CN1806917A - Activation of ZSM-5 series catalyst and method for catalytic cracking butane to prepared light olefines thereby - Google Patents

Activation of ZSM-5 series catalyst and method for catalytic cracking butane to prepared light olefines thereby Download PDF

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CN1806917A
CN1806917A CNA2005100024149A CN200510002414A CN1806917A CN 1806917 A CN1806917 A CN 1806917A CN A2005100024149 A CNA2005100024149 A CN A2005100024149A CN 200510002414 A CN200510002414 A CN 200510002414A CN 1806917 A CN1806917 A CN 1806917A
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catalyst
temperature
butane
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molecular sieve
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CN100560205C (en
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赵震
陆江银
徐春明
段爱军
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China University of Petroleum Beijing
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Abstract

The invention provides the method for improving the activity of ZSM-5 series molecular sieve catalyst, comprising the following steps: using inorganic salt, inorganic acid or organic acid to heat change treat and calcine the said catalyst more than one time. The invention also provides the method of using the ZSM-5 series molecular sieve catalyst whose activity is improved to crack the C4 paraffin to produce lower carbon number olefin.

Description

The activation of ZSM-5 catalyst series and the method for catalytic cracking butane to prepared light olefines thereby thereof
Technical field
The present invention relates to improve the method for porous silicoaluminate activity of such catalysts, and realize the method for butane producing low-carbon alkene by catalytic pyrolysis, the invention belongs to the petrochemical industry application by improving catalyst activity.
Background technology
C-4-fraction mainly comes catalytic cracking and steam cracking process, and the present worldwide recoverable amount of C-4-fraction is appreciable.According to estimates, C-4-fraction will be the valuable petrochemical materials that may make full use of after ethene and propylene.To the chemical utilization rate of C-4-fraction at the U.S., Japan and west european developed country up to more than 55%, and China has only 41%, and mainly concentrates on the utilization of C 4 olefin, butane is also mainly as the fuel utilization.So research is to the more effective processing and utilization of C-4-fraction, especially the alkane in the C-4-fraction being carried out effective processing and utilization also is to be subjected to the problem that petrochemical industry is paid close attention to.In the various researchs that utilize approach are sought, it is a kind of very promising application technology that butane is implemented producing low-carbon alkene by catalytic pyrolysis, the realization of this technology can make full use of cheapness and superfluous, that added value is lower relatively butane raw material on the one hand, can obtain the wide low-carbon alkene of purposes on the other hand again, especially at present ethene, propylene product very in short supply.
Nineteen nineties begins in early days, catalytic pyrolysis research for naphtha, direct steaming gasoline, low-carbon alkanes mainly comprises the research and development of catalyst and the research of cracking technology, especially adopting alkali metal or alkaline earth oxide is the Deep Catalytic Cracking process of catalyst, and as the exploitation of the former Soviet Union is the Deep Catalytic Cracking process technology of catalyst with the potassium vanadate.The characteristics of this type of catalyst are to make yield of light olefins nearly 50%, but reaction temperature is higher, and general the requirement is higher than 750 ℃.With this understanding, the easy coking of catalyst, so the catalyst that requires to use should have very high heat endurance, common catalyst is difficult to be competent at.
In recent years, mainly concentrate on the aluminosilicate molecular sieves system about the catalytic pyrolysis of hydrocarbon and the Study on Cleavage of low-carbon alkanes, as various ZSM molecular sieves, ZRP and SAPO equimolecular sieve.A kind of technology that C 4 olefin and above alkene thereof is converted into propylene has been proposed among the CN1413965A.Catalyst directly uses SiO in the document 2/ Al 2O 3(abbreviation silica alumina ratio) is 38～500 ZSM-5 molecular sieve, and reaction temperature is 540～580 ℃, and raw material olefin liquid air speed is 15 hours -1This technology is used the C-4-fraction that steam cracking produces in mixed c 4 that carbon four raw materials produce as the plant catalytic cracking or the ethylene plant, characteristics are the yields that improved purpose product propylene at a lower temperature, the yield of propylene reaches as high as 29.2wt%, but course of reaction is detected the normal butane and the iso-butane that show in the raw material cracking does not take place substantially, that is what, under this catalyst action cracking takes place mainly is alkene.
