CN106607081A - Method for modifying ZSM-5 molecular sieve through organophosphorous compound - Google Patents
Method for modifying ZSM-5 molecular sieve through organophosphorous compound Download PDFInfo
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Abstract
The invention provides a method for modifying a ZSM-5 molecular sieve through an organophosphorous compound. The method comprises mixing an HZSM-5 molecular sieve and one or more organophosphorous compounds such as tetrabutylphosphonium hydroxide, tetrabutylphosphonium bromide, di-n-butyl phosphate, 1-butylphosphoric acid, tri-n-butylphosphonium oxide, tributylphosphine, fosetyl-aluminum, tetraphenylphosphonium bromide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide and triphenylbenzylphosphonium bromide, and drying and calcining the mixture. The organophosphorous compound-modified ZSM-5 molecular sieve has a high pore volume and a high specific surface area and contains more B acid centers.
Description
Technical field
The present invention is with regard to the method for modified zsm-5 zeolite, the zeolite product that obtains and application, more
Specifically, the present invention is produced with regard to the method for phosphorous modified ZSM-5 molecular sieve, the phosphorous molecular sieve that obtains
Product and the application in hydrocarbon oil conversion.
Background technology
ZSM-5 molecular sieve is a kind of mesoporous molecular sieve (USP of the high silicon 3 D straight channel with MFI structure
3702886), it has unique pore passage structure, and has good shape selective catalysis and isomerization performance, high
Heat and hydrothermal stability, high-specific surface area, wide silica alumina ratio excursion, unique surface acidity and relatively low
The characteristics of knot carbon amounts.ZSM-5 molecular sieve is widely used as catalyst and catalyst carrier, and is used successfully to alkane
The production technologies such as base, isomerization, disproportionation, catalytic cracking, preparing gasoline by methanol and methanol-to-olefins.
Propylene is the important petrochemical industry base stock for being only second to ethylene, is mainly used to produce polypropylene, propylene
The chemical products such as nitrile, expoxy propane, isopropylbenzene, acrylic acid and isopropanol.In recent years, due to spreading out downstream
Biological need is increased rapidly, and the rate of increase of propylene demand is more than the rate of increase of ethylene requirements.Current propylene
Steam cracking and catalytic cracking process are mainly derived from, the 66% and 32% of propylene total output is accounted for respectively.In order to increase
Propylene is produced, from nineteen eighty-three, ZSM-5 molecular sieve starts to be applied to urge as catalytic cracking octane enhancing additive
Change process, it is intended to improve the octane number of catalytically cracked gasoline and the selectivity of low-carbon alkene.HZSM-5 point
Although with good Shape-selective and isomerization performance, its weak point is that hydrothermal stability is poor to son sieve,
Easy in inactivation under harsh high temperature hydrothermal condition, reduces catalytic performance.
ZSM-5 molecular sieve introduces inorganic phosphorous compound and is modified, and can slow down skeleton under harsh hydrothermal condition
Dealuminzation, and as active component preparing catalyst, is mainly used in increasing propylene yield and improves gasoline octane
The catalytic cracking process (FCC) of value and DCC (DCC) process of light olefin maximum production.
On the premise of propylene, butylene yield are suitable, under dry gas, cracking light oil and coke is had by a relatively large margin
Drop, significantly increases the yield of high added value gasoline, and output more has significant economic benefit.Wherein, phosphorus is carried
The amount of holding is generally in the range of 1～7wt%.The widest method being modified using inorganic phosphorous compound is first to use ammonium
Ion exchange sodium form molecular sieve obtains Hydrogen ZSM-5 molecular sieve, then is carried out by phosphoric acid or phosphate solution
Dipping, obtains (H4PO4)+(ZSM-5)-, drying, roasting obtain PHZSM-5.
