CN104209139A - Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof - Google Patents
Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof Download PDFInfo
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- CN104209139A CN104209139A CN201310218415.1A CN201310218415A CN104209139A CN 104209139 A CN104209139 A CN 104209139A CN 201310218415 A CN201310218415 A CN 201310218415A CN 104209139 A CN104209139 A CN 104209139A
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and a preparation method thereof. The catalyst comprises an active component, a carrier, a modified binder and a metal oxide, wherein the active component is ZSM-11 molecular sieve, the ZSM-11 molecular sieve has mesopore and micropore cascade pore structure and nanorod splice morphology, the volume ratio of mesopore and micropore is (0.2-3): 1, the grain size is 50-1900nm, the silicon aluminum ratio is 30-300, the modified binder is composed of a modified binder I and a modified binder II in the ratio of 0.1-10:1, the modified binder I is prepared by using a metal modification method, and the modified binder II is prepared by using a static hydrothermal crystallization method. The catalyst prepared by the preparation method can produce gasoline and also give consideration to propylene yield during methanol conversion reaction, realizes the adjustment of gasoline and propylene yield in the methanol conversion reaction, is adapted to market changes in gasoline and propylene, and improve the ability to resist the market risk of the methanol conversion technology.
Description
Technical field
The present invention relates to methanol conversion and produce the Catalysts and its preparation method that propene yield taken into account by gasoline, especially relate to a kind of methanol conversion containing ZSM-11 molecular sieve active component and produce the Catalysts and its preparation method that propene yield taken into account by gasoline.
Background technology
It is take methyl alcohol as raw material that methanol conversion produces gasoline technology, by the technology of Catalyst Production gasoline.Relative to catalytically cracked gasoline, the gasoline that methanol conversion is produced shows good character, such as: its alkene, aromatic hydrocarbons and S content, all within the scope of clean gasoline, meet restriction strict to S content in state IV, state V gasoline standard.
Methanol conversion production process of gasoline develops on the basis that the methyl alcohol of Mobil company exploitation changes into aromatic hydrocarbons on ZSM-5 molecular sieve catalyst.Mobil method methanol conversion is produced gasoline technology and is first made raw material production synthesis gas with coal or natural gas, then with synthesising gas systeming carbinol, finally crude carbinol is converted into high-knock rating gasoline.
It is based on taking methyl alcohol as raw material that methanol conversion generates propylene technology, by alkene production catalyst and other hydro carbons.It is while minimizing carbon emission, and can carry out the technology of Appropriate application to excessive methanol, advantage is more obvious.
At present, ZSM-5 molecular sieve catalyst is that methanol conversion produces catalyst conventional in gasoline and propylene, shows good catalytic performance in the reaction of methanol conversion.But at present, ZSM-5 molecular sieve catalyst, due to the restriction of the aspects such as pore structure, Acidity and pattern, can not improve propene yield in gasoline and liquefied gas when producing reaction for methanol conversion simultaneously.
Simultaneously in order to meet the strict demand of technique to catalyst abrasion index, domain size distribution, suitable binding agent should be selected, and binding agent is as a part for catalyst, and the performance of catalyst is also closely related.At present, the binding agent of the semi-synthetic catalyst of common preparation has aluminium base binding agent, based binder and sial binding agent.Also have the acidity by modification regulating catalysts such as rare earths and anti-metal poisoning capability in prior art, but it is expensive, applicability is little simultaneously.CN1098130A patent discloses a kind of composite aluminum base binding agent, and this binding agent improves wearability and the coke selectivity of semi-synthetic catalyst.Above-mentioned modification is used in catalytic cracking catalyst, but due to the difference of raw material, during methanol conversion, required Acidity transitivity is different from the former, therefore, carry out modification to the binding agent of the catalyst being applied to the reaction of methanol conversion, the activity for catalyst has important impact.