Except that various molecular sieves, also have adopt metal particularly noble metal load on acid carrier such as the activated alumina, carry out the catalytic pyrolysis research of C-4-fraction.CN1026100C discloses with infusion process noble metal platinum or palladium is loaded on the catalytic cracking catalyst that activated alumina obtains and utilize the cracking of this catalytic cracking catalyst to low-carbon alkanes.Small stationary self-heating reactor is adopted in reaction, and the reaction temperature of determining in the experiment is 550 ℃, and reaction mass is low-carbon alkanes and diluent gas (hydrogen, nitrogen, oxygen).The alkane that is suitable for is ethane, propane, butane, iso-butane and mixed alkanes thereof.At working load the aluminium oxide of platinum during as catalyst cracking normal butane, the highest yield of total olefin can reach 53.0%, but wherein propene yield is very low, only is 8.0%; Under the same close condition, the catalytic pyrolysis iso-butane can get higher propene yield, but yield of ethene is then lower.Also study simultaneously platinum or palladium and loaded on self-heating catalytic pyrolysis on other carrier, obtained similar result.
In a word, owing to the butane in the cheap C-4-fraction that enrich has advantages of higher stability, the employing butane is a raw material, promptly when iso-butane and normal butane or its mixture, and normal butane particularly, the temperature of catalytic cracking reaction needs is generally higher.Improve activity of such catalysts and selectivity, reduce the catalytic cracking reaction temperature, improve the yield of the rare hydrocarbon of low-carbon (LC), ethene and propylene cheaply are provided especially simultaneously, obviously have the very economic implications of reality.
Summary of the invention
The objective of the invention is to research and propose a kind of method of the aluminosilicate molecular sieves catalyst being carried out activation processing, activity of such catalysts is improved, can be implemented under the temperature conditions of obvious reduction butane is implemented catalytic pyrolysis, obtain higher yield of light olefins.
The present invention also aims to provide a kind of method of butane being carried out catalytic cracking to prepare lower carbon olefin, use catalyst through activation processing, improved the yield of low-carbon alkene simultaneously in the shortcoming that has solved present cracking reaction temperature drift, important and in short supply chemical material ethylene and propylene can be provided efficiently.
In order to reduce the cracking temperature of butane, improve the yield of ethene and propylene in the catabolite simultaneously, the inventor studies the catalytic performance of various catalyst, discovery is to the aluminosilicate catalyst in the present report, especially wherein commercial type ZSM 5 molecular sieve catalyst is suitably handled, can significantly improve the catalytic activity of catalyst, thereby under relatively low temperature, realize catalytic pyrolysis butane.So the present invention at first provides the method that improves the aluminosilicate catalyst activity, described aluminosilicate catalyst is preferably ZSM-5 series molecular sieve, this method comprises that with inorganic salts, inorganic acid or organic acid described aluminosilicate catalyst being carried out once above heat exchange process makes hydrogen type molecular sieve, 30～100 ℃ of treatment temperatures, thermal bake-out under 200～1000 ℃ temperature then, roasting process is 1～10 hour; In this processing procedure, when adopting inorganic salts to handle, the consumption of salt is 5～45 mMs/gram catalyst, and when adopting inorganic acid or organic acid to handle, the consumption of acid is 0.3～40 mM/gram catalyst.
In the said method, preferably, the inorganic salts that are used to handle catalyst are ammonium chloride, ammonium nitrate or ammonium carbonate; The organic acid or the inorganic acid that are used to handle catalyst are oxalic acid, formic acid or hydrochloric acid; Improve active effect for reaching, require catalyst is carried out once above reprocessing, total processing time is preferably 2～6 hours.
