CN106552666A - A kind of catalyst for preparing olefin by catalytic cracking and its preparation method and application - Google Patents
A kind of catalyst for preparing olefin by catalytic cracking and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of catalyst for preparing olefin by catalytic cracking, with alkali-earth metal modified MFI molecular sieves as carrier, with heteropoly acid as active component, wherein in alkali-earth metal modified MFI molecular sieves, alkaline-earth metal accounts for the 0.5%～2.5% of MFI molecular sieves, and active component accounts for the 0.2%～4% of vehicle weight；And adopt alkali metal oxide or alkali metal salt to catalyst modification, account for the 0.1%～4% of catalyst quality.The preparation method of the catalyst is：With the nitrate solution of alkaline-earth metal to impregnated zeolite, to the dry materials after dipping, roasting；Active component load is carried out using heteropoly acid aqueous solution to modified molecular screen, and to dry materials after dipping；Above-mentioned material, suitable quantity of water, binding agent beating, kneading, agent bar molding are dried and roasting；Alkali metal oxide is carried out to above-mentioned material or alkali metal salt is modified, after modified material drying, roasting, obtain final catalyst.The catalyst has the advantages that olefin yields are high, reaction temperature is low, catalyst stability is good.
Description
Technical field
The present invention relates to a kind of catalyst for preparing olefin by catalytic cracking and its preparation method and application, relates in particular to catalyst of a kind of naphtha catalytic pyrolysis preparing ethylene and propylene and its preparation method and application.
Background technology
Into new century since, worldwide petrochemical raw material and petroleum chemicals demand will sustainable growths, to continue to increase as the demand of petrochemical industry basic material ethylene, propylene, and the steam pyrolysis technology production capacity of routine can not meet the propylene demand of rapid growth, and conventional tubular stove steam thermal cracking is the process for consuming the energy in a large number, process conditions are harsh.Compared with steam thermal cracking, the process reaction temperature reacts about low 50-200 DEG C than Standard cleavage to naphtha catalytic cracking, therefore, than common steam thermal cracking less energy consumption, cracking furnace pipe inwall coking rate is reduced, and so as to extend the operation cycle, increases the boiler tube life-span.Carbon monoxide emission can also be reduced, and product structure can be adjusted flexibly.Compared with traditional steam pyrolysis technology, this new technique can increase the total recovery of ethylene and propylene, and feed naphtha used by production equal number ethylene can be reduced, and production cost of ethylene is greatly lowered.
USP3767567 is using any one oxide in CaO, BeO, SrO（>20wt%）Be catalyst with aluminium oxide, with boiling point in 70-180 DEG C of Petroleum as raw material, reaction temperature 650-900 DEG C, water-oil factor 0.5-10, wherein CaO-Al2O3Type catalyst for best, in product ethylene highest yield up to 52.5%, propene yield 16.3%.Using this quasi-metal oxides or its mixture as catalyst, reaction temperature requires very high, although can improve the yield and selectivity of ethylene, but generate substantial amounts of dry gas, CO and CO during the course of the reaction2, many difficulties are brought to Product recycling.
US4620051 and US4705769 are employed with manganese oxide or ferrum oxide as active component, with the addition of rare-earth elements La, and the oxide catalyst of alkaline-earth metal Mg, crack C3, C4 raw material.With Mn, Mg/Al2O3For catalyst, iso-butane is adopted for raw material, 700 DEG C of reaction temperature, fixed bed reactors evaluation, butanes conversion are 80%, and the selectivity of ethylene and propylene is respectively 34% and 20%.And claim that catalyst can be used for Petroleum and fluidized-bed reactor.
Catalytic cracking reaction is carried out using the catalyst containing molecular sieve, larger amount of ethylene can be not only obtained, moreover it is possible to produce more propylene, butylene.CN101279285A is used for naphtha catalytic pyrolysis preparing ethylene propylene using the catalyst of the Group IVB element in Payload element periodic chart on ZSM-5/ mercerization zeolite symbiosis molecular screens, ZSM-5/ beta zeolite coexistings molecular sieve or ZSM-5/Y zeolite coexisting molecular sieves or at least one element in VB races element or its oxide composition.In fixed bed reactors, reaction temperature 600-700 DEG C, naphtha catalytic cracking obtain ethylene, propylene total recovery up to 54%.