The content of the invention
The present inventor is on the basis of lot of experiments, it has unexpectedly been found that when with HZSM-5 molecular sieves as original
Material, using raw material and P Modification process different from prior art, can obtain higher pore volume and surface
The modified zsm-5 zeolite of long-pending, more B-acid acid centres, the modified molecular screen splits in n-tetradecane hydrocarbon
Solution reaction in have the conversion ratio of the higher n-tetradecane hydrocarbon pyrolysis, excellent Propylene Selectivity, while have compared with
Hydro-thermal well and activity stability.Based on this, the present invention is formed.
Therefore, it is an object of the invention to provide a kind of modified HZSM-5 molecular sieve different from prior art
Method, the two of purpose is to provide the modified HZSM-5 molecular sieve that the method is obtained, and the three of purpose is to provide
Application of the modified HZSM-5 molecular sieve in hydrocarbon ils cracking reaction.
In order to realize an object of the present invention, the method for the modified HZSM-5 molecular sieve that the present invention is provided, its
It is characterised by mixing organic phosphorus compound with HZSM-5 molecular sieves, mixture drying, roasting, wherein institute
The organic phosphorus compound said is selected from tetrabutylammonium hydroxide phosphorus, tetrabutyl phosphonium bromide phosphorus, phosphoric acid di-n-butyl, 1- fourths
Base phosphoric acid, three normal-butyl phosphorous oxide, tributylphosphine, phosethyl-Al, tetraphenyl phosphonium bromide, triphenyl second
One or more of base phosphonium bromide, triphenylbut base phosphonium bromide and triphenylbenzylphosphonium phosphonium bromide.
In order to realize the second object of the present invention, present invention also offers above-mentioned method of modifying obtain it is modified
HZSM-5 molecular sieves.
In order to realize the third object of the present invention, invention further provides a kind of hydrocarbon ils cleavage method, its
It is characterised by the active component with above-mentioned modified HZSM-5 molecular sieve as hydrocarbon ils catalyst for cracking.
The method of the modified HZSM-5 molecular sieve that the present invention is provided, is with special organic phosphorus compound pair
HZSM-5 molecular sieves are modified, and compared with conventional inorganic phosphide modified zsm-5 zeolite, can cause
To modified HZSM-5 molecular sieve show higher pore volume and surface area, more B-acid acid centres,
Its hydrothermal activity stability is improve, and slow down framework dealumination.It is modified that method of modifying of the present invention is obtained
HZSM-5 molecular sieves have higher conversion in hydrocarbon ils cracking reaction, such as n-tetradecane hydrocarbon pyrolysis reaction
The selectivity of rate, excellent propylene, while having preferable hydro-thermal and activity stability.
Specific embodiment
The invention provides a kind of method of modified HZSM-5 molecular sieve, it is characterised in that by organic phosphorus compound
Mix with HZSM-5 molecular sieves, mixture drying, roasting, wherein described organic phosphorus compound is selected from four
Butyl phosphonium hydroxide, tetrabutyl phosphonium bromide phosphorus, phosphoric acid di-n-butyl, 1- butyl phosphoric acids, three normal-butyl phosphorous oxide,
Tributylphosphine, phosethyl-Al, tetraphenyl phosphonium bromide, triphenyl ethyl phosphonium bromide phosphorus, triphenylbut bromide
One or more of phosphorus and triphenylbenzylphosphonium phosphonium bromide.
Wherein, described HZSM-5 molecular sieves, typically refer to alkali metal content less than in the case of 0.1wt%
ZSM-5 molecular sieve.HZSM-5 molecular sieves can be by way of ammonium well known in the art hands over drop sodium by sodium form
ZSM-5 molecular sieve is converted into HZSM-5 molecular sieves.HZSM-5 molecular sieves can have different silica alumina ratio (oxygen
SiClx/alumina molar ratio) HZSM-5 molecular sieves, preferred silica alumina ratio be 25～1000, more preferably
Silica alumina ratio is 40～600.
Wherein, organic phosphorus compound mix with HZSM-5 molecular sieves obtained by mixture in, phosphorus have with
P2O5Meter, at least loading amount of 0.1wt%；Preferably, phosphorus has with P2O5Meter, 0.5～10wt% hold
Amount；It is furthermore preferred that phosphorus has with P2O5Meter, the loading amount of 2.0～7.0wt%.