Carrying out the above-mentioned hydrotreated while, making the molecular sieve that obtains load base metal again, can produce the effect of better raising activity.That is, through catalyst supported active base metal under 10～100 ℃ temperature, the then heat treatment under 200～1000 ℃ of temperature earlier after inorganic salts, organic acid or the mineral acid treatment; The consumption of the used slaine of this loading process is 0.001～100 mM/gram catalyst, and load time is 0.5～10 hour.Be applicable to that metal of the present invention can be one or more in titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten or the aluminium etc.Used slaine is carbonate, sulfate, nitrate, oxalates, phosphate or the chloride of above-mentioned selected metal during load, also can be corresponding ammonium salt etc.Can control consumption 0.02～10 mM/gram catalyst of slaine in the loading process, and the mode of metal load is ion-exchange, infusion process, coprecipitation or mixing method commonly used.
According to the method described above ZSM-5 series molecular sieve is handled, obtained the catalyst that activity significantly improves, can be used for the catalytic pyrolysis of butane is prepared in the production of low-carbon alkene.
According to a further aspect in the invention, the method of butane being carried out producing low-carbon alkene by catalytic pyrolysis is provided, promptly, adopt the type ZSM 5 molecular sieve catalyst, carry out activation processing at first according to the method described above, be used for the catalytic cracking reaction of butane then, this catalytic cracking reaction is 400～700 ℃ of temperature, pressure 0.01～0.20MPa, gas phase air speed 2000～40000 hours -1Take place under the condition.
When according to method of the present invention low-carbon alkanes being carried out catalytic pyrolysis, preferred described butane is normal butane or iso-butane, and the purpose product that obtains---low-carbon alkene is mainly C2～C4 alkene.
Deep Catalytic Cracking process of the present invention is by adopting the type ZSM 5 molecular sieve catalyst through activation processing, realized cracking to alkane, thereby the butane that can make full use of in the cheap C-4-fraction is produced low-carbon alkene, solved that butane catalytic pyrolysis temperature was higher in the past, the difficult problem that the character of custom catalysts is difficult to satisfy the demand, and low-carbon alkene (especially propylene) problem that yield is lower of C2～C4 in the pyrolysis product, in pyrolysis product, triolefin yield (ethene, propylene or butylene) can reach more than 50%, and be that raw material carries out that triolefin reaches as high as more than 65% in the product of cracking with the iso-butane, the yield of propylene reaches as high as more than 32% in the triolefin, is used for suitability for industrialized production and will brings good prospects for application.
According to preferred version of the present invention, silica alumina ratio in the commercial type ZSM 5 molecular sieve that uses is 1～200, be preferably 10～200, because silica alumina ratio has certain influence to the cracking reaction of alkane, in actual production, can screen according to actual needs, in general, the catalyst of low silica alumina ratio helps improving the conversion ratio of alkane, and the catalyst of high silica alumina ratio more helps improving the selectivity of propylene.
Reaction temperature has remarkable influence to the process of alkane producing low-carbon alkene by catalytic pyrolysis, because the present invention adopts the catalyst through activation processing, in experiment, find, generally speaking, the raising temperature helps the generation of ethene, propylene and butylene are in certain temperature range, and yield increases with the rising of temperature, but the too high productive rate that influences it on the contrary of temperature.So, make the cracking temperature of alkane can be lower than 700 ℃ according to the present invention program, and preferred catalytic cracking reaction temperature is 550～680 ℃.Course of reaction pressure is at 0.01～0.2MPa, with the inlet of control and adjustment raw material alkane.
According to cracking reaction method provided by the invention, the concentration of gas-phase reaction raw material is 2.5～20%, and the diluent gas of gas-phase reaction raw material can be nitrogen, hydrogen, helium, argon gas, carbon dioxide or its two or more gaseous mixtures.