CN1955255A provides a kind of petroleum hydrocarbon catalytic pyrolysis catalyst and its application.The component of its petroleum hydrocarbon catalytic pyrolysis catalyst includes 1）Rare earth element, 2）Phosphorus or boron, 3）Alkali metal, alkaline-earth metal and transition metal, 4）Carrier.The catalyst is used for the heavy hydrocarbons such as cracking naphtha, diesel oil and vacuum gas production low-carbon alkene, and raw material does not need nitrogen dilution, can improve ethylene, propylene, butylene and butadiene yield more than 5%.
Above-mentioned catalyst generally existing one or more deficiencies such as high cost, olefin yields are low, reaction temperature is higher, catalyst too fast, less stable of inactivation.
The content of the invention
For the existing deficiency that naphtha catalytic pyrolysis preparing ethylene propylene yield is not high, reaction temperature is high, the present invention provides a kind of catalyst for naphtha catalytic pyrolysis preparing ethylene propylene and its preparation method and application.
Catalyst for preparing olefin by catalytic cracking of the present invention is with alkali-earth metal modified MFI molecular sieves as carrier, with heteropoly acid as active component, in wherein alkali-earth metal modified MFI molecular sieves, alkaline-earth metal accounts for the 0.5%～2.5% of MFI molecular sieves, active component accounts for the 0.2%～4% of vehicle weight, preferably 0.5%-3.0%；And catalyst is modified using alkali metal oxide or alkali metal salt, alkali metal oxide or alkali metal salt account for the 0.1%～4% of catalyst quality, preferably 0.5%-3.0%.
In the present invention, described alkaline-earth metal includes beryllium, magnesium, calcium, strontium, barium, radium, preferably magnesium, calcium；MFI molecular sieves are preferably ZSM-5 molecular sieve, more preferably Hydrogen ZSM-5 molecular sieve.Described heteropoly acid is selected from H3PO40W12Or H3PO4·12MoO3In one kind, preferably H3PO40W12, heteropoly acid loaded on carrier using conventional impregnation method.The alkali metal is selected from IA races metal, can such as be selected from one or more in Na, Li, K, Rb, Cs etc., preferably its vanadate, more preferably KVO3。
In catalyst of the present invention, appropriate binding agent can be contained, binder dosage accounts for the 10%～50% of final catalyst quality, preferably 20%～40%.Binding agent is generally aluminium oxide etc..
The preparation method of catalyst for preparing olefin by catalytic cracking of the present invention, including following content：
（1）Select or prepare ZSM-5 molecular sieve；
（2）To step（1）In ZSM-5 molecular sieve be modified, using infusion process, with the nitrate solution of alkaline-earth metal to impregnated zeolite, then to the dry materials after dipping, roasting；
（3）To step（2）In alkali-earth metal modified ZSM-5 molecular sieve carry out the load of active component, using heteropoly acid aqueous impregnation, and to the dry materials after dipping；
（4）Appropriate binding agent is selected, by suitable quantity of water, binding agent and step（3）Middle material beating, kneading, agent bar molding are dried and roasting；
（5）Using step impregnation method to step（4）In material carry out the modified of alkali metal oxide or alkali metal salt, obtain final catalytic cracking catalyst after modified material drying, roasting.
Step（1）Middle ZSM-5 molecular sieve is prepared using hydrothermal synthesis method.Silicon source is the one kind in metso, waterglass, Ludox or metasilicate；Silicon source is aluminium salt or the one kind in aluminate；Template is the one kind in n-butylamine, triethylamine, 4-propyl bromide or ethylenediamine.The desired amount of silicon source and silicon source are taken, and solution are made with distillation water dissolution respectively, after two kinds of solution mixing, strong stirring, while template needed for adding, using dilute acid for adjusting pH value in the range of 9-11, obtains white gels and stop stirring.Gel is moved to into autoclave, crystallization 20～80 hours at a temperature of 50～300 DEG C obtain ZSM-5 molecular sieve after products therefrom washing, filtration.
Step（2）Described in it is alkali-earth metal modified, using the nitrate solution dipping ZSM-5 molecular sieve of alkaline-earth metal, the nitrate solution of alkaline-earth metal is magnesium nitrate or calcium nitrate solution, preferably magnesium nitrate solution, dip time 2～12 hours, preferably 2～10 hours；It is dried at a temperature of 70～350 DEG C, and in 250～650 DEG C of roasting temperatures 2～20 hours, is dried at a temperature of preferably 100～300 DEG C, and in 300～600 DEG C of roasting temperatures 2～10 hours.Ammonium exchange process can also be entered before modification, Hydrogen ZSM-5 molecular sieve is obtained.