Wherein, described organic phosphorus compound is selected from tetrabutylammonium hydroxide phosphorus, tetrabutyl phosphonium bromide phosphorus, di(2-ethylhexyl)phosphate
N-butyl, 1- butyl phosphoric acids, three normal-butyl phosphorous oxide, tributylphosphine, phosethyl-Al, tetraphenylphosphonibromide bromide
One or more of phosphorus, triphenyl ethyl phosphonium bromide phosphorus, triphenylbut base phosphonium bromide and triphenylbenzylphosphonium phosphonium bromide.
Preferably, described organic phosphorus compound is tetrabutylammonium hydroxide phosphorus and/or three normal-butyl phosphorous oxide.Send out
A person of good sense is especially it was unexpectedly observed that using tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide as common organophosphors
The molar ratio of compound, tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide is 10～15:1st, phosphorus holds
The HZSM-5 molecular sieves for obtaining that are modified in 2.5～5.5wt% are measured, higher pore volume and specific surface can be obtained
Product, organophosphors species can stablize more framework aluminums, and retain more B-acid centers.Therefore, most preferably
Organic phosphorus compound be molar ratio be 10～15:1 tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide
Mixture.
The mode that described organic phosphorus compound mixes with HZSM-5 molecular sieves can be dipping stirring, as long as
Ensure that organic phosphorus compound is to be sufficiently mixed uniformly with HZSM-5 molecular sieves.
During described drying, roasting, drying meanss and condition are conventional drying meanss and condition,
For example in the drying 4～24 hours of 100～120 DEG C of baking oven；Method of roasting and condition are adopted by molecular sieve activation
Conventional method and condition, such as in Muffle kiln roasting, sintering temperature is at least 300 DEG C, roasting time
For 2～6 hours.
Present invention also offers the HZSM-5 molecular sieves that above-mentioned method of modifying is obtained, its phosphorus content is 0.5～
10wt%, preferably 2～7wt%.
Invention further provides a kind of hydrocarbon ils cleavage method, it is characterised in that obtained with above-mentioned method of modifying
HZSM-5 molecular sieves for catalyst active component.Described hydrocarbon ils can be n-tetradecane hydrocarbon, its molecule
Size can be entered in MFI molecular sieve pore passages, and characterizes the catalytic active site performance that cracking reaction occurs.
By taking the probe reaction of n-tetradecane hydrocarbon catalytic pyrolysiss as an example, can be in 400～650 DEG C of reaction temperature,
Weight space velocity is 0.5～8hr-1, the mass values of molecular sieve/feed oil are 0.1～3：Under 1 reaction condition
Carry out.Preferably, it is 1～6hr of weight space velocity in 450～550 DEG C of reaction temperature-1, molecular sieve/feed oil
Mass values 0.5～2.5：1.
Below by comparative example and embodiment, the present invention will be further described, but does not therefore limit this
Bright content.
In comparative example and embodiment, described raw material HZSM-5 is the production of Zibo catalyst plant, relative to crystallize
Degree is respectively 97.0%, and oxygen aluminum ratio is 49, and alkali metal content 0.08wt%, specific surface area is 378m2/ g, always
Pore volume is 0.206ml/g.
In comparative example and embodiment, the element chemistry composition of molecular sieve is determined with x-ray fluorescence method.
The relative crystallinity is with the X-ray diffraction of products therefrom and ZSM-5 molecular sieve standard specimen (XRD) spectrum
The ratio of the peak area sum of five characteristic diffraction peaks of 2 θ of figure between 22.5～25.0 ° is with percent
To represent, the ZSM-5 molecular sieve that the method for embodiment 1 in CN1056818C synthesizes is adopted for standard specimen, by it
Degree of crystallinity is set to 100%.X-ray diffraction spectrogram is determined on Rigaku TTR-3 powder x-ray diffractions,
Instrument parameter：Copper target (tube voltage 40kV, tube current 250mA), scintillation counter, 0.02 ° of step width,
Sweep speed 0.4 (°)/min.