Summary of the invention
In order to solve the problem in prior art in the reaction of methanol conversion, embodiments providing a kind of methanol conversion and producing the Catalysts and its preparation method that propene yield taken into account by gasoline.Described technical scheme is as follows:
One aspect of the present invention provides a kind of catalyst taking into account propene yield for methanol conversion production gasoline, described catalyst is made up of active component, carrier, modified binder and metal oxide, it is characterized in that, described active component is ZSM-11 molecular sieve, this molecular sieve has step pore structure and the nanometer rods grafting pattern of mesopore and micropore, and mesopore wherein and the volume ratio of micropore are (0.2-3.0): 1, crystal grain is 50-1900nm, silica alumina ratio is 30-300; With the quality of catalyst for benchmark, the quality proportioning of the active component of described catalyst, carrier, modified binder and metal oxide is (3-60): (80-5): (2.0-55): (0.1-50); Described modified binder is made up of modified binder I and modified binder II, described modified binder I adopts metal-modified method to obtain, modified binder II adopts static hydrothermal crystallization method to obtain, and the mass ratio of described modified binder I and modified binder II is 0.1-10:1.
Preferably, with the quality of catalyst for benchmark, the mass ratio of described active component, carrier, modified binder and metal oxide is (10-35): (20-60): (7.0-35): (1.0-40).
Preferably, the described mesopore of ZSM-11 molecular sieve and the volume ratio of micropore are (0.5-2.0): 1, crystal grain is 200-1700nm, silica alumina ratio is 30-100.
Concrete, described carrier is selected from kaolin, MgO, sepiolite, Al
2o
3, SiO
2with at least one in diatomite.
Concrete, the preparation method of described modified binder comprises:
Metal-modified process: by binding agent and 2mol/L metal salt solution mix and blend 4h under 60 DEG C of water bath condition, after in left at room temperature 4-6h, obtain modified binder I; Wherein, in metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal, described metal oxide is selected from least one in Zn, W, B, P, Zr, Mg and Mn oxide, and the quality of described metal oxide is the 0.5%-15% of described binding agent quality;
Static hydrothermal crystallization process: binding agent is put into crystallizing kettle, static crystallization 2-8h at 100 DEG C, after in left at room temperature 4-6h, obtain modified binder II;
The ratio of modified binder I and modified binder II 0.1-10:1 is in mass ratio mixed, after stirring, obtains described modified binder.
Concrete, described binding agent is selected from least one in Ludox, Alumina gel and waterglass.
Concrete, when described binding agent is Ludox, its quality is in the quality of silica, and wherein the mass fraction of silica in described Ludox is 40.0%; When described binding agent is waterglass, its quality is in the quality of silica, and wherein the mass fraction of silica in described waterglass is 27.5%; When described binding agent is Alumina gel, its quality is in the quality of monohydrate alumina, and wherein the mass fraction of monohydrate alumina in described Alumina gel is 20.0%.
Concrete, described metal oxide is selected from least one in Zn, Ce, P, Co, B, K, Cs, Ca, Mg, Sr and Ba oxide.
The present invention provides a kind of method preparing above-mentioned catalyst on the other hand, said method comprising the steps of:
The binding agent of described active component, carrier and modification is mixed with deionized water by regulation order, mechanical agitation is even, make catalyst gel;
Metal salt solution is joined in described catalyst gel, in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, the catalyst granules of 80-200 μm is sieved out after cooling, in described metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal, generally selects the amount of metal salt solution according to following principle: preparation 50g catalyst granules needs preparation 70g metal salt solution.
Third aspect present invention provides a kind of method preparing above-mentioned catalyst, said method comprising the steps of:
Described active component, carrier and modified binder are mixed with deionized water by regulation order, mechanical agitation is even, make catalyst gel; By above-mentioned catalyst gel in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, after cooling, sieve out the catalyst granules of the intermediary form of 80-200 μm;
Under normal temperature, impregnating metal salting liquid on the catalyst granules of above-mentioned intermediary form, subsequently in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, obtained catalyst granules; In described metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal, generally selects the amount of metal salt solution according to following principle: the catalyst granules of dipping 50g intermediary form needs 70g metal salt solution.