Step（3）Described in heteropoly acid be selected from H3PO40W12Or H3PO4·12MoO3In one kind, preferably H3PO40W12.Using conventional impregnation method by loaded by heteropoly acid to ZSM-5 molecular sieve, load capacity for molecular sieve quality 0.2%～4%, preferably 0.5%～3%；Molecular sieve after load is dried 1～5h at a temperature of 80～300 DEG C.
Step（4）Described binding agent generally selects Al2O3.10%-50% of the binder dosage for catalyst quality, preferably the 20%～40% of catalyst quality.By the ZSM-5 after appropriate distilled water, load and binding agent beating, extruded moulding after kneading, article shaped can be through roastings or without roasting.
Step（5）Alkali metal in the alkali metal oxide or alkali metal salt is selected from IA races metal, can such as be selected from one or more in Na, Li, K, Rb, Cs etc., more preferably preferred vanadate, KVO3.Alkali metal oxide or alkali metal salt account for the 0.1%～4% of catalyst quality, and preferably 0.5%～3%.Using step impregnation method to step（4）Material be modified, impregnate 1-7h, preferred 2-6h every time.
Application of the catalytic cracking catalyst of the present invention in naphtha catalytic pyrolysis preparing ethylene and propylene, with C5～C10Petroleum is raw material, and reaction temperature is 500～700 DEG C, and 0.01～0.5MPa of reaction pressure in terms of gauge pressure, Petroleum weight space velocity are 0.1～3h-1, under the conditions of water oil volume is than 0.5～5, ethylene, propylene total recovery are up to 61.24%（Account for Petroleum weight）.
The present invention selects to select the ZSM-5 molecular sieve of type and acidity as carrier with uniqueness, and which is modified using alkaline-earth metal, selection heteropoly acid is active component, heteropoly acid is equably carried on molecular sieve using infusion process, during for producing olefin hydrocarbon by catalytic pyrolysis of naphtha, catalytic cracking reaction carrying out at a lower temperature can be effectively facilitated.Then select alkali metal oxide or alkali metal salt to be modified catalyst, can effectively reduce the amount of strong acid in catalyst, be favorably improved the selectivity of ethylene, propylene, and effectively inhibit the formation of carbon deposit in course of reaction and heavily cracked carry out.Not only activity is good for the catalytic cracking catalyst, also with good stability.Catalyst prepared by the present invention not only can improve the yield of purpose product, on the basis of catalyst activity is ensured improve its stability, moreover it is possible to reduce reaction temperature, save energy consumption.
Specific embodiment
The technology of the present invention is described further below by enforcement.
Example 1
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 100ml containing 90 grams of waterglass is prepared, the aqueous solution 30ml containing 13 grams of aluminum sulfate, strong stirring is added thereto to.Add 16 grams of 4-propyl bromides as template simultaneously, it is 10 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 40 hours is incubated at 140 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 50 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 12gMg (NO3)270ml aqueous solutions are made into, and are added thereto to 65 grams of ZSM-5 molecular sieves, stirred, after 6 hours, drying at room temperature, 100 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 0.8% to dipping after 500 DEG C of roastings.
（3）Load H3PO40W12.Take 0.5 gram of H3PO40W12It is dissolved in 30ml distilled water, adds 20 grams of Mg modified zsm-5 zeolites, stir, stand overnight, 120 DEG C of rotary evaporations is dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 0.9%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, wherein binding agent account for the 26% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO38g is made into 20ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 1.0%.
Evaluating catalyst is carried out using fixed bed reactors, Petroleum is raw material, 2 grams of catalyst quality, water oil volume compare 1.2, mass space velocity 1.5h-1, 560 DEG C of reaction temperature, reaction pressure 0.04MPa in terms of gauge pressure, ethylene, propylene total recovery reach 58.13%.
Example 2
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 120ml containing 95 grams of waterglass is prepared, the aqueous solution 30ml containing 12 grams of aluminum sulfate, strong stirring is added thereto to.Add 18 grams of 4-propyl bromides as template simultaneously, it is 11 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 30 hours is incubated at 150 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 80 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 15gMg (NO3)2100ml aqueous solutions are made into, and are added thereto to 85 grams of ZSM-5 molecular sieves, stirred, after 6 hours, drying at room temperature, 130 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 1.2% to dipping after 500 DEG C of roastings.
