CN1072032C - Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene - Google Patents
Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene Download PDFInfo
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Abstract
The present invention relates to a molecular sieve composite for high yield of ethylene and propylene by catalytic pyrolysis. The molecular sieve composite is prepared by activating and modifying a five-membered-ring molecular sieve whose SiO2/Al2O3 mole ratio is from 15 to 60 by P, alkaline earth metal and transition metal. The modified molecular sieve contains 2 to 10 wt% of P2O5, 0.3 to 5 wt% of alkaline earth metal oxide and 0.3 to 5 wt% of transition metal oxide. The molecular sieve has high thermal and hydrothermal stability in the structure and the active center. The molecular sieve composite has the obvious characteristics that a catalyst prepared from the composite enables ethene yield to reach more than 18% and yield of ethene to butylene to reach more than 50% under the condition of catalytic thermal cracking.
Description
The present invention relates to a kind of Pentasil type zeolite molecules screen composition that is used for catalytic pyrolysis fecund ethene and propylene.
ZSM-5 (USP3 by the invention of U.S. Mobil company, 702,886,1976), ZSM-8 (GB1334243A) and ZSM-11 (USP3,709,979,1973 years) or ZSM-5/ZSM-11 (USP4,289,607,1981) etc. penta-basic cyclic molecular sieve through after the modification, be widely used in the reactions such as the hydrocarbon conversion such as alkylating aromatic hydrocarbon, disproportionation, isomerization, catalytic cracking, catalytic dewaxing and methanol synthesized gasoline, wherein the application of ZSM-5 molecular sieve is the most successful.
Early stage synthetic ZSM-5 molecular sieve need use the agent of organic amine template, comprises four n-pro-pyl ammoniums, tetraethyl ammonium, hexamethylene diamine, ethylenediamine, n-butylamine, ethamine etc.Because organic amine price height and contaminated environment, so people have also carried out a large amount of explorations to the synthetic method of not using organic amine when using the synthetic ZSM-5 molecular sieve of organic amine.For example reported among the EP111748A (1984) that use waterglass, aluminum phosphate and phosphoric acid synthesize the ZSM-5 zeolite, CN85100463A has reported that with waterglass, inorganic aluminate and inorganic acid be the synthetic ZSM-5 zeolite of raw material, it is that raw material and REY or REHY are the synthetic ZSM-5 zeolite that contains rare earth of crystal seed that CN1058382A has reported with waterglass, aluminum phosphate and inorganic acid, JP8571519 and JP8577123 have reported under no amine condition, by adding synthetic ZSM-5 molecular sieve of ZSM-5 crystal seed or the like.
In order to adapt to the needs of variety classes reaction, many method and effects thereof of the ZSM-5 molecular sieve being carried out the modification processing have been reported in the document.USP3 has for example reported the method for handling the ZSM-5 molecular sieve with the phosphorus-containing compound modification in 972,382 and USP3,965,208, promptly uses SiO
2/ Al
2O
3Be that 70 HZSM-5 and Trimethyl phosphite react, be prepared into phosphorous molecular sieve, this method preparation condition is complicated, and cost is higher, and prepared sample activity is lower than not phosphorous sample, but the selectivity of reaction improves.
U.S. Pat P4,365,104,4,137,195,4,128,592 and 4, reported method in 086,287, its objective is that the molecular sieve with modification is used for reactions such as xylene isomerization, toluene and methanol alkylation, toluene disproportionation to improve the selectivity of paraxylene with P and Mg modified zsm-5 zeolite.Introducing P and Mg mainly is in order to strengthen the shape selectivity energy of molecular sieve.But then, the reactivity of the acidity of molecular sieve and the hydrocarbon conversion then reduces after the modification.In these patents, P and Mg adopt in the method load of step impregnation, are about to molecular sieve or contain the catalyst NH of molecular sieve
4H
2PO
4Or (NH
4)
2HPO
4Behind the aqueous solution dipping, after filtration, oven dry, roasting; And then with Mg (NO
3)
2Or the aqueous solution of magnesium acetate dipping, and after filtration, oven dry, roasting, promptly obtain with the molecular sieve of P and Mg modification or contain the catalyst sample of molecular sieve.In this method, the content of P and Mg has uncertainty, and is relevant with conditions such as the temperature of reacting, time, roastings.The state of Mg is difficult for evenly simultaneously.
