle eutectic zeolite be among ZSM-5/ZSM-11 and the ZSM-5/Beta one or both; To account for weight ratio be 50～90wt% to ZSM-5 in the eutectic zeolite, and the grain fineness number of ultrafine particle eutectic zeolite is 20～500 nanometers; Consist of: transition metal oxide (one or more in nickel oxide, molybdenum oxide and the zinc oxide) content is 0.5～10wt%; Lanthanide rare MOX (lanthanum trioxide/or cerium oxide) content is 0.5～5wt%; Ultrafine particle eutectic zeolite content 50～90wt%, surplus is an inorganic oxide adhesive.Zeolite support carries out hydrothermal treatment consists, and (water/solid volume ratio is: be warming up to 500～600 ℃ under 1: 1～10: 1 the steam atmosphere; And thermostat(t)ed water thermal treatment 3～15 hours under this temperature); Adding equivalent concentration in the ratio of liquid/solid volume than 2: 1.0～5.0: 1.0 then is dilute inorganic acid solution (hydrochloric acid, nitric acid, phosphoric acid or the carbonic acid of 0.1～2.0 mol; Its equivalent concentration is 0.2～1.0 mol; 20～100 ℃ stir down rinsings, 110～140 ℃ dry 8～15 hours down, 400～500 ℃ of following roastings 3～10 hours).This catalyst applications significantly reduces FCC gasoline sulfur and olefin(e) centent in FCC gasoline hydrodesulfurizationmethod/aromizing combination process.
CN 1552821A (2004) has disclosed a kind of ultrafine particle zeolite aromatized catalyst; The ultrafine particle zeolite is that grain fineness number is the HZSM-5 and/or the Hbeta of 20～800 nanometers; (the content sum is 1.0～10wt%), gets said aromatized catalyst through steam treatment, pickling, drying and roasting afterwards through carrying transition metal oxide compound and lanthanide rare MOX.
CN 1586721A (2004) has disclosed a kind of Catalysts and its preparation method of carbon four LPG liquefied petroleum gas aromizing; With grain fineness number is the ZSM-5 zeolite of 10～500 nanometers; The ZSM-8 zeolite; The ZSM-11 zeolite is a matrix, gets said aromatized catalyst through steam treatment, pickling, drying, roasting.
But; Though the aromatized catalyst with existing method preparation has good Aromatizatian catalytic performance; But the coking and deactivation speed of catalyzer is fast, and one way is short running period, and operations such as loaded metal, steam treatment and pickling have increased the Preparation of catalysts cost.Template is a kind of effective ways that prepare mesoporous zeolite.ZSM-11 adopts hydrothermal method synthetic, the synthetic middle specific template that needs to adopt.Mostly above-mentioned carbon four aromizing catalyst system therefors are metal-modified micro porous molecular sieve, and the application of superfine mesoporous ZSM-11 molecular sieve in the reaction of carbon four hydrocarbon aromatizings do not appear in the newspapers.
Summary of the invention
Technical problem to be solved by this invention is to exist the catalyzer that uses to be prone to the problem of carbon distribution inactivation in the technology in the past, provides a kind of new carbon four hydrocarbon aromatizings reaction to produce the method for aromatic hydrocarbons.This method has that catalyzer anti-carbon performance is good, the advantage of long service life.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of mixed c 4 aromizing prepares the method for aromatic hydrocarbons, is raw material with the mixed c 4 hydrocarbon, is 300～600 ℃ in temperature of reaction; Reaction pressure is 0.1～1MPa, and mass space velocity is 0.1～20 hour
-1Condition under, material carbon four hydrocarbon contact with catalyzer and aromatization takes place generate aromatic hydrocarbons in fixed-bed reactor, wherein used catalyzer is silica alumina ratio SiO
2/ Al
2O
3Be 40～200, size of microcrystal is the mesoporous ZSM-11 zeolite of≤500 nanometers.
