CN100531910C - Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene - Google Patents

Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene Download PDF

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CN100531910C
CN100531910C CNB2007100390765A CN200710039076A CN100531910C CN 100531910 C CN100531910 C CN 100531910C CN B2007100390765 A CNB2007100390765 A CN B2007100390765A CN 200710039076 A CN200710039076 A CN 200710039076A CN 100531910 C CN100531910 C CN 100531910C
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zsm
molecular sieve
catalyst
catalytic pyrolysis
zeolite
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CN101279286A (en
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马广伟
谢在库
胡永君
肖景娴
杨霞琴
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention relates to a catalyst used for manufacturing ethylene and propylene by naphtha catalytic pyrolysis which mainly solves the problems of high reaction temperature and low yield of catalyst to ethylene and propylene in the existing catalytic pyrolysis reaction. The present invention better solves the problems by adopting the technical proposal of taking a ZSM-5/Y zeolite symbiosis molecular sieve as the catalyst. The present invention can be used for the industrial production of ethylene and propylene by naphtha catalytic pyrolysis.

Description

The catalyst of naphtha catalytic pyrolysis preparing ethylene propylene
Technical field
The present invention relates to a kind of catalyst of naphtha catalytic pyrolysis preparing ethylene propylene.
Background technology
Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.Whole world ethene is raw material with naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard cracking reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the aperture molecular sieve between 0.5～0.65 is a catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower;
Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550～600 ℃, and conversion of raw material is lower.
Mobil Oil Corporation (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyst and elementary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the serviceability temperature of catalyst, conversion of raw material and product yield are all lower.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst activity that uses in the existing naphtha catalytic cracking reaction is lower, and the problem that the yield of ethylene, propylene is lower, serviceability temperature is high provides a kind of catalyst of new naphtha catalytic pyrolysis preparing ethylene propylene.This catalyst has active height, ethylene, propylene yield height, advantage that serviceability temperature is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of naphtha catalytic pyrolysis preparing ethylene propylene, catalyst are SiO 2/ Al 2O 3Mol ratio is 12～500 ZSM-5/Y zeolite coexisting molecular sieve, in the ZSM-5/Y zeolite coexisting molecular sieve by weight percentage the content of ZSM-5 molecular sieve be 49.8～99.5%.
In the technique scheme, the SiO of ZSM-5/Y zeolite coexisting molecular sieve 2/ Al 2O 3Mol ratio is that preferable range is 14～200, and more preferably scope is 16～50.In the ZSM-5/Y zeolite coexisting molecular sieve by weight percentage the content preferable range of ZSM-5 molecular sieve be 60～99%.
At least a as in silicate, metasilicate sodium or the Ludox of the preparation coexisting molecular sieve silicon source of using, the aluminium source is at least a in aluminium salt or the aluminate, the template agent is at least a in ethylenediamine, ethamine, n-butylamine, triethylamine, 4-propyl bromide, the TPAOH, and the pH value of regulating colloidal sol with diluted acid is 10～12.
The synthetic method of ZSM-5/Y zeolite coexisting molecular sieve is, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds the template agent of aequum then, stirs after 30 minutes with rare acid for adjusting pH value in 10～12 scopes, add the Y zeolite seed crystal, supply distilled water again.Colloidal sol is put into autoclave, control required temperature crystallization after 10～100 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain ZSM-5/Y zeolite coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes hydrogen type molecular sieve after repeating twice, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed bed reactors and check and rate.