In the preparation method of above-mentioned catalyst, described active component, carrier and modified binder mix concrete standby by following regulation sequential system by regulation order with deionized water:
Boehmite is selected to prepare the Al being used as carrier
2o
3time, first by boehmite, water and mixed in hydrochloric acid, mechanical agitation 0.5h plastic.In above-mentioned solution, add active component and carrier, then add modified binder and deionized water, mechanical agitation is even, obtains described catalyst gel.
When selecting other carrier, first deionized water is added in modified binder, then adds carrier, under normal temperature mechanical agitation evenly after add active component and deionized water, mechanical agitation evenly after, obtain described catalyst gel.
In the preparation method of catalyst described in the invention described above, described metal salt solution is prepared as follows: the slaine taking required quality according to quality proportioning, is dissolved in deionized water, namely makes this metal salt solution.
In the preparation method of catalyst described in the invention described above, at normal temperatures, on the catalyst granules of described intermediary form, the concrete operations of impregnating metal salting liquid are: dropwise dripped on the catalyst granules of intermediary form by metal salt solution dropper, dry after all just wetting, repeat 3-4 time, until all metal salt solutions are finished.
The present invention's preferred embodiment is: a kind of methanol conversion produces the catalyst that propene yield taken into account by gasoline, described catalyst is made up of active component, carrier, modified binder and metal oxide, described active component is ZSM-11 molecular sieve, the mesopore of this ZSM-11 molecular sieve and the volume ratio of described micropore are (0.5-2.0): 1, crystal grain is 200-1700nm, and silica alumina ratio is 30-100; With the quality of catalyst for benchmark, the quality proportioning of the active component of described catalyst, carrier, modified binder and metal oxide is: (10-35): (20-60): (7.0-35): (1.0-40); The preparation method of described catalyst is: first take described active component, carrier, modified binder and metal oxide according to the quality proportioning of each component, under normal temperature, taken active component, carrier, modified binder are mixed with deionized water by regulation order, mechanical agitation is even, make catalyst gel, then by above-mentioned catalyst gel in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, sieve out the catalyst granules of the intermediary form of 80-200 μm after cooling; Be prepared into corresponding metal salt solution by water-soluble for metal oxide, under normal temperature, on the catalyst granules of described intermediary form, flood above-mentioned metal salt solution, in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, obtained catalyst granules.
Principle of the present invention is as follows:
In conventional the reaction of methanol conversion, the yield of gasoline and the yield of propylene belong to conflict body, namely can only obtain a kind of product of high yield, can not take into account the yield of propylene by voluminous gasoline simultaneously, or can not take into account the yield of gasoline by producing more propylene simultaneously.And embodiments provide a kind of catalyst for the reaction of methanol conversion, propylene can be produced and take into account yield of gasoline or produce gasoline and take into account propene yield, overturn conventional thought at the production field of liquefied gas, provided a new developing direction.
The described active component of catalyst described in the embodiment of the present invention is ZSM-11 molecular sieve, described ZSM-11 molecular sieve has step pore structure and the nanometer rods grafting pattern of mesopore and micropore, the crystal grain of described ZSM-11 molecular sieve is 50-1900nm, silica alumina ratio is 30-300, and the mesopore of described ZSM-11 molecular sieve and the volume ratio of micropore are (0.2-3.0): 1.
Adopt and there is the step pore structure of micropore and mesopore and the ZSM-11 molecular sieve of the nanometer rods grafting pattern active component as catalyst, by regulating the crystal grain of ZSM-11 molecular sieve, pattern and silica alumina ratio etc., prepare a series of catalyst, realize the object that propene yield taken into account by the reaction of methanol conversion fecund gasoline, and suitably can regulate the yield of gasoline and propylene in product.The micropore of described ZSM-11 molecular sieve and the step pore structure of mesopore effectively reduce molecular diffusion resistance, prevent the further generation of secondary response, are conducive to the raising of olefine selective.
The nanometer rods grafting pattern of described ZSM-11 molecular sieve refers to that described molecular sieve has uniformly by the spherical morphology of bar-shaped crystallite self assembly, overcomes the defect of mesopore molecular sieve and loaded down with trivial details last handling process.