（3）Load H3PO40W12.Take 0.6 gram of H3PO40W12It is dissolved in 20ml distilled water, the ZSM-5 molecular sieve for adding 25 grams of Mg modified stirs, stands overnight, 150 DEG C of rotary evaporations are dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 2%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 32% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO312g is made into 25ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 1.4%.
Using fixed bed reactors, Petroleum is raw material, and 2.5 grams of catalyst quality, water oil volume compare 0.6, mass space velocity 2h-1, 520 DEG C of reaction temperature, reaction pressure 0.1MPa in terms of gauge pressure, ethylene, propylene total recovery reach 57.84%.
Example 3
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 90ml containing 75 grams of waterglass is prepared, the aqueous solution 50ml containing 23 grams of aluminum sulfate, strong stirring is added thereto to.Add 16 grams of 4-propyl bromides as template simultaneously, it is 10 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 25 hours is incubated at 150 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 30 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 13gMg (NO3)290ml aqueous solutions are made into, and are added thereto to 65 grams of ZSM-5 molecular sieves, stirred, after 5 hours, drying at room temperature, 130 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 1.0% to dipping after 450 DEG C of roastings.
（3）Load H3PO40W12.Take 0.8 gram of H3PO40W12It is dissolved in 30ml distilled water, the ZSM-5 molecular sieve for adding 30 grams of Mg modified stirs, stands overnight, 120 DEG C of rotary evaporations are dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 1.6%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 22% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO315g is made into 25ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 1.8%.
Using fixed bed reactors, Petroleum is raw material, and 3 grams of catalyst quality, water oil volume compare 1.5, mass space velocity 2h-1, 630 DEG C of reaction temperature, reaction pressure 0.2MPa in terms of gauge pressure, ethylene, propylene total recovery reach 61.24%.
Example 4
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 80ml containing 65 grams of waterglass is prepared, the aqueous solution 20ml containing 8 grams of aluminum sulfate, strong stirring is added thereto to.Add 10 grams of 4-propyl bromides as template simultaneously, it is 11 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 20 hours is incubated at 180 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 70 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 21gMg (NO3)290ml aqueous solutions are made into, and are added thereto to 68 grams of ZSM-5 molecular sieves, stirred, after 5 hours, drying at room temperature, 150 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 2.5% to dipping after 500 DEG C of roastings.
（3）Load H3PO40W12.Take 0.8 gram of H3PO40W12It is dissolved in 20ml distilled water, the ZSM-5 molecular sieve for adding 20 grams of Mg modified stirs, stands overnight, 150 DEG C of rotary evaporations are dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 2%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 36% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO315g is made into 20ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 2.4%.
Using fixed bed reactors, Petroleum is raw material, and 3 grams of catalyst quality, water oil volume compare 1.5, mass space velocity 2 hours-1, 650 DEG C of reaction temperature, reaction pressure 0.2MPa in terms of gauge pressure, ethylene, propylene total recovery reach 60.34%.
Example 5
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 110ml containing 90 grams of waterglass is prepared, the aqueous solution 25ml containing 10 grams of aluminum sulfate, strong stirring is added thereto to.Add 13 grams of 4-propyl bromides as template simultaneously, it is 9 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 35 hours is incubated at 150 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 90 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 15gMg (NO3)280ml aqueous solutions are made into, and are added thereto to 60 grams of ZSM-5 molecular sieves, stirred, after 6 hours, drying at room temperature, 130 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 1.5% to dipping after 500 DEG C of roastings.
（3）Load H3PO40W12.Take 1.8 grams of H3PO40W12It is dissolved in 30ml distilled water, adds 20 grams of Mg modified zsm-5 zeolites, stir, stand overnight, 120 DEG C of rotary evaporations is dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 3.3%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 32% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO38g is made into 30ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 0.8%.
Using fixed bed reactors, Petroleum is raw material, and 1.5 grams of catalyst quality, water oil volume compare 3, mass space velocity 2.5 hours-1, 600 DEG C of reaction temperature, reaction pressure 0.3MPa in terms of gauge pressure, ethylene, propylene total recovery reach 56.32%.
Example 6
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 90ml containing 75 grams of waterglass is prepared, the aqueous solution 50ml containing 23 grams of aluminum sulfate, strong stirring is added thereto to.Add 16 grams of 4-propyl bromides as template simultaneously, it is 10 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 25 hours is incubated at 150 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 30 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Ca (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 18gCa (NO3)290ml aqueous solutions are made into, and are added thereto to 60 grams of ZSM-5 molecular sieves, stirred, after 5 hours, drying at room temperature, 130 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Ca contents for molecular sieve 0.8% to dipping after 450 DEG C of roastings.