In the technique scheme, raw material is 50～90% mixed c 4 for the alkene weight content; Mesoporous ZSM-11 zeolite particle diameter is 100～500 nanometers; The value of the mesoporous volume/micro pore volume of mesoporous ZSM-11 zeolite is 2.5～4; Temperature of reaction is 370～530 ℃, and reaction pressure is 0.1～1MPa, and the raw materials quality air speed is 0.5～6 hour
-1
Used mesoporous ZSM-11 prepare zeolite method among the present invention comprises:
A) earlier with the alkali source solution I that gets soluble in water, the aluminium source is joined in the solution I, get the solution II, in the solution II, add the organic ammonium template and get the solution III, in the solution III, add silicon source, organic polymer template at last, obtain raw mix.Wherein raw mix is counted SiO by mole
2/ Al
2O
3=40～200, Na
2O/SiO
2=0.05～0.2, H
2O/SiO
2=8～50, organic ammonium/SiO
2=0.03～0.3, organic polymer/SiO
2=0.0001～0.1.Wherein said organic ammonium is selected from least a in tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide or the 4-propyl bromide; Said alkali source is selected from least a in Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, rubidium hydroxide or the cesium hydroxide; Said silicon source is selected from least a in tetraethoxy, silicon sol, silica gel, water glass, the white carbon black; Said aluminium source is selected from least a in aluminum oxide, sodium aluminate, sodium metaaluminate, aluminum nitrate, aluminum chloride, white lake, kaolin, Tai-Ace S 150, the aluminum isopropylate; Said organic polymer is selected from least a in starch or the polyoxyethylene glycol;
B) raw mix that a) step is made is under 60～200 ℃ of conditions at crystallization temperature, hydrothermal crystallizing 24～480 hours, the mesoporous ZSM-11 zeolite of size of microcrystal≤500 nanometers.
C) with b) step make product through routine washing to neutral, centrifugal, dry; 550 ℃ of roastings 5～10 hours; Is the ammonium ion solution of 0.1～1.0 mol with the mesoporous ZSM-11 zeolite powder after the roasting with concentration, and the liquid-solid volume ratio according to 1～100 exchanges 1～4 time under 70～90 ℃ of conditions; Each ammonium swap time is 1～6 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
This mesoporous HZSM-11 zeolite prepares scheme and is further characterized in that: a) step, the raw material constitutive molar ratio of described synthesis reaction mixture is SiO
2/ Al
2O
3=40～200, Na
2O/SiO
2=0.05～0.15, H
2O/SiO
2=10～40, template/SiO
2=0.05～0.25, organic polymer/SiO
2=0.0001～0.01.
B) step, hydrothermal crystallizing temperature are 100～180 ℃, and crystallization time is 24～360 hours.
The present invention adopts two kinds of template; Organic polymer participates in the building-up process of zeolite crystal as the hard template material of pore-creating agent with the impurity form; Be wrapping in the zeolite crystal of formation; Subsequently template is removed, then stayed the space, obtain multilevel ordered mesopore orbit structure in the position of template.Because mesoporous zeolite aperture big (aperture can reach 5.9 nanometers) can assist and hold carbon, and size of microcrystal is little, the duct short, the aperture is many; Product can be derived from the duct fast; Be difficult for to stop up the duct, reduced the probability of plug-hole inactivation, thereby have excellent anti-carbon performance and than stable catalytic performance.
Judge among the present invention whether synthetic ZSM-11 zeolite has the value that mesoporous foundation is mesoporous volume/micro pore volume; The value of the mesoporous volume/micro pore volume of conventional ZSM-11 zeolite is about about 2.0, and the value of the mesoporous volume/micro pore volume of synthetic ZSM-11 zeolite of the present invention can reach 2.5～4.
The life of catalyst basis for estimation is through after the identical time response among the present invention, obtains the carbon distribution total amount of catalyzer through DTA, thereby obtains the carbon distribution weight of unit time unit weight catalyzer, be i.e. carbon distribution speed (unit: mgg
-1H
-1).This carbon distribution speed is big more, and the deactivation rate that catalyzer is corresponding is just fast more, and life of catalyst is just short more.
Carbon distribution speed≤the 1.58mgg of mesoporous ZSM-11 zeolite among the present invention
-1H
-1, catalyzer steady running 168 hours, considerable change does not take place in activity, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of [embodiment 1] product.
Fig. 2 is the XRD figure spectrum of [Comparative Examples 1] product.
Fig. 3 is the XRD figure spectrum of [Comparative Examples 2] product.
Fig. 4 is the SEM collection of illustrative plates of [embodiment 1] product.
Fig. 5 is the TEM collection of illustrative plates of [embodiment 1] product.
Fig. 6 is the TEM collection of illustrative plates of [Comparative Examples 1] product.