The middle micropore pore volume ratio of described ZSM-11 molecular sieve and the selective relevant of product.Mesopore proportion is larger, and macromolecular substances is easier in molecular sieve diffusion inside, and the yield of the gasoline obtained is higher; Meanwhile, middle micropore pore volume ratio is different, and the content of middle species and low-carbon alkene is also different.
The crystal grain of described ZSM-11 molecular sieve can affect catalytic activity and selective.Less zeolite crystal size can increase outer surface, and expose more internal capillary and contact with reactant, shorten low-carbon alkene intermediate product in the molecular sieve catalytic active supercentral time of staying, inhibit the formation of accessory substance, improve object selectivity of product, be beneficial to and improve catalyst activity and life-span.
The silica alumina ratio of described ZSM-11 molecular sieve can affect acid distribution and the acid strength of molecular sieve surface, and when silica alumina ratio is lower, acidic site increased number, easily secondary response occurs, and olefine selective reduces.Silica alumina ratio is too high, and sour density reduces, and conversion ratio can significantly reduce.
The ratio that the crystal grain of described ZSM-11 molecular sieve is 200-1700nm, silica alumina ratio is 30-100, mesopore volume and micro pore volume is (0.5-2.0): when 1, activity and the object selectivity of product of the catalyst obtained are the highest.
The described carrier of the catalyst that the embodiment of the present invention provides mainly plays the effect of the active component in dispersion and support catalyst, for catalyst provides certain mechanical strength and hot and hydrothermal stability.Different according to the content of active component, carrier content is in the catalyst also different.
Active component and carrier are mainly bonded together by described binding agent, meet the requirement to catalyst abrasion index and domain size distribution in technique.In addition, as the part of catalyst, it also can play certain promotor action to the reactivity worth of catalyst.The embodiment of the present invention provides catalyst to select modified binder.Adopt described modified binder can regulating catalyst Acidity.According to the difference of active component and carrier content in the catalyst, modified binder content is in the catalyst also different.
In order to regulate the acidity on described ZSM-11 zeolite crystal surface, adding metal oxide in the catalyst, described acidity of catalyst can be made to reduce, thus improve described catalyst olefin product selective in the reaction of methanol conversion.Different according to the content of active component, the oxide content in the catalyst of described alkali metal or alkaline-earth metal is also different.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
Adopt ZSM-11 molecular sieve to be active component and mate applicable carrier and the catalyst of modified binding agent, carry out the reaction of methanol conversion, can produce gasoline take into account propene yield or produce propylene take into account yield of gasoline, achieve the adjustment to gasoline and propene yield in the reaction of methanol conversion, adapt to the turn of the market of gasoline and propylene, improve the ability that methanol conversion technology resists the market risk.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below embodiment of the present invention is described further in detail.
The catalyst that the embodiment of the present invention provides is prepared as follows:
First with the quality of catalyst for benchmark, according to quality proportioning (3-60): (80-5): (2.0-55): (0.1-50) calculates and take active component, carrier, modified binder and metal oxide, described active component, carrier, modified binder are added in 50-100g deionized water, under normal temperature, mechanical agitation is even, makes catalyst gel; Metal oxide is dissolved in deionized water, makes metal salt solution, generally select the amount of metal salt solution according to following principle: preparation 50g catalyst granules needs preparation 70g metal salt solution; Joined by metal salt solution in described catalyst gel, in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, sieve out the catalyst granules of 80-200 μm after cooling.
The catalyst that the embodiment of the present invention provides can also be prepared as follows:
First with the quality of catalyst for benchmark, according to quality proportioning (3-60): (80-5): (2.0-55): (0.1-50) calculates and take active component, carrier, modified binder and metal oxide, described active component, carrier, binding agent are added in 50-100g deionized water, under normal temperature, mechanical agitation is even, make, then by catalyst gel in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, sieve out the catalyst granules of the intermediary form of 80-200 μm after cooling; Metal oxide is dissolved in deionized water, makes metal salt solution, generally select the amount of metal salt solution according to following principle: the catalyst granules of dipping 50g intermediary form needs preparation 70g metal salt solution; Then on described intermediary form catalyst granules, above-mentioned metal salt solution is flooded, finally in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h.