U.S. Pat P4,260,843 have reported the method for selecting the shaped reaction performance with P and Be modified zsm-5 zeolite with raising.USP4,288,647 have reported the method for selecting the shaped reaction performance with Ca, Sr, Ba and P modified zsm-5 zeolite with raising.In these patents, the method for the used modified molecular screen method with the P-Mg modification basically is identical, but lower through the activity of molecular sieve after the modification.
In above-mentioned patent, be SiO for the description of molecular sieve parent
2/ Al
2O
3Greater than 12, generally require SiO
2/ Al
2O
3Greater than 30 (USP3,972,832).Be generally greater than 0.25 heavy % for the content of modifying element P, greater than 0.25 heavy %, and content range is between 0.25～25 heavy % to the content requirement of alkali earth metal.In an embodiment, the content of the general alkali earth metal (Mg, Ca etc.) that adopts is greater than the content of P.The application purpose of above-mentioned patent mainly is in order to improve the shape selectivity energy of molecular sieve, and all is to be used for reactions such as isomerization, disproportionation to increase the selectivity of paraxylene.It is generally acknowledged that the acidity through alkali-earth metal modified back molecular sieve reduces.The activity of hydrocarbon conversion reactions also reduces simultaneously.
Catalytic pyrolysis preparing ethylene is the new way of increasing output of ethylene.Traditional preparing ethylene by steam cracking has the cracking temperature height, to the shortcomings such as requirement harshness of raw material.It is generally acknowledged that preparing ethylene by steam cracking is undertaken by radical reaction mechanism, so reaction temperature is very high.The applicant has proposed the Deep Catalytic Cracking process and the catalyst of a series of low-carbon olefines high-outputs in patents such as CN1031834A, CN1072201A, CN1085825A, CN1085885A, CN1093101A, CN1099788A, CN1102431A, CN1114916A and CN1117518A, generally all adopt the catalyst for cracking of the five-membered ring silica-rich zeolite of phosphorous and rare earth in these patents, they are all with volume increase C
3 =～C
5 =Alkene is purpose, and its ethylene yield is not very high.Under the catalytic cracking reaction condition, adopt when containing the catalyst of ZSM-5 molecular sieve C in the product
3 =～C
5 =Alkene significantly increases, and this is because the ZSM-5 molecular sieve has mesopore, the result that the shape slective cracking ability is stronger, but reaction mechanism is carried out according to carbonium ion mechanism.CN1083092A has reported the method for catalytic pyrolysis system ethene and propylene, and this method adopts the catalyst that contains clay molecular sieve with layer structure or contain the penta-basic cyclic molecular sieve of rare earth, in 680 ℃～780 ℃ scopes of reaction temperature, can increase the output of ethene.
Consider that voluminous ethene needs higher reaction temperature and regeneration temperature, therefore require the molecular sieve active component aspect structure and the activated centre good heat and hydrothermal stability will arranged, promptly under the steam treatment condition of harshness, molecular sieve can keep high activity, in addition, need to increase the generation and the directly cracking of carbonium ion, wherein particularly increase the generation and the directly cracking of primary carbon cation, suppress uncle's carbonium ion to the second month in a season, the isomery of uncle's carbonium ion, therefore need to increase the shape slective cracking ability of molecular sieve, preferably have certain dehydrogenation ability simultaneously to increase the productive rate of alkene.
The penta-basic cyclic molecular sieve composite that the purpose of this invention is to provide voluminous ethene of a kind of energy and propylene, said composition have good hydro-thermal activity stability, and compared with prior art can further improve the productive rate of ethene when being used for the catalytic pyrolysis reaction.