According to cracking reaction of the present invention, air speed also can produce remarkable influence to the catalytic pyrolysis product, in general, improves the selectivity that reaction velocity helps the product propylene, selectivity of ethylene is changed not quite, but can reduce the conversion of olefines rate.So the gas phase air speed preferably may be controlled to 6000～36000 hours in the present invention's reaction -1, more preferably be controlled at 6000～30000 hours -1
In a word, enforcement of the present invention has effectively improved catalyst activity, is solving the higher shortcoming of present alkane cracking reaction temperature, has not only improved the yield of low-carbon alkene, and important and in short supply chemical material ethylene and propylene can be provided as required efficiently.
The specific embodiment
Below in conjunction with the beneficial effect that specific embodiment is introduced realization of the present invention in detail and produced, understand essence of the present invention better to help the reader, but can not be interpreted as qualification the scope of the present invention.
[embodiment 1～5]
With the 20 commercial silica alumina ratios of gram (mol ratio) is 50 ZSM-5 molecular sieve, and placing 300 ml concns is the NH of 1 mol 4In the Cl solution, under 85～100 ℃ of temperature, implemented heat exchange process 2 hours, filter filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, obtained the SC-0 catalyst in 4 hours through 700 ℃ of roastings again, 40～80 orders are got in the compressing tablet screening.
Control differential responses temperature is carried out the catalytic pyrolysis experiment on small fixed.Pressure is 0.01～0.20MPa.This catalyst activates 2 hours down at 400 ℃ before the reaction.
Reaction raw materials: normal butane, gas phase air speed (WHSV): 1.2 * 10 4Hour -1Diluent gas is a nitrogen, and unstripped gas gas volume concentration is 5.0%.
Reaction result is as shown in table 1.
Table 1
Project Raw material is formed (mol%) Product is formed (mol%)
500℃ 550℃ 625℃ 650℃ 675℃
Methane 0.79 2.49 8.37 10.00 11.17
Ethane 1.55 4.28 9.77 9.86 9.25
Ethene 1.74 5.98 23.80 29.31 33.28
Propane 0.34 0.91 1.65 1.60 1.26
Propylene 2.46 8.10 19.82 19.47 17.54
Normal butane ＞99.90 90.60 67.28 17.68 6.52 1.64
Iso-butane 0.39 0.49 0.19 0.08 0.00
Butylene 1.95 4.75 6.12 4.00 2.08
Butadiene 0.00 0.16 0.23
Aromatic hydrocarbons 1.52 10.93 16.30 21.16
More than the C5 0.18 4.20 1.67 2.70 2.39
Conversion ratio 9.40 32.72 82.32 93.48 98.36
The alkene summation 6.15 18.83 49.74 52.78 52.90
[embodiment 6～10]
With the 40 commercial silica alumina ratios of gram (mol ratio) is 50 ZSM-5 molecular sieve, and placing 600 ml concns is the NH of 1 mol 4NO 3In the solution, under 60～85 ℃ of temperature, implemented heat exchange process 2 hours, filter filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, obtained the SC-1 catalyst in 6 hours through 700 ℃ of roastings again, 40～80 orders are got in the compressing tablet screening.
Control different WHSV, on small fixed, carry out the catalytic pyrolysis experiment.This catalyst activates 2 hours down at 400 ℃ before the reaction.
Reaction raw materials: normal butane, reaction temperature: 650 ℃, diluent gas is a nitrogen, and unstripped gas gas volume concentration is 5.0%.
Reaction result is as shown in table 2.