Particularly, described active component is ZSM-11 molecular sieve, and in the embodiment of the present invention, active component ZSM-11 molecular sieve used is the present inventor oneself synthesis, concrete synthetic method referenced patent CN102557071A.
Particularly, described carrier is kaolin, MgO, sepiolite, Al
2o
3, SiO
2with at least one in diatomite, in the embodiment of the present invention purity of used carrier and manufacturer as shown in the table.
Particularly, the preparation method of described modified binder comprises:
Metal-modified process: by binding agent and 2mol/L metal salt solution mix and blend 4h under 60 DEG C of water bath condition, after in left at room temperature 4-6h, obtain modified binder I; Wherein, in metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal, described metal oxide is selected from least one in Zn, W, B, P, Zr, Mg and Mn oxide, and the quality of described metal oxide is the 0.5%-15% of described binding agent quality;
Static hydrothermal crystallization process: binding agent is put into crystallizing kettle, static crystallization 2-8h at 100 DEG C, after in left at room temperature 4-6h, obtain modified binder II;
The ratio of modified binder I and modified binder II 0.1-10:1 is in mass ratio mixed, after stirring, obtains described modified binder.
Described binding agent is at least one in Ludox, Alumina gel and waterglass.When binding agent is Ludox, the quality of described Ludox is in the quality of silica, and the mass fraction of silica in described Ludox is 40.0%; When binding agent is waterglass, the quality of described waterglass is in the quality of silica, and the mass fraction of silica in described waterglass is 27.5%; When binding agent is Alumina gel, the quality of described Alumina gel is in the quality of monohydrate alumina, and its mass fraction in described Alumina gel is 20.0%.Purity and the manufacturer of binding agent used in the embodiment of the present invention are as shown in the table.
Concrete, described metal oxide is at least one in Zn, Ce, P, Co, B, K, Cs, Ca, Mg, Sr and Ba oxide.
Purity and the manufacturer of slaine used in the embodiment of the present invention represent as follows:
Embodiment 1
The preparation of modified silicasol: first by 20g Ludox under 60 DEG C of water bath condition with the zinc nitrate solution mix and blend 4h of 5mL2mol/L, after in left at room temperature 6h, obtain modified silicasol I; Then 20g Ludox is put into crystallizing kettle, static crystallization 6h at 100 DEG C, after in left at room temperature 4h, obtain modified silicasol II; Finally the ratio of modified silicasol I and modified silicasol II 1:1 is in mass ratio mixed, after stirring, obtain described modified silicasol.
Embodiment 2
The preparation of modified aluminium colloidal sol: first by 10g waterglass under 60 DEG C of water bath condition with the magnesium nitrate solution mix and blend 4h of 8mL2mol/L, after in left at room temperature 4h, obtain modified aluminium colloidal sol I; Then 30g waterglass is put into crystallizing kettle, static crystallization 4h at 100 DEG C, after in left at room temperature 4h, obtain modified aluminium colloidal sol II; Finally the ratio of modified aluminium colloidal sol I and modified aluminium colloidal sol II 1:3 is in mass ratio mixed, after stirring, obtain described modified aluminium colloidal sol.
Embodiment 3
The preparation of modified water glass: first by 50g waterglass under 60 DEG C of water bath condition with the ammonium dihydrogen phosphate mix and blend 4h of 30mL2mol/L, after in left at room temperature 4h, obtain modified water glass I; Then 10g waterglass is put into crystallizing kettle, static crystallization 4h at 100 DEG C, after in left at room temperature 4h, obtain modified water glass II; Finally the ratio of modified water glass I and modified water glass II 5:1 is in mass ratio mixed, after stirring, obtain described modified water glass.
Modified silicasol used in following examples 4-23 is provided by embodiment 1, and modified aluminium colloidal sol used is provided by embodiment 2, and modified water glass used is provided by embodiment 3.