The penta-basic cyclic molecular sieve composite of voluminous ethene of energy provided by the present invention and propylene is by 85～95 heavy %, the SiO of preferred 88～98 heavy %
2/ Al
2O
3Mol ratio is 15～60 five-membered ring (Pentasil type) molecular sieve, 2～10 heavy %, the phosphorus of preferred 2～8 heavy % (in oxide), 0.3～5 heavy %, a kind of alkaline-earth metal of preferred 0.5～3 heavy % (in oxide) and 0.3～5 heavy %, a kind of transition metal of preferred 0.5～3 heavy % (in oxide) is formed.
Said penta-basic cyclic molecular sieve is the molecular sieve of ZSM-5, ZSM-8 or ZSM-11 structure type in the combination of molecular sieve of the present invention, the molecular sieve of ZSM-5 structure type preferably wherein, its silica alumina ratio is 15～60, be more preferably 15～40, and silica alumina ratio is low more favourable more for voluminous ethene.
Preferably magnesium or calcium of said alkaline-earth metal in the combination of molecular sieve of the present invention.
Said transition metal is a kind of metal with dehydrogenation functionality that is selected from periodic table of elements I B, II B, VI B, VII B or the VIII family in the combination of molecular sieve of the present invention, preferably be selected from a kind of metal among Cr, Mn, Fe, Co, Ni, Cu, the Zn, more preferably be selected from a kind of metal among Ni, Cu or the Zn.
Said phosphorus, alkaline-earth metal and transition metal are to introduce the said molecular sieve by methods such as dipping, mixing from their compound in the combination of molecular sieve of the present invention, with roasting itself and said molecular sieve are had an effect and strong bonded is in the same place by dry again; Wherein the compound of said phosphorus can be phosphoric acid, hydrophosphate or phosphate, and the compound of said alkaline-earth metal and transition metal can be nitrate, sulfate or chloride.
In the former patent report, introduce active element and can strengthen and selects the shaped reaction performance, but reactive activity reduces, this is because molecular sieve is introduced quantitative limitation to active element.In research of the present invention, find that active element introducing amount is subjected to the restriction of the silica alumina ratio of molecular sieve own.Be that silica alumina ratio is low more, big more to introducing the active element capacity, the molecular sieve that silica alumina ratio is low when introducing active element amount is big, still can keep high reactivity.In view of the active element amount of introducing big more, then molecular sieve to select the shaped reaction performance strong more, therefore selecting the low molecular sieve parent of silica alumina ratio for use is favourable to catalytic pyrolysis system ethene, and generally emphasizes that all the high molecular sieve of silica alumina ratio is to reacting favourable in the prior art.This is characteristics of the present invention.
In the present invention, the B acid site that active elements such as discovery introducing alkaline-earth metal can reduce molecular sieve, the L acid site increases relatively simultaneously, and the increase in L acid site is favourable to increasing output of ethylene.
In penta-basic cyclic molecular sieve, introduce transition metal such as Ni, Co, Zn, Cu, Cr, Mn, generally be used as reactive activity constituent elements such as adding dehydrogenation or aromatisation, this is because these yuan have stronger hydrogen transfer reaction performance in the catalytic pyrolysis preparing ethylene reaction, introducing these elements can increase the hydrogen migration ability of molecular sieve, and this is disadvantageous to increasing the olefin product selectivity.But result of study of the present invention finds that in the presence of the P element, the hydrogen transfer reaction ability of transition metal is subjected to obvious suppression, and simultaneously owing to certain dehydrogenation activity is arranged, the alkene particularly selectivity of ethene and propylene improves on the contrary.Therefore in the present invention, introduce at penta-basic cyclic molecular sieve on the basis of P, alkaline-earth metal, introduced transition metals such as Ni, Zn, Cu again, to increase ethylene yield; The existence of phosphorus is very favourable for the hydro-thermal activity stability that improves molecular sieve simultaneously.This is another characteristics of the present invention.
In a word, combination of molecular sieve provided by the present invention the time compared with prior art can significantly improve the particularly productive rate of ethene and propylene of low-carbon alkene being used for the catalytic pyrolysis reaction, and it also has good hydro-thermal activity stability simultaneously.