Table 2 (the product amount is in mol%)
Project Raw material is formed (mol%) Air speed (WHSV) * 10 4Hour -1
0.6 1.2 1.8 2.4 3.6
Methane 11.25 10.00 9.83 8.14 6.53
Ethane 13.02 9.86 7.02 7.72 5.86
Ethene 32.30 29.31 29.95 24.39 18.61
Propane 1.44 1.60 2.05 1.50 1.23
Propylene 17.92 19.47 19.77 20.31 17.10
Normal butane ＞99.90 3.22 6.52 8.24 19.74 27.17
Iso-butane 0.04 0.08 0.10 0.20 0.27
Butylene 2.63 4.00 4.69 8.29 8.56
Butadiene 0.13 0.16 0.24 0.74 0.20
Aromatic hydrocarbons 17.54 16.30 16.74 8.05 6.98
More than the C5 0.51 2.70 1.37 0.92 7.49
Conversion ratio 96.78 93.48 91.76 80.26 72.83
The alkene summation 52.86 52.78 54.42 52.99 44.27
[embodiment 11～15]
With 40 gram silica alumina ratios (mol ratio) is 30 ZSM-5 molecular sieve, places the oxalic acid solution of 600 ml concns, 0.3 mol, implements heat exchange process 2 hours under 30～50 ℃ of temperature, filters filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, 120 ℃ of oven dry down.Catalyst after the above-mentioned processing of 10 grams is under 90 ℃ in temperature, adopts infusion process loading metal-salt ferric nitrate.The consumption of slaine is 0.010 mM/gram catalyst, under 30～40 ℃ of temperature, refluxes 10 hours.Then again in 120 ℃ of oven dry 8 hours, 900 ℃ of temperature roasting heats were handled 3 hours.Obtain the SCA-1 catalyst through above step.
[embodiment 16-20]
Method according to embodiment 11～15 exchanges processing to catalyst, Hydrogen ZSM-5 molecular sieve 10 grams of obtaining, in temperature is under 30～40 ℃, adopt infusion process loading metal-salt chromic nitrate, the consumption of slaine is 0.015 mM/gram catalyst, and return time is 2 hours (80 ℃ of reflux temperatures).Then again 120 ℃ of oven dry 8 hours, 800 ℃ of temperature roasting heats were handled 1 hour.Obtain the SCA-2 catalyst through above step.
40～80 orders are got in catalyst S CA-1, SCA-2 compressing tablet, screening, carry out the catalytic pyrolysis experiment on small fixed.The reaction procatalyst activates 2 hours down at 400 ℃.
Change reaction temperature, reaction result is as shown in table 3.Diluent gas is a helium, unstripped gas gas volume concentration 10%.
Table 3
Catalyst Temperature (℃) Conversion ratio (%) The yield of pyrolysis product alkene (mol%)
Ethene Propylene Butylene The alkene total amount
SCA-1 500 15.27 3.77 3.89 2.11 9.77
550 36.31 8.07 10.22 3.57 21.86
625 77.25 22.40 20.04 6.64 49.08
650 90.29 28.72 20.86 4.89 54.47
675 97.71 33.29 19.04 2.71 55.04
SCA-2 500 15.33 3.32 4.01 3.02 10.35
550 39.28 9.51 10.82 5.35 25.68
625 85.68 24.08 18.58 5.26 47.92
650 94.51 28.41 17.85 3.25 49.51
675 98.17 31.72 15.88 2.02 49.62
Raw material: normal butane WHSV=1.2*10 4Hour -1
[embodiment 21～25]
With 40 gram silica alumina ratios (mol ratio) is 30 ZSM-5 molecular sieve, places the oxalic acid solution of 600 ml concns, 0.3 mol, implements heat exchange process 2 hours under 30～50 ℃ of temperature, filters filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, 120 ℃ of oven dry down.Getting the catalyst of 10 grams after the above-mentioned processing is under 90 ℃ in temperature, adopts ion-exchange loading metal-salt zinc nitrate.The consumption of slaine is 0.008 mM/gram catalyst, and under 30～40 ℃ of temperature, the Hydrogen ZSM-5 molecular sieve catalyst after 10 grams are handled is 0.08 mM/rise in the zinc nitrate and refluxed 10 hours at 150 ml concns.Filtration is dried filter cake down at 120 ℃.Repeat 2 times, then handled 3 hours at 900 ℃ of temperature roasting heats.Obtain the SCA-3 catalyst through above step.