Fig. 7 is the SEM collection of illustrative plates of [Comparative Examples 1] product.
Fig. 8 is the SEM collection of illustrative plates of [Comparative Examples 2] product.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=100, Na
2O/SiO
2=0.14, H
2O/SiO
2=40, organic ammonium/SiO
2=0.15, organic polymer/SiO
2=0.0002, organic ammonium is a Tetrabutyl amonium bromide, and said alkali source is a sodium hydroxide, and said silicon source is a silicon sol, and said aluminium source is a sodium metaaluminate, and said organic polymer is a polyoxyethylene glycol.
B) step, hydrothermal crystallizing temperature are 140 ℃, and crystallization time is 192 hours.Product is washed with distilled water to 550 ℃ of roastings in air after neutrality, spinning, the oven dry.Product X RD collection of illustrative plates shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically, sees Fig. 1.Product S EM photo shows that ZSM-11 zeolite granular particle diameter is 300 nanometers, and the SEM collection of illustrative plates and the TEM collection of illustrative plates of product are seen Fig. 4, Fig. 5 respectively, and the mesoporous ZSM-11 zeolite pore of gained structural parameter are seen table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test
The performance evaluation of catalyzer is carried out on fixed-bed reactor; Adopting internal diameter is 12 millimeters stainless steel reactor, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step, loadings is 6 milliliters; Temperature of reaction is 450 ℃; Reaction pressure is 0.5MPa, and raw material is mixed c 4 hydro carbons (containing C 4 olefin 71.8 (weight) %), air speed 6 hours
-1The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 2]
With preparation catalyzer among the embodiment 1 and examination catalyzer, crystallization time is 216 hours when just preparing catalyzer, and the XRD figure spectrum diffraction peak intensity of 216 hours after products of crystallization has growth slightly, shows that percent crystallinity raises.Product S EM photo shows that mesoporous ZSM-11 zeolite granular size and pore structure parameter see table 1.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 3]
With preparation catalyzer among the embodiment 1 and examination catalyzer, just crystallization time is 240 hours, and the XRD figure spectrum of 240 hours after products of crystallization is with relatively there not being considerable change among the embodiment 2.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen table 1.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 4]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=100, Na
2O/SiO
2=0.14, H
2O/SiO
2=40, organic ammonium/SiO
2=0.15, organic polymer/SiO
2=0.0005; Organic ammonium is a Tetrabutyl amonium bromide, and said alkali source is a sodium hydroxide, and said silicon source is a silicon sol, and said aluminium source is a sodium metaaluminate, and said organic polymer is a starch.
B) step; A) the prepared raw mix of step is moved to autoclave in 140 ℃ of crystallization 24 hours; Temperature programming to 160 afterwards ℃ continues crystallization, and crystallization time is 48 hours, and product is washed with distilled water to 550 ℃ of roastings in air after neutrality, spinning, the oven dry.Product X RD collection of illustrative plates shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 5]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=100, Na
2O/SiO
2=0.14, H
2O/SiO
2=40, organic ammonium/SiO
2=0.15, organic polymer/SiO
2=0.01; Organic ammonium is a TBAH, and said alkali source is a sodium hydroxide, and said silicon source is a water glass, and said aluminium source is a Tai-Ace S 150, and said organic polymer is a polyoxyethylene glycol.
B) step, hydrothermal crystallizing temperature are 125 ℃, and crystallization time is 192 hours, and product is washed with distilled water to 550 ℃ of roastings in air after neutrality, spinning, the oven dry.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 6]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=80, Na
2O/SiO
2=0.10, H
2O/SiO
2=35, organic ammonium/SiO
2=0.12, organic polymer/SiO
2=0.0008; Organic ammonium is a tetrabutylammonium iodide, and said alkali source is a sodium hydroxide, and said silicon source is a tetraethoxy, and said aluminium source is a sodium aluminate, and said organic polymer is a starch.
B) step, hydrothermal crystallizing temperature are 120 ℃, and crystallization time is 192 hours, and product is washed with distilled water to 550 ℃ of roastings in air after neutrality, spinning, the oven dry.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 7]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=40, Na
2O/SiO
2=0.07, H
2O/SiO
2=20, organic ammonium/SiO
2=0.09, organic polymer/SiO
2=0.001; Organic ammonium is the TBAH ammonium, and said alkali source is a Pottasium Hydroxide, and said silicon source is a WHITE CARBON BLACK, and said aluminium source is an aluminum isopropylate, and said organic polymer is a polyoxyethylene glycol.