The synthetic ZSM-5 molecular sieve that obtains belongs to rhombic system, through inorganic NH
4 +The salt exchange is prepared into NH4ZSM-5, passes through roasting (500～600 ℃) again and is prepared into HZSM-5.In these preparation process, the structural symmetry of molecular sieve is constant substantially.But after the high-temperature water vapor processing, the structural symmetry of ZSM-5 molecular sieve can change, its typical feature is the peak generation broadening even the division of 2 θ=24.4 ° in X-ray diffraction (XRD) spectrogram, and the variation of this structural symmetry is consistent relation with the remarkable reduction of molecular sieve cracking reactivity.Therefore, in various embodiments of the present invention and Comparative Examples, the hydrothermal stability in activated centre is judged according to XRD figure.Use n-tetradecane (nC simultaneously
14) the pulse micro-inverse activity estimated judgement.
In the present invention, used molecular sieve raw material and the character of each embodiment and Comparative Examples is as follows:
1.ZSM-5A Qilu Petrochemical company Zhou village catalyst plant is produced, and is synthetic for the template agent with ethamine, roasting removed template method, silica alumina ratio 52.0, ammonium exchange its Na of back
2The heavy % in O≤0.10.
2.ZSM-5B Chang Ling oil-refining chemical factory catalyst plant is produced, silica alumina ratio 25.0 is through NH
4 +Its Na of exchange back
2The heavy % in O≤0.15.
3.ZSM-5C (embodiment 1) is synthesized in the laboratory, silica alumina ratio 19.0 is through NH
4 +After the exchange, its Na
2The heavy % of O=0.05.
Other used chemicals is commercially available chemically pure reagent in each embodiment and the Comparative Examples.
The used analytical method of various embodiments of the present invention and Comparative Examples is as follows:
1. the X-ray diffraction of molecular sieve (XRD) spectrogram is measured with Japanese D/Max-III A type X-ray diffractometer of science.
2. the chemical composition of combination of molecular sieve is measured with x ray fluorescence spectrometry (XRF), and used instrument is Japanese 3271E type Xray fluorescence spectrometer of science.
The following examples will the present invention is further illustrated.
Embodiment 1
Synthesizing of the low silica-alumina ratio ZSM-5 zeolite that present embodiment explanation the present invention is used.
24.6g sodium metaaluminate (Beijing Chemical Plant's production) is dissolved in the 667g deionized water, and under agitation adding 71.7g concentration is the H of 85 heavy %
3PO
4, join 643g waterglass (SiO after this mixture stirred
228 heavy %, Na
2O 9.0 heavy %) in, stir down and placed 4 hours, (the Zhou village catalyst plant is produced, SiO to add the 19.5gZSM-5 molecular sieve then
2/ Al
2O
3=52.0) as crystal seed, continue to stir after 2 hours and be encased in the stainless steel autoclave, under 175 ℃ temperature, stirred crystallization 15 hours, take out crystallization product after being cooled to room temperature, through filtration, washing, 120 ℃ of oven dry, obtain the ZSM-5C sample.Analyze with XRD, the relative crystallinity of this sample (with respect to ZSM-5A) is 92%.
With this sample at molecular sieve: ammonium nitrate: in 90 ℃ of exchanges 2 hours, filter, after the washing, press the similarity condition repeated exchanged once under the condition of deionized water (weight ratio)=1: 1: 20, after 120 ℃ of oven dry, obtain ammonium type ZSM-5C sample, its Na
2O content is 0.05 heavy %.
Comparative Examples 1
This Comparative Examples illustrates the effect of conventional Hydrogen ZSM-5 molecular sieve.