[embodiment 26～30]
Method according to embodiment 11～15 exchanges processing to catalyst, Hydrogen ZSM-5 molecular sieve 10 grams of obtaining, in temperature is under 30～40 ℃, adopt ion-exchange loading metal-salt silver nitrate, the consumption of slaine is 0.118 mM/gram catalyst, under 30～40 ℃ of temperature, the Hydrogen ZSM-5 molecular sieve catalyst after 10 grams are handled is 1.180 mMs/rise in the silver nitrate and refluxed 2 hours at 150 ml concns.Filtration is dried filter cake down at 120 ℃.Repeat 2 times, then handled 1 hour at 800 ℃ of temperature roasting heats again.Obtain the SCA-4 catalyst through above step.
40～80 orders are got in catalyst S CA-3, SCA-4 compressing tablet, screening, carry out the catalytic pyrolysis experiment on small fixed.The reaction procatalyst activates 2 hours down at 400 ℃.
Change reaction temperature, reaction result is as shown in table 4.Diluent gas is helium and carbon dioxide, and both volume ratios are 1: 1, and unstripped gas gas volume concentration is 15%.
Table 4
Catalyst Temperature (℃) Conversion ratio (%) The yield of pyrolysis product alkene (mol%)
Ethene Propylene Butylene The alkene total amount
SCA-3 500 11.09 2.44 3.41 2.30 8.15
550 38.40 8.07 10.16 4.91 23.14
600 71.78 18.91 17.70 6.29 42.90
625 85.75 24.69 19.04 5.40 49.13
650 94.52 29.63 18.06 3.69 51.38
SCA-4 500 15.09 2.00 2.91 2.38 7.29
550 40.61 7.82 9.56 4.98 22.36
600 79.81 20.05 16.24 5.30 41.59
625 92.63 25.64 15.89 3.76 45.29
650 98.34 29.56 13.68 2.08 45.32
Raw material: normal butane WHSV=1.2*10 4Hour -1
[embodiment 31～35]
With 60 gram silica alumina ratios (mol ratio) is 80 ZSM-5 molecular sieve, places 900 milliliters, in the HCl solution of 0.1 mol, implements heat exchange process 2 hours under 50～75 ℃ of temperature, filters filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, 120 ℃ of oven dry down.650 ℃ of roastings obtained the SC-2 catalyst in 2 hours, and 40～80 orders are got in the compressing tablet screening, and control differential responses temperature is carried out the catalytic pyrolysis experiment on small fixed.Activate 2 hours through this catalyst down at 400 ℃ before the reaction.
Reaction raw materials: iso-butane, gas phase air speed (WHSV): 1.2 * 10 4Hour -1Diluent gas hydrogen, unstripped gas gas volume concentration is 20%.Reaction result is as shown in table 5
Table 5
Project Raw material is formed (mol%) Product is formed (mol%)
500℃ 550℃ 575℃ 600℃ 625℃
Methane 2.12 6.86 9.63 12.48 12.66
Ethane 0.04 0.16 0.22 0.35 0.36
Ethene 1.86 8.37 12.76 18.22 21.32
Propane 0.70 1.72 2.15 2.53 2.18
Propylene 7.81 21.52 27.33 31.41 28.08
Normal butane 1.21 1.38 1.36 1.23 0.82
Iso-butane ＞99.90 81.96 48.76 19.73 6.64 1.17
Butylene 4.30 10.02 11.98 11.90 9.09
Butadiene
Aromatic hydrocarbons 1.21 4.52 9.41 14.53
More than the C5 10.32 5.83 9.79
Conversion ratio 18.04 51.24 80.27 93.36 98.83
The alkene summation 13.97 39.91 52.07 61.54 58.49
[embodiment 36～40]
With 60 gram silica alumina ratios (mol ratio) is 120 ZSM-5 molecular sieve, places 900 milliliters, in the formic acid solution of 0.2 mol, implements heat exchange process 2 hours under 90～100 ℃ of temperature, filters filter cake 120 ℃ of oven dry down.Repeat 2 times, obtain Hydrogen ZSM-5 molecular sieve catalyst.Take out (Hydrogen) molecular sieve catalyst after exchange is handled, 120 ℃ of oven dry down.Catalyst after 10 grams are handled is under 90 ℃ in temperature, adopts solid mixing method loading metal-salt ferric nitrate, and the consumption of slaine is 0.010 mM/gram catalyst, takes by weighing 10 gram hydrogen type molecular sieve and 40 milligrams of Fe (NO 3) 39H 2O mechanical agitation 1 hour.Then handled 3 hours at 600 ℃ of temperature roasting heats.Obtain the SCC-1 catalyst through above step.