Catalyst involved in the present invention, owing to adopted the coexisting molecular sieve that contains ZSM-5 molecular sieve and Y zeolite simultaneously, this molecular sieve is owing to contain acid strong Y zeolite, so its acid amount is bigger, acidity is stronger, is suitable for the higher alkane cracking of cracking energy.Because coexisting molecular sieve contains multistage pore canal, can handle the different mixture material of molecular diameter.Because the degree that comes to the surface, acidity, duct and the specific surface of coexisting molecular sieve and having than big difference of two kinds of molecular sieve mechanical mixture so catalytic performance is preferably arranged, are used for the naphtha catalytic pyrolysis preparing ethylene propylene reaction, with C 4～C 10The naphtha of hydrocarbon is raw material (the raw material physical index sees Table 1), is 12 millimeters down examination of fixed bed reactors normal pressure with diameter, and range of reaction temperature is 600～700 ℃, and reaction pressure is 0.001MPa～0.5MPa, and weight space velocity is 0.25～2 hour -1, water/feedstock oil mass ratio is that ethene and propylene total recovery can reach 51.47% and obtain better technical effect under 1～4: 1 the condition.
Description of drawings
Fig. 1 is the XRD figure spectrum of ZSM-5/Y zeolite coexisting molecular sieve
Curve 1 is the XRD diffracting spectrum of FH-1 sample among Fig. 1, and curve 2 is the XRD diffracting spectrum of FH-12 sample.
Table 1 feed naphtha index
Project Data
Density (20 ℃) kilogram/rice 3 704.6
Boiling range is boiling range ℃ just 40
Whole boiling range ℃ 160
Saturated vapor pressure (20 ℃) kPa 50.2
Alkane % (weight %) 65.18
N-alkane % (weight %) in the alkane >32.5
Cycloalkane % (weight %) 28.44
Alkene % (weight %) 0.17
Aromatic hydrocarbons % (weight %) 6.21
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, after stirring a period of time, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethamine: H 2O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite seed crystals, mixed solution is put into autoclave, 130 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/Y zeolite coexisting molecular sieve, the XRD diffracting spectrum quantitatively contains 94.5% ZSM-5 and 5.5% Y zeolite in the coexisting molecular sieve as can be known by weight percentage with the XRD diffraction shown in curve among Fig. 11.It with concentration 5% ammonium nitrate solution, twice of 70 ℃ of exchange, 550 ℃ of roastings are 3 hours then, after repeating twice, make Hydrogen ZSM-5/Y zeolite coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed bed reactors, be 0.02MPa, weight space velocity 0.5 hour in 650 ℃ of reaction temperatures, reaction pressure -1, check and rate under water/condition of 3: 1 of feedstock oil weight ratio, the results are shown in Table 5.
[embodiment 2～4]
According to the method for embodiment 1, the pH of control solution is respectively 10.5,11 and 12, synthesizes ZSM-5/Y zeolite coexisting molecular sieve respectively, is designated as FH-2 respectively, FH-3, FH-4.The ratio of ZSM-5 and Y zeolite sees Table 4.Method examination according to embodiment 1 the results are shown in Table 5.
[embodiment 5～12]
According to the method for embodiment 1, the different mole proportionings of control solution, He Cheng ZSM-5/Y zeolite coexisting molecular sieve sees Table 2 respectively, and the ratio of ZSM-5 and Y zeolite sees Table 4.Method examination according to embodiment 1 the results are shown in Table 5.
Table 2
Embodiment Solution mole proportioning Sample number into spectrum
Embodiment
5 Si∶Al∶M∶H 2O＝1∶0.005∶0.4∶40 FH-5
Embodiment 6 Si∶Al∶M∶H2O＝1∶0.01∶0.4∶40 FH-6
Embodiment 7 Si∶Al∶M∶H 2O＝1∶0.05∶0.4∶40 FH-7
Embodiment 8 Si∶Al∶M∶H 2O＝1∶0.125∶0.4∶40 FH-8
Embodiment 9 Si∶Al∶M∶H 2O＝1∶0.143∶0.4∶40 FH-9
Embodiment 10 Si∶Al∶M∶H 2O＝1∶0.1∶0.2∶30 FH-10
Embodiment 11 Si∶Al∶M∶H 2O＝1∶0.1∶0.5∶100 FH-11
Embodiment 12 Si∶Al∶M∶H 2O＝1∶0.1∶0.4∶80 FH-12
[embodiment 13～16]