Get NH
4 +ZSM-5A molecular sieve after the exchange is an amount of, puts into the roasting ware, and in 550 ℃ of roastings after 2 hours, compression molding and sieve are got 20～40 purpose particles in Muffle furnace.Getting an amount of this granulin molecule sieve and pack in the stainless steel tube, is 8 hours at 800 ℃, deionized water air speed
-1Condition under, carry out the burin-in process of 4 hours 100% water vapour atmosphere, to the ZSM-5B after the ammonium exchange, the ZSM-5C sample carries out roasting and high-temperature water vapor burin-in process respectively under similarity condition, and the sample that obtains is designated as DZSM-5A, DZSM-5B, DZSM-5C respectively.Sample after above-mentioned three kinds of processing is carried out XRD analysis and n-tetradecane (nC
14) the pulse micro-inverse evaluation, its evaluation result is listed in the table 1.Wherein the pulse micro-inverse appreciation condition is: the molecular sieve loading amount is 0.g, 480 ℃ of reaction temperatures, carrier gas N
2Flow velocity is 30 ml/min (ml/min), nC
14Sample size is 0.5 microlitre (μ l).
Table 1
| Molecular sieve | 24.4 ° of peak-to-peak shapes of XRD | nC 14Conversion ratio, % |
| DZSM-5A | Bimodal | 26.6 |
| DZSM-5B | Bimodal | 33.1 |
| DZSM-5C | Bimodal | 30.5 |
After conventional as can be seen Hydrogen ZSM-5 molecular sieve was handled through high-temperature water vapor, the structure of molecular sieve changed, in the XRD spectra 24.4 ° diffraction maximum be split into bimodal, nC
14Conversion ratio also significantly descend.
Comparative Examples 2
Use the effect of the ZSM-5 molecular sieve of P and Mg modification in this Comparative Examples explanation prior art.
Get ZSM-5B sieve sample 19g (dry basis), put into (NH by 1.9g
4)
2HPO
4In the solution that is mixed with the 40g deionized water, stir after 12 hours, under the room temperature in 120 ℃ of oven dry, then 550 ℃ of following roastings 2 hours.With the gained sample again with by 1.51g Mg (CH
3COO)
24H
2The solution that O and 40g deionized water are mixed with mixes, and stirs after 12 hours under the room temperature, and in 120 ℃ of oven dry, 550 ℃ of following roastings 2 hours, the gained molecular sieve was designated as D-2 then.The analysis showed that the P of this sample by xrf method
2O
5Content is 5.0 heavy %, and MgO content is 1.4 heavy %.According to Comparative Examples 1 described method,, after 800 ℃/4h, 100% water vapour atmosphere burin-in process, carry out XRD and nC with above-mentioned sample D-2 compression molding
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Comparative Examples 3
Get ZSM-5A sieve sample 19g (dry basis), put into (NH by 1.9g
4)
2HPO
4In the solution that is mixed with the 40g deionized water, stir after 12 hours, under the room temperature in 120 ℃ of oven dry, then 550 ℃ of following roastings 2 hours.
With the gained sample again with by 0.43g ZnCl
2The solution that is mixed with the 40g deionized water mixes, and stirs after 12 hours under the room temperature, and in 120 ℃ of oven dry, 550 ℃ of following roastings 2 hours, the gained molecular sieve was designated as D-3 then.The analysis showed that the P of this sample by xrf method
2O
5Content is 5.0 heavy %, and ZnO content is 1.3 heavy %.
According to Comparative Examples 1 described method,, behind 800 ℃/4 hours, 100% water vapour atmosphere burin-in process, carry out XRD and nC with above-mentioned sample D-3 compression molding
14Pulse micro-inverse is estimated, and it the results are shown in Table 2.
Embodiment 2
Get 19g (butt) ZSM-5B sieve sample, and by the heavy %H of 1.62g 85
3PO
4, 40g deionized water, 1.48g MgCl
26H
2O and 0.70g Ni (NO
3)
26H
2The solution that O makes at room temperature stirred 2 hours after mixing, and again 120 ℃ of oven dry, in 550 ℃ of roastings 2 hours, the gained molecular sieve was designated as ZEP-11 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, MgO 1.4 heavy %, NiO 0.86 heavy %.