[embodiment 41～45]
The ZSM-5 molecular sieve 10 that obtains Hydrogen according to the method among the embodiment 36～40 restrains, and is under 70 ℃ in temperature, and loading metal-salt chromic nitrate, the consumption of slaine are 0.015 mM/gram catalyst, takes by weighing 10 gram hydrogen type molecular sieve and 60 milligrams of Cr (NO 3) 39H 2O mechanical agitation 1 hour.Then handled 2 hours at 800 ℃ of temperature roasting heats of 120 ℃ of oven dry.Obtain the SCC-2 catalyst through above step.
40～80 orders are got in catalyst S CC-1, SCC-2 screening, carry out the catalytic pyrolysis experiment on small fixed, and the reaction procatalyst activates 2 hours down at 400 ℃.
Change reaction temperature, reaction result is as shown in table 6.Diluent gas is a hydrogen, and unstripped gas gas volume concentration is 20%.
Table 6
Catalyst Temperature (℃) Conversion ratio (%) The yield of pyrolysis product alkene (mol%)
Ethene Propylene Butylene The alkene total amount
SCC-1 500 10.11 1.10 6.66 3.66 11.42
550 51.49 7.58 12.35 9.83 29.76
575 77.58 14.63 31.45 10.44 56.52
600 94.04 18.92 32.82 11.63 63.36
625 99.07 24.60 32.37 8.66 65.62
SCC-2 500 15.26 2.60 8.29 3.40 14.29
550 60.87 13.22 22.55 7.95 43.72
575 82.85 19.70 27.55 8.76 56.01
600 96.97 26.26 28.37 7.33 61.96
625 99.66 30.84 25.28 4.72 60.83
Raw material: iso-butane WHSV=1.2*10 4Hour -1
[embodiment 46～50]
Get Hydrogen ZSM-5 molecular sieve 100 grams that embodiment 36～40 obtains in temperature for being under 30 ℃～40 ℃ in temperature, adopt solid mixing method loading metal-salt ferric nitrate.Take by weighing several parts 10 the gram hydrogen type molecular sieve respectively with 80,328,664,1360,2640 milligrams of Fe (NO 3) 39H 2O mechanical agitation 1 hour.Loading metal-salt ferric nitrate, return time are 8 hours.Then again 120 ℃ of oven dry, 600 ℃ of temperature roasting heats were handled 6 hours.Obtain the SCC-3 catalyst through above step.
[embodiment 51～55]
ZSM-5 molecular sieve 100 grams of the Hydrogen that embodiment 36～40 is obtained are under 30 ℃～40 ℃ in temperature, adopt solid mixing method loading metal-salt chromic nitrate.Take by weighing several parts 10 the gram hydrogen type molecular sieve respectively with 100,240,2656,4920,7680 milligrams of Cr (NO 3) 39H 2O mechanical agitation 1 hour.Then handled 8 hours at 800 ℃ of temperature roasting heats.Obtain the SCC-4 catalyst series through above step.
40～80 orders are got in SCC-3, the screening of SCC-4 catalyst series, carry out the catalytic pyrolysis experiment on small fixed.The reaction procatalyst activates 2 hours down at 400 ℃.