The AS-3 that nitrogen adsorption desorption curve is produced in Quantachrome instrument companies, AS-6 static nitrogens are inhaled
Attached instrument.Instrument parameter：Sample is placed in into sample processing system, at 300 DEG C 1.33 × 10-2Pa is evacuated to,
Heat-insulation pressure keeping 4h, purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing on year-on-year basis P/P0
Under the conditions of adsorbance and desorption rate to nitrogen, obtain N2Adsorption-desorption isothermal curve.Then using two ginsengs
Number BET formula calculates specific surface area, takes the pore volume than pressing the adsorbance of below P/P0=0.98 to be sample,
The pore-size distribution of hollow sections is calculated using BJH formula.
The FTS3000 type Fourier infrared spectrographs that acid test is produced using BIO-RAD companies of the U.S..Instrument
Device parameter：To be placed in after sample tabletting in the pond in situ of infrared spectrometer and seal, be evacuated at 350 DEG C
10-3Pa, keeps 1h, and the gas molecule for making sample surfaces is desorbed totally, is cooled to room temperature.To in pond in situ
Pyridine steam of the pressure for 2.67Pa is imported, after balance 30min, 200 DEG C is warming up to, is evacuated to again
10-3Pa, keeps 30min, room temperature is cooled to, in 1400cm-1-1700cm-1Scanning in wave-number range, record
The infrared spectrum spectrogram of lower 200 DEG C of pyridine adsorptions.Again the sample in cell for infrared absorption is moved to into heat-treatment zone,
350 DEG C are warming up to, 10 are evacuated to-3Pa, keeps 30min, is cooled to room temperature, records 350 DEG C of pyridines and inhales
Attached infrared spectrum.B-acid and L acid center value are the peak height value on infrared spectrum behind buckle back bottom.
Comparative example 1
This comparative example illustrates the process of diammonium phosphate modified HZSM-5 molecular sieve.
Weigh diammonium phosphate (Tianjin Standard Science company limited analyzes pure, similarly hereinafter) and add deionization
After water wiring solution-forming, the HZSM-5 molecular sieves (Shandong catalyst plant, solid content 93%) of 54.0g are added,
Dipping stirring forms wherein P2O5For the mixture of 3.5wt%, mixture drying, roasting and recovery product are obtained
To modified HZSM-5.It is designated as P-Z-1.
The degree of crystallinity of P-Z-1 is 80.
Acid data are shown in Table 1, explanation P-Z-1 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 1
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 2.Table 2 illustrates P-Z-1 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Embodiment 1
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
(Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure, TBPOH contents to weigh tetrabutylammonium hydroxide phosphorus
40%, similarly hereinafter) add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g, dipping stirring shape
Into wherein P2O5For the mixture of 3.5wt%, by mixture drying and roasting, it is modified that recovery product obtains the present invention
HZSM-5 molecular sieves, it is designated as P-Z-2.
The degree of crystallinity of P-Z-2 is 83.5.
Acid data are shown in Table 1, explanation P-Z-2 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 1
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 2.Table 2 illustrates P-Z-2 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Table 1
Table 2
Although as it can be seen from table 1 P-Z-1 and P-Z-2 are with identical P2O5The phosphorus source of mass fraction is modified,
But due to Phos (diammonium phosphate) and the difference of organophosphors (tetrabutylammonium hydroxide phosphorus), P-Z-2
The B-acid center of reservation is relatively more.
From table 2 it can be seen that after hydrothermal treatment consists 17h at 100% vapor and 800 DEG C, with Phos (phosphorus
Sour hydrogen diammonium) modified P-Z-1 compares, and organophosphors (tetrabutylammonium hydroxide phosphorus) modified P-Z-2 has
Higher pore volume and specific surface area.