（3）Load H3PO40W12.Take 1.0 grams of H3PO40W12It is dissolved in 30ml distilled water, the ZSM-5 molecular sieve for adding 35 grams of Ca modified stirs, stands overnight, 120 DEG C of rotary evaporations are dried, H3PO40W12
Content for Mg modified zsm-5 zeolite weight 1.8%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 25% of catalyst quality.
（5）Using KVO3Aqueous solution carries out step impregnation to the material after molding.Take KVO315g is made into 25ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, KVO3Content for catalyst quality 1.8%.
Using fixed bed reactors, Petroleum is raw material, and 3 grams of catalyst quality, water oil volume compare 1.5, mass space velocity 2h-1, 630 DEG C of reaction temperature, reaction pressure 0.2MPa in terms of gauge pressure, ethylene, propylene total recovery reach 56.24%.
Example 7
（1）Prepare ZSM-5 molecular sieve.The aqueous solution 80ml containing 65 grams of waterglass is prepared, the aqueous solution 20ml containing 8 grams of aluminum sulfate, strong stirring is added thereto to.Add 10 grams of 4-propyl bromides as template simultaneously, it is 11 to adjust pH value with dilute sulfuric acid.Continue stirring, until obtaining jelly, gained jelly is moved in autoclave, 20 hours is incubated at 180 DEG C.After crystallization terminates, products therefrom washing obtains the ZSM-5 molecular sieve that silicon/aluminum ratio is 70 after filtration, ammonium obtains the ZSM-5 molecular sieve of Hydrogen after exchanging.
（2）Hydrogen ZSM-5 is modified, using Mg (NO3)2Aqueous solution is modified to ZSM-5 dippings.Take 21gMg (NO3)290ml aqueous solutions are made into, and are added thereto to 68 grams of ZSM-5 molecular sieves, stirred, after 5 hours, drying at room temperature, 150 DEG C of drying obtain the Mg modified zsm-5 zeolites of Hydrogen, Mg contents for molecular sieve 2.3% to dipping after 500 DEG C of roastings.
（3）Load H3PO4·12MoO3.Take 0.8 gram of H3PO4·12MoO3It is dissolved in 20ml distilled water, the ZSM-5 molecular sieve for adding 20 grams of Mg modified stirs, stands overnight, 150 DEG C of rotary evaporations are dried, H3PO4·12MoO3Content for Mg modified zsm-5 zeolite weight 1.9%.
（4）Using Al2O3For binding agent, the mixing of above-mentioned material, binding agent and distilled water is made into into suspension, extruded moulding after being dried, binding agent account for the 36% of catalyst quality.
（5）Using NaVO3Aqueous solution carries out step impregnation to the material after molding.Take NaVO312g is made into 20ml aqueous solutions, right（4）In material dipping 2h after 100 DEG C be dried 5h, then carry out double-steeping again, after dipping 4h, 100 DEG C are dried 6h, NaVO3Content for catalyst quality 2.2%.
Using fixed bed reactors, Petroleum is raw material, and 3 grams of catalyst quality, water oil volume compare 1.5, mass space velocity 2 hours-1, 630 DEG C of reaction temperature, reaction pressure 0.2MPa in terms of gauge pressure, ethylene, propylene total recovery reach 55.11%.
Comparative example 1
The preparation process of catalyst such as example 2, does not simply adopt alkali metal vanadate (KVO after material forming in preparation process3) be modified, appreciation condition such as example 3, ethylene, propylene total recovery reach 45.12%.
Comparative example 2
The preparation process of catalyst such as example 2, does not simply adopt alkaline-earth metal to be modified ZSM-5 molecular sieve in preparation process, appreciation condition such as example 3, ethylene, propylene total recovery reach 49.12%.
Claims (13)
1. a kind of catalyst for preparing olefin by catalytic cracking, it is characterised in that：With alkali-earth metal modified MFI molecular sieves as carrier, with heteropoly acid as active component, in wherein alkali-earth metal modified MFI molecular sieves, alkaline-earth metal accounts for the 0.5%～2.5% of MFI molecular sieves, active component accounts for the 0.2%～4% of vehicle weight, and catalyst is modified using alkali metal oxide or alkali metal salt, alkali metal oxide or alkali metal salt account for the 0.1%～4% of catalyst quality.
2. catalyst according to claim 1, it is characterised in that：Described alkali metal is selected from IA races metal, and alkali metal oxide or alkali metal salt account for the 0.5%～3.0% of catalyst quality.