According to the method for Comparative Examples 1, gained ZEP-11 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Embodiment 3
Get 19g (butt) ZSM-5B sieve sample, and by the heavy %H of 1.62g 85
3PO
4, 40g deionized water, 0.98g MgCl
26H
2O and 2.09g Ni (NO
3)
26H
2The solution that O makes at room temperature stirred 2 hours after mixing, and again 120 ℃ of oven dry, in 550 ℃ of roastings 2 hours, the gained molecular sieve was designated as ZEP-12 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, MgO 0.91 heavy %, NiO 2.6 heavy %.
According to the method for Comparative Examples 1, gained ZEP-12 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Embodiment 4
Get 19g (butt) ZSM-5B sieve sample, and by the heavy %H of 1.62g 85
3PO
4, 40g deionized water, 1.48g MgCl
26H
2O and 0.33g ZnCl
2The solution of making at room temperature stirred 1 hour after mixing, and again 120 ℃ of oven dry, in 550 ℃ of roastings 2 hours, the gained molecular sieve was designated as ZEP-13 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, MgO 1.4 heavy %, the heavy % of ZnO0.94.
According to the method for Comparative Examples 1, gained ZEP-13 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Embodiment 5
Get 19g (butt) ZSM-5C sieve sample, and by the heavy % H of 1.62g 85
3PO
4, 40g deionized water, 1.00g MgCl
26H
2O and 0.65g ZnCl
2The solution of making at room temperature stirred 2 hours after mixing, and again 120 ℃ of oven dry, in 650 ℃ of roastings 1 hour, the gained molecular sieve was designated as ZEP-14 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, MgO 0.94 heavy %, ZnO 1.9 heavy %.
According to the method for Comparative Examples 1, gained ZEP-14 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Embodiment 6
Get 19g (butt) ZSM-5B sieve sample, and by the heavy %H of 1.62g 85
3PO
4, 40g deionized water, 1.48g MgCl
26H
2O and 0.57g Cu (NO
3)
23H
2The solution that O makes at room temperature stirred 2 hours after mixing, and again 120 ℃ of oven dry, in 550 ℃ of roastings 2 hours, the gained molecular sieve was designated as ZEP-15 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, MgO 1.4 heavy %, CuO 0.91 heavy %.
According to the method for Comparative Examples 1, gained 7EP-15 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Embodiment 7
Get 19g (butt) ZSM-5C sieve sample, and by the heavy %H of 1.62g 85
3PO
4, 40g deionized water, 0.53g CaCl
22H
2O and 1.15g Cu (NO
3)
23H
2The solution that O makes at room temperature stirred 2 hours after mixing, and again 120 ℃ of oven dry, in 550 ℃ of roastings 2 hours, the gained molecular sieve was designated as ZEP-16 then.According to XRF analysis, this sample contains P
2O
54.9 heavy %, CaO 1.0 heavy %, CuO 1.9 heavy %.
According to the method for Comparative Examples 1, gained ZEP-16 sample carried out the high-temperature water vapor burin-in process after, carry out XRD and nC
14Pulse micro-inverse is estimated.The results are shown in Table 2.
Table 2
| Molecular sieve | 24.4 ° of peak-to-peak shapes of XRD | nC 14Conversion ratio, % |
| D-2 | Unimodal | 98.0 |
| D-3 | Unimodal | 95.5 |
| ZEP-11 | Unimodal | 99.6 |
| ZEP-12 | Unimodal | 98.9 |
| ZEP-13 | Unimodal | 99.3 |
| ZEP-14 | Unimodal | 97.5 |
| ZEP-15 | Unimodal | 92.2 |
| ZEP-16 | Unimodal | 90.5 |
By table 2 as seen, behind introducing transition metal Ni, the Zn, 24.4 ° of peaks still keep unimodal, nC in the XRD figure of molecular sieve
14Conversion ratio is also very high.