Comparative example 2
Weigh 5.40g diammonium phosphate and add the HZSM-5 that 54.0g is added after 55g deionized water wiring solution-formings
In molecular sieve, dipping stirring forms P therein2O5For the mixture of 5.5wt%, by mixture drying and roasting after,
Recovery product obtains the modified HZSM-5 molecular sieves of diammonium phosphate.It is designated as P-Z-3.
The degree of crystallinity of P-Z-3 is 75.0.
Acid data are shown in Table 3, explanation P-Z-3 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 3
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 4.Table 4 illustrates P-Z-3 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Embodiment 2
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
(Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure, TBPOH contents to weigh tetrabutylammonium hydroxide phosphorus
40%, similarly hereinafter) add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g, dipping stirring shape
Into wherein P2O5For the mixture of 5.5wt%, by mixture drying and roasting, it is modified that recovery product obtains the present invention
HZSM-5 molecular sieves, are designated as P-Z-4.
The degree of crystallinity of P-Z-4 is 85.3.
Acid data are shown in Table 3, explanation P-Z-4 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 3
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 4.Table 4 illustrates P-Z-4 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Table 3
Table 4
Although from table 3 it can be seen that P-Z-3 and P-Z-4 are with identical P2O5The phosphorus source of mass fraction is modified,
But due to Phos (diammonium phosphate) and the difference of organophosphors (tetrabutylammonium hydroxide phosphorus), P-Z-4
The B-acid center of reservation is relatively more.
From table 4, it can be seen that after hydrothermal treatment consists 17h at 100% vapor and 800 DEG C, with Phos (phosphorus
Sour hydrogen diammonium) modified P-Z-3 compares, and organophosphors (tetrabutylammonium hydroxide phosphorus) modified P-Z-4 has
Higher pore volume and specific surface area.
Comparative example 3
(Tianjin Standard Science company limited analyzes pure, P to weigh 6.50g diammonium phosphate2O5Mass fraction
For 7.0wt%) add 63.0g deionized water wiring solution-formings after, add 55.0g HZSM-5 molecular sieves in,
After dipping stirring a period of time, after drying and roasting, obtain the modified HZSM-5 molecular sieves of diammonium phosphate and be designated as
P-Z-5。
The degree of crystallinity of P-Z-5 is 76.0.
Acid data are shown in Table 5, explanation P-Z-5 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 5
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 6.Table 6 illustrates P-Z-5 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Embodiment 3
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
Weigh tetrabutylammonium hydroxide phosphorus to add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g,
Dipping stirring forms wherein P2O5For the mixture of 7.0wt%, by mixture drying and roasting, recovery product is obtained
Modified HZSM-5 molecular sieve of the present invention, is designated as P-Z-6.
The degree of crystallinity of P-Z-6 is 86.0.
Acid data are shown in Table 5, explanation P-Z-6 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 5
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 6.Table 6 illustrates P-Z-6 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pore structure data afterwards.
Table 5
Table 6
As can be seen from Table 5, although P-Z-5 and P-Z-6 are with identical P2O5The phosphorus source of mass fraction is modified,
But due to Phos (diammonium phosphate) and the difference of organophosphors (positive tributylphosphine oxide), P-Z-6
The B-acid center of reservation is relatively more.
As can be seen from Table 6, after hydrothermal treatment consists 17h at 100% vapor and 800 DEG C, with Phos (phosphorus
Sour hydrogen diammonium) modified P-Z-5 compares, and organophosphors (positive tributylphosphine oxide) modified P-Z-6 has
Higher pore volume and specific surface area.
Embodiment 4
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
Weigh tetrabutylammonium hydroxide phosphorus to add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g,
Dipping stirring forms wherein P2O5For the mixture of 2.0wt%, by mixture drying and roasting, recovery product is obtained
Modified HZSM-5 molecular sieve of the present invention,.It is designated as P-Z-7.
The degree of crystallinity of P-Z-7 is 86.7.