B) step, hydrothermal crystallizing temperature are 180 ℃, and crystallization time is 192 hours, product with distilled water wash, spinning, oven dry after 550 ℃ of roastings in air.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 8]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=200, Na
2O/SiO
2=0.15, H
2O/SiO
2=50, organic ammonium/SiO
2=0.05, organic polymer/SiO
2=0.006; Organic ammonium is a TBAH, and said alkali source is a sodium hydroxide, and said silicon source is a silica gel, and said aluminium source is an aluminum isopropylate, and said organic polymer is a polyoxyethylene glycol.
B) step, hydrothermal crystallizing temperature are 100 ℃, and crystallization time is 192 hours, product with distilled water wash, spinning, oven dry after 550 ℃ of roastings in air.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 9]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=120, Na
2O/SiO
2=0.05, H
2O/SiO
2=25, organic ammonium/SiO
2=0.25, organic polymer/SiO
2=0.0015; Organic ammonium is a TBAH, and said alkali source is a sodium hydroxide, and said silicon source is a silicon sol, and said aluminium source is an aluminum isopropylate, and said organic polymer is a starch.
B) step, hydrothermal crystallizing temperature are 160 ℃, and crystallization time is 192 hours, product with distilled water wash, spinning, oven dry after 550 ℃ of roastings in air.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 10]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=60, Na
2O/SiO
2=0.09, H
2O/SiO
2=20, organic ammonium/SiO
2=0.20, organic polymer/SiO
2=0.005; Organic ammonium is a TBAH, and said alkali source is a sodium hydroxide, and said silicon source is a tetraethoxy, and said aluminium source is a Tai-Ace S 150, and said organic polymer is a polyoxyethylene glycol.
B) step, hydrothermal crystallizing temperature are 150 ℃, and crystallization time is 192 hours, product with distilled water wash, spinning, oven dry after 550 ℃ of roastings in air.The product X RD collection of illustrative plates of handling 192 hours shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 11]
ZSM-11 prepare zeolite method comprises the steps:
A) step, said raw mix is counted SiO by mole
2/ Al
2O
3=200, Na
2O/SiO
2=0.15, H
2O/SiO
2=25, organic ammonium/SiO
2=0.25, organic polymer/SiO
2=0.008; Organic ammonium is a Tetrabutyl amonium bromide, and said alkali source is a sodium hydroxide, and said silicon source is a silicon sol, and said aluminium source is an aluminum isopropylate, and said organic polymer is a starch.
B) step, hydrothermal crystallizing temperature are 140 ℃, and crystallization time is 8 days, product with distilled water wash, spinning, oven dry after 550 ℃ of roastings in air.The product X RD collection of illustrative plates of handling 8 days shows that product is the ZSM-11 zeolite, and baseline straightening shows and do not contain unformed material basically.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.
C) step; With b) to make product be the ammonium ion solution of 1.0 mol with concentration to step, is 10 according to liquid-solid volume ratio, exchange is 4 times under 90 ℃ of conditions; Each ammonium swap time is 1 hour, after spinning, drying, roasting, obtains mesoporous HZSM-11 zeolite.
Catalytic performance test is with embodiment 1, and catalyzer is c) the mesoporous HZSM-11 zeolite that makes in the step.The appraisal result of successive reaction after 168 hours seen table 2.
[embodiment 12]
By each step of [embodiment 1], just raw material is mixed c 4 hydro carbons (containing C 4 olefin 80 (weight) %), and reaction conditions and result see table 2.
[embodiment 13～26]
By each step and the raw material of [embodiment 1], just change the examination reaction conditions, reaction conditions and result see table 2.
[Comparative Examples 1]
By each step and condition in [embodiment 1], just do not add the organic polymer template in the raw mix.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.Product X RD collection of illustrative plates is seen Fig. 3, and the SEM collection of illustrative plates is seen Fig. 8.ZSM-11 zeolite pore structural parameter are seen table 1.The appraisal result of successive reaction after 168 hours seen table 2.