Embodiment 8
According to molecular sieve: aluminium colloidal sol is (with Al
2O
3Meter): the butt weight score of kaolin=15: 15: 70 is not prepared into five catalyst without aging D-2, D-3, ZEP-11,7EP-13 and ZEP-15 sieve sample according to the spray-dired method of routine with gained, also is catalyst (the containing HZSM-5 molecular sieve 20 heavy %) catalyst as a comparison of CHP-1 in addition with the trade names that are used for low-carbon olefines high-output of Qilu Petrochemical company Zhou village catalyst plant production.These six kinds of catalyst are carried out the little anti-and fixed fluidized bed reaction evaluating of light oil through behind 800 ℃/4 hours, 100% water vapour atmosphere burin-in process.
The results are shown in Table 3 for the light oil micro anti-evaluation.Appreciation condition is: 520 ℃ of reaction temperatures, oil ratio 3.2, weight space velocity are 16 hours
-1, catalyst loading amount 5.0g.229～340 ℃ of feedstock oil boiling range scopes.
Fixed fluidized bed catalytic pyrolysis evaluation result is listed in the table 4.Appreciation condition is: 700 ℃ of reaction temperatures, oil ratio 10, charging air speed 10 hours
-1, water injection rate 80 heavy %.Raw materials used oil is the grand celebration wax oil, 346～546 ℃ of boiling range scopes.
By table 3 and table 4 result as seen, introducing transition metal such as Ni, Zn, Cu in molecular sieve can obviously increase ethylene yield.
Table 3
| Molecular sieve | HZSM-5 | D-2 | D-3 | ZEP-11 | ZEP-13 | ZEP-15 |
| Conversion ratio, heavy % | 44.0 | 62.38 | 61.01 | 63.92 | 64.05 | 63.21 |
| The cracked gas productive rate, heavy % therein ethylene propylene butene | 16.76 0.82 6.50 5.63 | 27.23 2.88 7.57 4.95 | 26.46 3.02 7.32 4.20 | 27.63 3.51 7.34 4.71 | 27.65 3.46 7.61 4.82 | 26.98 3.32 7.92 5.22 |
Table 4
| Molecular sieve | HZSM-5 | D-2 | D-3 | ZEP-11 | ZEP-13 | ZEP-15 |
| Conversion ratio, heavy % | 89.93 | 91.02 | 90.51 | 92.72 | 93.63 | 90.75 |
| Product distributes, heavy % cracked gas productive rate therein ethylene propylene butene C 2 =+C 3 =+C 4 =Gasoline (C 5～221 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke | 62.75 17.25 18.91 12.11 48.27 24.81 6.51 3.56 6.37 | 69.70 20.77 22.47 10.69 53.13 15.22 5.33 3.65 6.10 | 70.50 20.32 19.57 11.39 51.28 13.16 5.77 3.72 6.85 | 70.18 23.20 21.66 8.37 53.23 14.33 4.18 3.10 8.21 | 71.30 23.95 22.08 7.68 53.71 14.96 3.79 2.58 7.37 | 69.80 20.98 21.33 9.35 51.66 14.21 5.38 3.87 6.74 |
Claims (9)
1. a penta-basic cyclic molecular sieve composite is characterized in that the SiO of said composition by 85～95 heavy %
2/ Al
2O
3Mol ratio is formed in a kind of alkaline-earth metal of oxide and a kind of transition metal with dehydrogenation functionality that is selected from periodic table of elements I B, II B, VI B, VII B or the VIII family in oxide of 0.3～5 heavy % by the phosphorus in oxide of 15～60 penta-basic cyclic molecular sieve, 2～10 heavy %, 0.3～5 heavy %'s.
2. according to the combination of molecular sieve of claim 1, it is characterized in that the SiO of said composition by 88～98 heavy %
2/ Al
2O
3Mol ratio is formed by 15～60 penta-basic cyclic molecular sieve, the phosphorus in oxide of 2～8 heavy %, a kind of alkaline-earth metal and 0.5～3 a kind of transition metal in oxide that weighs % in oxide of 0.5～3 heavy %.
3. according to the combination of molecular sieve of claim 1, wherein said penta-basic cyclic molecular sieve is the molecular sieve of ZSM-5, ZSM-8 or ZSM-11 structure type.