Acid data are shown in Table 7, explanation P-Z-7 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 7
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 8, explanation P-Z-7 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 8
Pore structure data afterwards.
Embodiment 5
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
Weigh tetrabutylammonium hydroxide phosphorus to add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g,
Dipping stirring forms wherein P2O5For the mixture of 3.0wt%, by mixture drying and roasting, recovery product is obtained
Modified HZSM-5 molecular sieve of the present invention,.It is designated as P-Z-8.
The degree of crystallinity of P-Z-8 is 83.2.
Acid data are shown in Table 7, explanation P-Z-8 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 7
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 8, explanation P-Z-8 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 8
Pore structure data afterwards.
Embodiment 6
Weigh tetrabutylammonium hydroxide phosphorus to add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g,
Dipping stirring forms wherein P2O5For the mixture of 4.5wt%, by mixture drying and roasting, recovery product is obtained
Modified HZSM-5 molecular sieve of the present invention, is designated as P-Z-9.
The degree of crystallinity of P-Z-9 is 82.7.
Acid data are shown in Table 7, and table 7 illustrates P-Z-9 after hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
Pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 8, explanation P-Z-9 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 8
Pore structure data afterwards.
Embodiment 7
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
Weigh tetrabutylammonium hydroxide phosphorus to add after deionized water, in adding the HZSM-5 molecular sieves of 54.0g,
Dipping stirring forms wherein P2O5For the mixture of 6.0wt%, by mixture drying and roasting, recovery product is obtained
Modified HZSM-5 molecular sieve of the present invention,.It is designated as P-Z-10.
The degree of crystallinity of P-Z-10 is 80.2.
Acid data are shown in Table 7, explanation P-Z-10 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 7
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 8, explanation P-Z-10 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 8
Pore structure data afterwards.
Table 7
Table 8
Embodiment 8
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
Weigh tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide (Hubei Ju Sheng Science and Technology Ltd.s, similarly hereinafter)
The mixture of the two is obtained, wherein, the mol ratio of tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide is
12.5:1, in adding the HZSM-5 molecular sieves of 54.0g, dipping stirring forms wherein P2O5For 3.5wt%
Mixture, by mixture drying and roasting, recovery product obtains modified HZSM-5 molecular sieve of the present invention.It is designated as
P-Z-11。
The degree of crystallinity of P-Z-11 is 82.7.
Acid data are shown in Table 9, explanation P-Z-11 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 9
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 10, the explanation P-Z-11 hydrothermal treatment consists at 100% vapor and 800 DEG C of table 10
Pore structure data after 17h.
Embodiment 9
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
With embodiment 8, it is 15 that difference is the mol ratio of tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide:1,
For P-Z-12.
The degree of crystallinity of P-Z-12 is 82.9.
Acid data are shown in Table 9, explanation P-Z-12 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 9
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 10, the explanation P-Z-12 hydrothermal treatment consists at 100% vapor and 800 DEG C of table 10
Pore structure data after 17h.
Embodiment 10
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
With embodiment 8, it is 10 that difference is the mol ratio of tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide:1,
For P-Z-13.
The degree of crystallinity of P-Z-13 is 82.1.
Acid data are shown in Table 9, explanation P-Z-13 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 9
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 10, the explanation P-Z-13 hydrothermal treatment consists at 100% vapor and 800 DEG C of table 10
Pore structure data after 17h.
Embodiment 11
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
With embodiment 8, it is 1 that difference is the mol ratio of tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide:1,
For P-Z-14.
The degree of crystallinity of P-Z-14 is 81.1.
Acid data are shown in Table 9, explanation P-Z-14 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 9
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 10, the explanation P-Z-14 hydrothermal treatment consists at 100% vapor and 800 DEG C of table 10
Pore structure data after 17h.
Embodiment 12
This example demonstrates that the process of the organic phosphorus compound modified HZSM-5 molecular sieve of the present invention.
With embodiment 8, it is 20 that difference is the mol ratio of tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide:1,
For P-Z-15.