3. catalyst according to claim 2, it is characterised in that：Described alkali metal is selected from one or more in Na, Li, K, Rb, Cs, and alkali metal salt is its vanadate.
4. catalyst according to claim 1, it is characterised in that：Described alkaline-earth metal includes beryllium, magnesium, calcium, strontium, barium or radium, and MFI molecular sieves are ZSM-5 molecular sieve；Described heteropoly acid is selected from H3PO40W12Or H3PO4·12MoO3In one kind, loaded on carrier using conventional impregnation method.
5. catalyst according to claim 1, it is characterised in that：Also contain appropriate binding agent aluminium oxide in the catalyst, binder dosage accounts for the 10%～50% of final catalyst quality.
6. the preparation method of the arbitrary catalyst for preparing olefin by catalytic cracking of claim 1-5, it is characterised in that including following content：
（1）Select or prepare ZSM-5 molecular sieve；
（2）To step（1）In ZSM-5 molecular sieve be modified, using infusion process, with the nitrate solution impregnated zeolite of alkaline-earth metal, then to the dry materials after dipping, roasting；
（3）To step（2）In alkali-earth metal modified ZSM-5 molecular sieve carry out the load of active component, using heteropoly acid aqueous impregnation, and to the dry materials after dipping；
（4）Appropriate binding agent is selected, by suitable quantity of water, binding agent and step（3）Middle material beating, kneading, agent bar molding are dried and roasting；
（5）Using step impregnation method to step（4）In material carry out the modified of alkali metal oxide or alkali metal salt, obtain final catalytic cracking catalyst after modified material drying, roasting.
7. method according to claim 6, it is characterised in that：Step（1）Middle ZSM-5 molecular sieve is prepared using hydrothermal synthesis method；Silicon source is the one kind in metso, waterglass, Ludox or metasilicate；Silicon source is aluminium salt or the one kind in aluminate；Template is the one kind in n-butylamine, triethylamine, 4-propyl bromide or ethylenediamine；The desired amount of silicon source and silicon source being taken, solution being made with distillation water dissolution respectively, after the mixing of two kinds of solution, strong stirring while template needed for adding, using dilute acid for adjusting pH value in the range of 9～11, obtains white gels and stops stirring；Gel is moved to into autoclave, crystallization 20～80 hours at a temperature of 50～300 DEG C obtain ZSM-5 molecular sieve after products therefrom washing, filtration.
8. method according to claim 6, it is characterised in that：Step（2）Described in it is alkali-earth metal modified, using the nitrate solution dipping ZSM-5 molecular sieve of alkaline-earth metal, the nitrate solution of alkaline-earth metal is magnesium nitrate or calcium nitrate solution, dip time 2～12 hours, it is dried at a temperature of 70～350 DEG C, and in 250～650 DEG C of roasting temperatures 2～20 hours.
9. method according to claim 6, it is characterised in that：Step（3）Described in heteropoly acid be selected from H3PO40W12Or H3PO4·12MoO3In one kind, using conventional impregnation method by loaded by heteropoly acid to ZSM-5 molecular sieve, load capacity for molecular sieve quality 0.2%～4%, the molecular sieve after load are dried 1～5h at a temperature of 80～300 DEG C.
10. method according to claim 6, it is characterised in that：Step（4）Described binding agent is Al2O3, 10%-50% of the consumption for catalyst quality.
11. methods according to claim 6, it is characterised in that：Step（5）Alkali metal in described alkali metal oxide or alkali metal salt is selected from one or more in Na, Li, K, Rb, Cs；Alkali metal oxide or alkali metal salt account for the 0.1%～4% of catalyst quality；Using step impregnation method to step（4）Material be modified, impregnate 1-7h every time.
12. methods according to claim 11, it is characterised in that：Step（5）Described alkali metal salt is its vanadate, and alkali metal vanadate accounts for the 0.5%～3% of catalyst quality.
13. applications according to the arbitrary catalyst for preparing olefin by catalytic cracking of claim 1-5 in naphtha catalytic pyrolysis preparing ethylene and propylene, it is characterised in that：With C5～C10Petroleum is raw material, and reaction temperature is 500～700 DEG C, counts reaction pressure as 0.01～0.5MPa with gauge pressure, and Petroleum weight space velocity is 0.1～3h-1, water oil volume ratio is 0.5～5.
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| CN113546674A (en) * | 2020-04-24 | 2021-10-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof, and catalytic cracking method |
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