Change reaction temperature, reaction result is as shown in table 7.The diluent gas carbon dioxide, unstripped gas gas volume concentration is 2.5%.
Table 7
Catalyst Load capacity (mM/gram) Conversion ratio (%) The yield of pyrolysis product alkene (mol%)
Ethene Propylene Butylene The alkene total amount
SCC-3 series 0.020 94.04 18.92 32.82 11.63 63.37
0.082 85.64 18.32 28.78 10.74 57.84
0.166 81.94 16.42 26.12 10.44 52.98
0.340 76.43 13.06 21.25 11.34 45.65
0.660 59.33 5.96 13.76 13.25 32.97
SCC-4 series 0.025 96.97 26.26 28.37 7.34 61.97
0.059 96.50 24.15 27.52 7.40 59.07
0.664 94.04 20.74 28.45 9.14 58.33
1.230 93.30 18.91 27.17 9.47 55.55
1.920 94.27 18.53 25.98 9.00 53.51
Raw material: 600 ℃ of WHSV=1.2*10 of iso-butane reaction temperature 4Hour -1

Claims (10)

1, improves the method for aluminosilicate catalyst activity, described aluminosilicate catalyst is a ZSM-5 series molecular sieve, this method comprises that with inorganic salts, inorganic acid or organic acid described aluminosilicate catalyst being carried out once above heat exchange process makes hydrogen type molecular sieve, 30～100 ℃ of treatment temperatures, thermal bake-out under 200～1000 ℃ temperature then, roasting process is 1～10 hour; When adopting inorganic salts to handle, the consumption of salt is 5～45 mMs/gram catalyst, and when adopting inorganic acid or organic acid to handle, the consumption of acid is 0.3～40 mM/gram catalyst.
2, the described method of claim 1, wherein, the silica alumina ratio during this aluminosilicate catalyst is formed is 1～200.
3, the described method of claim 1, wherein, through the elder generation of the catalyst after inorganic salts, organic acid or mineral acid treatment load base metal under 10～100 ℃ temperature, the consumption of used slaine is 0.001～100 mM/gram catalyst, load time is 0.5～10 hour, then thermal bake-out under 200～1000 ℃ of temperature.
4, each described method of claim 1～3, wherein, the inorganic salts that are used to handle catalyst are ammonium chloride, ammonium nitrate or ammonium carbonate; The organic acid or the inorganic acid that are used to handle catalyst are oxalic acid, formic acid or hydrochloric acid.
5, the described method of claim 3, wherein, the metal of catalyst cupport is titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, zirconium, molybdenum, tungsten or aluminium, used slaine is carbonate, sulfate, nitrate, oxalates, phosphate or the chloride of selected metal, or its corresponding ammonium salt.
6, the described method of claim 5, wherein, the mode of carried metal is ion-exchange, infusion process, coprecipitation or mixing method.
7, adopt the method for butane producing low-carbon alkene by catalytic pyrolysis, use ZSM-5 series molecular sieve catalyst to handle the catalyst of back as cracking reaction according to each method of claim 1～6, this catalytic cracking reaction is 400～700 ℃ in temperature, pressure is 0.01～0.20MPa, and the gas phase air speed is 2000～40000 hours -1Take place under the condition.
8, the described method of claim 7, wherein, described butane is normal butane or iso-butane, low-carbon alkene is C2～C4 alkene.
9, claim 7 or 8 described methods, wherein, the concentration of gas-phase reaction raw material is 2.5～20%.
10, claim 7 or 8 described methods, wherein, the diluent gas of gas-phase reaction raw material is nitrogen, hydrogen, helium, argon gas, carbon dioxide or its two or more gaseous mixtures.
CNB2005100024149A 2005-01-20 2005-01-20 The activation of ZSM-5 catalyst series and the method for catalytic cracking butane to prepared light olefines thereby thereof Expired - Fee Related CN100560205C (en)

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