4. according to the combination of molecular sieve of claim 3, wherein said penta-basic cyclic molecular sieve is the molecular sieve of ZSM-5 structure type.
5. according to the combination of molecular sieve of claim 1, wherein said its silica alumina ratio of penta-basic cyclic molecular sieve is 15～60.
6. according to the combination of molecular sieve of claim 5, wherein said its silica alumina ratio of penta-basic cyclic molecular sieve is 15～40.
7. according to the combination of molecular sieve of claim 1, wherein said alkaline-earth metal is magnesium or calcium.
8. according to the combination of molecular sieve of claim 1, wherein said transition metal is a kind of metal that is selected among Cr, Mn, Fe, Co, Ni, Cu, the Zn.
9. according to the combination of molecular sieve of claim 8, wherein said transition metal is a kind of metal that is selected among Ni, Cu or the Zn.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116445A CN1072032C (en) | 1997-09-17 | 1997-09-17 | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene |
| US09/154,581 US6080698A (en) | 1997-09-17 | 1998-09-17 | Pentasil-type molecular sieve containing composition and its preparation method |
| EP98307583A EP0903178B2 (en) | 1997-09-17 | 1998-09-17 | A pentasil-type molecular sieve containing composition, its preparation method and use |
| NO19984332A NO321464B1 (en) | 1997-09-17 | 1998-09-17 | Composition containing a pentasil-type molecular sieve, and its preparation and use |
| JP26370398A JP3741548B2 (en) | 1997-09-17 | 1998-09-17 | Pencil-type molecular sieve-containing composition and preparation method thereof |
| DE69819989T DE69819989T3 (en) | 1997-09-17 | 1998-09-17 | Composition containing pentasil-type molecular sieves, and their preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116445A CN1072032C (en) | 1997-09-17 | 1997-09-17 | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene |
Publications (2)
| Publication Number | Publication Date |
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| CN1211470A CN1211470A (en) | 1999-03-24 |
| CN1072032C true CN1072032C (en) | 2001-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97116445A Expired - Lifetime CN1072032C (en) | 1997-09-17 | 1997-09-17 | Pentabasic cyclic molecular sieve composite for high output of ethylene and propylene |
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| Country | Link |
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| CN (1) | CN1072032C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391610C (en) * | 2005-08-15 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
| US9895686B2 (en) | 2009-10-30 | 2018-02-20 | Petrochina Company Limited | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| WO2020078434A1 (en) | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| US11964262B2 (en) | 2018-10-18 | 2024-04-23 | China Petroleum & Chemical Corporation | Phosphorus-containing rare-earth-containing MFI structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| US11975980B2 (en) | 2018-10-18 | 2024-05-07 | China Petroleum & Chemical Corporation | MFI structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
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| CN1301794C (en) * | 2004-08-06 | 2007-02-28 | 董家禄 | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process |
| CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
| CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| JP5840840B2 (en) | 2007-12-20 | 2016-01-06 | 中国石油化工股▲分▼有限公司 | An improved integrated method for hydrogenating and catalytically cracking hydrocarbon oils |
| CN102166533B (en) * | 2010-02-25 | 2013-07-31 | 中国石油天然气股份有限公司 | Composite modified molecular sieve improving activity and hydrothermal stability and preparation method thereof |
| US11680210B2 (en) * | 2021-11-04 | 2023-06-20 | Chevron U.S.A. Inc. | Catalytic cracking of glyceride oils with deactivated phosphorus-containing ZSM-5 light olefins additives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391610C (en) * | 2005-08-15 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
| US9895686B2 (en) | 2009-10-30 | 2018-02-20 | Petrochina Company Limited | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| WO2020078434A1 (en) | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| US11964262B2 (en) | 2018-10-18 | 2024-04-23 | China Petroleum & Chemical Corporation | Phosphorus-containing rare-earth-containing MFI structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| US11975980B2 (en) | 2018-10-18 | 2024-05-07 | China Petroleum & Chemical Corporation | MFI structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
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|---|---|
| CN1211470A (en) | 1999-03-24 |
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