Method according to embodiment 1, the mole proportioning of control solution is identical, adding Y zeolite seed crystal amount respectively is 5.68 grams, 11.3 grams, 22.6 grams and 28.4 grams, synthetic ZSM-5/Y zeolite coexisting molecular sieve, be designated as FH-13, FH-14, FH-15, FH-16 respectively, the XRD diffracting spectrum of FH-13 is shown in curve among Fig. 12, and the ratio of ZSM-5 and Y zeolite sees Table 4.Method examination according to embodiment 1 the results are shown in Table 5.
[embodiment 17～20]
According to the method for embodiment 1, the mole proportioning of control solution is identical, selects different template agent for use, has synthesized ZSM-5/Y zeolite coexisting molecular sieve respectively, sees Table 3.The ratio of ZSM-5 and Y zeolite sees Table 4.Method examination according to embodiment 1 the results are shown in Table 5.
Table 3
Embodiment Template agent kind Template agent molar ratio Sample number into spectrum
Embodiment 17 N-butylamine — FH-17
Embodiment 18 Ethamine — FH-18
Embodiment 19 Ethylenediamine and n-butylamine 1∶1 FH-19
Embodiment 20 =ethamine, n-butylamine and ethamine 1∶1∶1 FH-20
[embodiment 21～22]
According to the method for embodiment 1, the mole proportioning of control solution is identical, and crystallization temperature is set to 120 ℃ and 140 ℃ respectively, has synthesized ZSM-5/Y zeolite coexisting molecular sieve respectively, is designated as FH-20, FH-21, and the ratio of ZSM-5 and Y zeolite sees Table 4.Method examination according to embodiment 1 the results are shown in Table 5.
Table 4
Sample number into spectrum Contain ZSM-5 ratio (weight %) Contain Y zeolite ratio (weight %)
FH-1 94.5 5.5
FH-2 98.4 1.6
FH-3 95.5 4.5
FH-4 87.6 12.4
FH-5 99.2 0.8
FH-6 98.9 1.1
FH-7 96.1 3.9
FH-8 80.5 19.5
FH-9 74.3 25.7
FH-10 90.5 9.5
FH-11 95.4 4.6
FH-12 95.0 5.0
FH-13 89.7 10.3
FH-14 71.4 29.6
FH-15 60.5 39.5
FH-16 49.8 50.2
FH-17 94.0 6.0
FH-18 93.6 6.4
FH-19 95.2 4.8
FH-20 94.7 5.3
FH-21 90.2 8.8
FH-22 96.4 3.6
Table 5
Sample number into spectrum Yield of ethene (weight %) Propene yield (weight %) Total recovery (weight %)
FH-1 23.42 26.67 50.09
FH-2 24.12 27.35 51.47
FH-4 22.17 25.43 47.60
FH-7 25.14 25.31 50.45
FH-8 22.45 24.23 46.68
FH-10 22.56 25.62 48.18
FH-13 23.67 24.39 48.06
FH-14 21.25 24.50 45.75
FH-20 24.69 25.54 50.23
[comparative example 1]
With the synthesis mode of embodiment 1, do not add the Y zeolite seed crystal, synthetic pure ZSM-5 molecular sieve, making the catalyst postscript is C-1, checks and rates according to the mode of embodiment 1, the results are shown in Table 5.
[comparative example 2]
In the mode of embodiment 1, add 11.3 gram Y zeolite seed crystals, crystallization temperature is 120 ℃, synthetic pure Y zeolite, making the catalyst postscript is C-2, checks and rates according to the mode of embodiment 1, the results are shown in Table 5.
[comparative example 3]
According to the ratio of ZSM-5 among the embodiment 13 and zeolite, prepare the mechanical impurity of the two, make catalyst, be designated as C-3, check and rate by the mode of embodiment 1, the results are shown in Table 6.
Table 6
Sample Yield of ethene (weight %) Propene yield (weight %) Total recovery (weight %)
C-1 23.16 22.28 45.44
C-2 20.22 21.47 41.69
C-3 23.55 23.62 47.17

Claims (4)

1, a kind of catalyst of naphtha catalytic pyrolysis preparing ethylene propylene is characterized in that catalyst is SiO 2/ Al 2O 3Mol ratio is 12～500 ZSM-5/Y zeolite coexisting molecular sieve, in the ZSM-5/Y zeolite coexisting molecular sieve by weight percentage the content of ZSM-5 molecular sieve be 49.8～99.5%.
2,, it is characterized in that the SiO of ZSM-5/Y zeolite coexisting molecular sieve according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1 2/ Al 2O 3Mol ratio 14～200.
3,, it is characterized in that the SiO of ZSM-5/Y zeolite coexisting molecular sieve according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 2 2/ Al 2O 3Mol ratio 16～50.
4,, it is characterized in that in the ZSM-5/Y zeolite coexisting molecular sieve that the content of ZSM-5 molecular sieve is 60～99% by weight percentage according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1.
CNB2007100390765A 2007-04-04 2007-04-04 Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene Active CN100531910C (en)

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