The degree of crystallinity of P-Z-15 is 80.1.
Acid data are shown in Table 9, explanation P-Z-15 hydrothermal treatment consists 17h at 100% vapor and 800 DEG C of table 9
Afterwards pyridine infrared spectrum measures acid site amount.
Pore structure data are shown in Table 10, the explanation P-Z-15 hydrothermal treatment consists at 100% vapor and 800 DEG C of table 10
Pore structure data after 17h.
Table 9
Table 10
Table 9 with listed file names with identical P in table 102O5The data of P-Z-1, P-Z-2 under fraction.
As can be seen from Table 9, although P-Z-2, P-Z-14, P-Z-15 and P-Z-11, P-Z-12, P-Z-13
With identical P2O5The organic phosphorus sources of mass fraction are modified, but because P-Z-2 is single organophosphors chemical combination
Thing tetrabutylammonium hydroxide P Modification is obtained, and P-Z-11, P-Z-12, P-Z-13 are tetrabutylammonium hydroxide phosphorus
It is with the mol ratio of the mixture of three normal-butyl phosphorous oxide, and tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide
10～15:1 is modified what is obtained, and the B-acid center that P-Z-11, P-Z-12, P-Z-13 retain is relatively more.From
Table 9 is it can also be seen that what the mixture modification for belonging to tetrabutylammonium hydroxide phosphorus and three normal-butyl phosphorous oxide together was obtained
The B-acid center that P-Z-14, P-Z-15 retain is suitable with P-Z-2.
As can be seen from Table 10, P-Z-11, P-Z-12, P-Z-13 have higher pore volume and specific surface
Product.
Comparative example 4-6
Comparative example 4-6 illustrates inorganic phosphide modified molecular screen sample P-Z-1, the catalysis of P-Z-3, P-Z-5
Performance.
P-Z-1, P-Z-3, P-Z-5 are entered after hydrothermal treatment consists 17h at 100% vapor and 800 DEG C
The reactivity worth evaluation of row n-tetradecane hydrocarbon catalytic pyrolysiss, reaction is carried out in fixed bed reactors.It is former
Material：N-tetradecane hydrocarbon, carrier gas：Nitrogen, gas flow rate 29.0mL/min, oil ratio is 1.30, reaction temperature
Spend for 500 DEG C, reaction pressure is 0.8MPa, weight space velocity is 2.90hr-1, after molecular sieve tabletting screening be
20～40 mesh granules, loadings 2g, sample analysis after reaction 970s carry out MaterialBalance Computation.
N-tetradecane hydrocarbon pyrolysis conversion ratio, the selectivity of material balance, propylene in cracked gas are shown in Table 11.
Embodiment 13-24
Sieve sample P-Z-2, P-Z-4, P-Z-6 that the organic phosphorus compound of embodiment 13-24 explanation is modified,
The catalytic performance of P-Z-7～P-Z-15.
The reactivity worth evaluation of n-tetradecane hydrocarbon catalytic pyrolysiss is carried out with comparative example 4.
N-tetradecane hydrocarbon pyrolysis conversion ratio, the selectivity of material balance, propylene in cracked gas are shown in Table 11.
Table 11
Can be seen that and identical P from characterize data and catalytic performance data2O5The inorganic phosphide of mass fraction
Modified ZSM-5 molecular sieve is compared, the modified ZSM-5 molecular sieve of organic phosphorus compound after hydrothermal treatment consists,
Pore volume and specific surface area retain higher, and phosphorus interacts with framework aluminum can retain more B-acid centers, just
The cracking conversion ratio (76.0%～82.5%) of tetradecane hydrocarbon and selectivity height (0.33～0.42) of propylene,
Further increase the hydrothermal activity stability of molecular sieve.Wherein, the sample of double organic P Modification of special proportioning
The cracking conversion ratio and the selectivity highest of propylene of the n-tetradecane hydrocarbon of product P-Z-11～P-Z-13, sample
The cracking conversion ratio of P-Z-11 and the selectivity of propylene respectively reach 82.5% and 0.42.