[Comparative Examples 2]
By each step and condition in [embodiment 1], just static crystallization.Product S EM photo demonstration ZSM-11 zeolite granular size and pore structure parameter are seen in the table 1.Product X RD collection of illustrative plates is seen Fig. 3, and the SEM collection of illustrative plates is seen Fig. 8.ZSM-11 zeolite pore structural parameter are seen table 1.The appraisal result of successive reaction after 168 hours seen table 2.
Table 1
| Embodiment | Mesoporous surface/micropore surface is long-pending | Mesoporous volume/micro pore volume | Aperture (nanometer) | Particle diameter (nanometer) |
| Embodiment 1 | 0.4356 | 3.5080 | 5.8326 | 300 |
| |
0.4421 | 3.6121 | 5.8537 | 300 |
| Embodiment 3 | 0.4406 | 3.5310 | 5.8416 | 300 |
| Embodiment 4 | 0.4527 | 3.0233 | 5.9041 | 500 |
| |
0.4487 | 3.6269 | 5.9041 | 400 |
| Embodiment 6 | 0.4593 | 3.6437 | 5.9132 | 400 |
| Embodiment 7 | 0.4577 | 3.2510 | 5.8804 | 400 |
| Embodiment 8 | 0.4420 | 2.5319 | 5.8519 | 400 |
| Embodiment 9 | 0.4508 | 2.6438 | 5.8631 | 400 |
| |
0.4562 | 3.9315 | 5.9118 | 200 |
| Embodiment 11 | 0.4624 | 3.9428 | 5.9237 | 100 |
| Comparative Examples 1 | 0.4343 | 2.0080 | 3.8949 | 300 |
| Comparative Examples 2 | 0.5465 | 1.0268 | 2.4329 | 5000 |
Table 2
Claims (5)
1. a mixed c 4 aromizing prepares the method for aromatic hydrocarbons, is raw material with the mixed c 4 hydrocarbon, is 300～600 ℃ in temperature of reaction, and reaction pressure is 0.1～1MPa, and mass space velocity is 0.1～20 hour
-1Condition under, material carbon four hydrocarbon contact with catalyzer and aromatization takes place generate aromatic hydrocarbons in fixed-bed reactor, wherein used catalyzer is silica alumina ratio SiO
2/ Al
2O
3Be 40～200, size of microcrystal is the mesoporous ZSM-11 zeolite of≤500 nanometers.
2. prepare the method for aromatic hydrocarbons according to the said mixed c 4 aromizing of claim 1, it is characterized in that mesoporous ZSM-11 zeolite particle diameter is 100～500 nanometers.
3. prepare the method for aromatic hydrocarbons according to the said mixed c 4 aromizing of claim 1, it is characterized in that the value of the mesoporous volume/micro pore volume of mesoporous ZSM-11 zeolite is 2.5～4.
4. the method for preparing aromatic hydrocarbons according to the said mixed c 4 aromizing of claim 1 is characterized in that raw material is 50～90% mixed c 4 for the alkene weight content.
5. prepare the method for aromatic hydrocarbons according to said carbon four aromizing of claim 1, it is characterized in that temperature of reaction is 370～530 ℃, reaction pressure is 0.1～1MPa, and the raw materials quality air speed is 0.5～6 hour
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103539619A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing arene from mixed C4 in aromatization mode |
| CN103739437A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method used for producing non-benzenoid aromatics from benzene and mixed C4 |
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| US4590321A (en) * | 1985-06-12 | 1986-05-20 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
| CN1586721A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | Catalyst for C4 liquefied petroleum gas aromatization and its preparing method |
| CN101530813A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve catalyst used in carbon 4 liquid gas aromatization reaction |
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| US4590321A (en) * | 1985-06-12 | 1986-05-20 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
| CN1586721A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | Catalyst for C4 liquefied petroleum gas aromatization and its preparing method |
| CN101530813A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve catalyst used in carbon 4 liquid gas aromatization reaction |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539619A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing arene from mixed C4 in aromatization mode |
| CN103539619B (en) * | 2012-07-12 | 2015-05-13 | 中国石油化工股份有限公司 | Method for preparing arene from mixed C4 in aromatization mode |
| CN103739437A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method used for producing non-benzenoid aromatics from benzene and mixed C4 |
| CN103739437B (en) * | 2012-10-17 | 2015-10-21 | 中国石油化工股份有限公司 | The method of non-benzene aromatic hydrocarbons is produced for mixed c 4 and benzene |
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