Claims (11)
1. a kind of method of organic phosphorus compound modified HZSM-5 molecular sieve, it is characterised in that with being selected from tetrabutyl hydrogen-oxygen
Change phosphorus, tetrabutyl phosphonium bromide phosphorus, phosphoric acid di-n-butyl, 1- butyl phosphoric acids, three normal-butyl phosphorous oxide, three
Butyl phosphine, phosethyl-Al, tetraphenyl phosphonium bromide, triphenyl ethyl phosphonium bromide phosphorus, triphenylbut bromide
Change the organic phosphorus compound of one or more and HZSM-5 molecular sieves of phosphorus and triphenylbenzylphosphonium phosphonium bromide
Mixing, mixture drying, roasting.
2., according to the method for claim 1 wherein, in described mixture, phosphorus has with P2O5Meter, at least
The loading amount of 0.1wt%.
3., according to the method for claim 1 wherein, in described mixture, phosphorus has with P2O5Meter, 0.5～
The loading amount of 10wt%.
4., according to the method for claim 1 wherein, in described mixture, phosphorus has with P2O5Meter, 2.0～
The loading amount of 7.0wt%.
5., according to the method for claim 1 wherein, the silica/alumina of described HZSM-5 molecular sieves is rubbed
You are than being 25～1000.
6. according to the method for claim 1 wherein, described roasting be carry out 2 at a temperature of at least 300 DEG C～
6 hours.
7., according to the method for claim 1 wherein, described hydrothermal aging is at 500～900 DEG C and 100%
Carry out under vapor 3～100 hours.
8. the phosphorous ZSM-5 molecular sieve that one of claim 1-7 method is obtained.
9. a kind of hydrocarbon oil catalytic cracking method, it is characterised in that with the phosphorous ZSM-5 molecular sieve of claim 8
For catalyst activity constituent element.
10. a kind of method of hydrocarbon oil catalytic cracking, it is characterised in that with the phosphorous ZSM-5 of claim 8 point
Son sieve is catalyst activity constituent element, is 400～650 DEG C in reaction temperature, and weight space velocity is 0.5～8hr-1,
The mass values of molecular sieve/feed oil be 0.1～3 under conditions of carry out.
11. according to claim 10 method, wherein, reaction temperature be 450～550 DEG C, weight space velocity be 1～
6hr-1, the mass values of molecular sieve/feed oil are 0.5～2.5.
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Cited By (9)
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| CN107892308A (en) * | 2017-12-12 | 2018-04-10 | 太原理工大学 | Molecular sieves of ZSM 5 and preparation method thereof |
| CN108439428A (en) * | 2018-03-30 | 2018-08-24 | 山东多友科技有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve of P Modification and preparation method thereof |
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| CN112537779A (en) * | 2020-07-09 | 2021-03-23 | 山西腾茂科技有限公司 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
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| CN107892308A (en) * | 2017-12-12 | 2018-04-10 | 太原理工大学 | Molecular sieves of ZSM 5 and preparation method thereof |
| CN108439428A (en) * | 2018-03-30 | 2018-08-24 | 山东多友科技有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve of P Modification and preparation method thereof |
| CN113526522A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN113526519A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus-containing hierarchical pore ZSM-5 molecular sieve and preparation method thereof |
| CN113526520A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
| CN113526519B (en) * | 2020-04-13 | 2023-01-13 | 中国石油化工股份有限公司 | Phosphorus-containing hierarchical pore ZSM-5 molecular sieve and preparation method thereof |
| CN113526522B (en) * | 2020-04-13 | 2023-02-21 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN112537779A (en) * | 2020-07-09 | 2021-03-23 | 山西腾茂科技有限公司 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
| CN111760588A (en) * | 2020-07-10 | 2020-10-13 | 山西腾茂科技有限公司 | Yield-increasing propylene catalytic cracking auxiliary agent |
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