Embodiment 4
In 13.75g modified silicasol, add 50g deionized water, then add 48.5g kaolin, mechanical agitation is even.The ZSM-11 molecular sieve powder that 46g1100nm, Si/Al are 100, middle micro pore volume ratio is 2.0 is added in above-mentioned solution, add 12.5g deionized water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Ba (NO of 2.56g
3)
2, be dissolved in 70g deionized water, make Ba (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 5
In 38.75g modified silicasol, add 50g deionized water, then add 64.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 20g1100nm, Si/Al35, middle micro pore volume ratio be 1.5 ZSM-11 molecular sieve powder, add 12.5g deionized water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the CsNO of 6.92g
3, be dissolved in 70g deionized water, made CsNO
3the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 6
In 5.0g modified silicasol, add 50g deionized water, more slowly added by 70.0g kaolin, mechanical agitation is even.In above-mentioned solution, add 28g1700nm, Si/Al100, middle micropore pore volume ratio be 1.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.Subsequently in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Ca (NO of 29.28g
3)
2, be dissolved in 70g deionized water, made Ca (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 7
In 50.0g modified silicasol, add 50g deionized water, more slowly added by 60.0g kaolin, mechanical agitation is even.In above-mentioned solution, add 20g1700nm, Si/Al35, middle micropore pore volume ratio be 1.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.Subsequently in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the KNO of 21.44g
3, be dissolved in 70g deionized water, made KNO
3the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 8
In 100.0g modified silicasol, add 50g deionized water, more slowly added by 10.0g sepiolite, mechanical agitation is even.In above-mentioned solution, add 50g1700nm, Si/Al35, middle micropore pore volume ratio be 2.0 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even, obtains catalyst gel.Take the Zn (NO of 34.91g
3)
26H
2o, is dissolved in 70g deionized water, makes Zn (NO
3)
2the aqueous solution, add in above-mentioned catalyst gel, subsequently in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, cooling after pulverizes and sieves out 80-200 μm of shaping catalyst particle.
Embodiment 9
In 105.0g modified aluminium colloidal sol, add 50g deionized water, more slowly added by 46.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 32.5g500nm, Si/Al100, middle micropore pore volume ratio be 1.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.Subsequently in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Sr (NO of 10.21g
3)
2, be dissolved in 70g deionized water, made Sr (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 10
In 135.0g modified aluminium colloidal sol, add 50g deionized water, more slowly added by 52.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 20.5g1700nm, Si/Al100, middle micropore pore volume ratio be 1.0 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.Subsequently in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Ba (NO of 8.52g
3)
2, be dissolved in 70g deionized water and stirred evenly, made Ba (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 11
In 62.5g modified silicasol, add 50g deionized water, more slowly added by 43.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 31.5g500nm, Si/Al35, middle micropore pore volume ratio be 1.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.In 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Zn (NO of 11.63g
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes Zn (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h.Take the NH of 8.46g again
4ce (NO
3)
6, be dissolved in 70g deionized water and stirred evenly, made NH
4ce (NO
3)
6the aqueous solution, impregnated of Zn (NO above-mentioned
3)
2the aqueous solution also dried catalyst floods NH
4ce (NO
3)
6the aqueous solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 12
In 38.75g modified silicasol, add 50g deionized water, more slowly added by 52.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 32g1100nm, Si/Al65, middle micropore pore volume ratio be 0.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Mg (NO of 18.40g
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes Mg (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 13
In 61.25g modified silicasol, add 50g deionized water, more slowly added by 45.5g kaolin, mechanical agitation is even.In above-mentioned solution, add 30g500nm, Si/Al65, middle micropore pore volume ratio be 1.0 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.In 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Ca (NO of 14.64g
3)
2, be dissolved in 70g deionized water and stirred evenly, made Ca (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 14
In 20.00g modified water glass, add 50g deionized water, more slowly added by 58.5g sepiolite, mechanical agitation is even.In above-mentioned solution, add 36g500nm, Si/Al35, middle micropore pore volume ratio be 0.5 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.In 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Zn (NO of 11.63g
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes Zn (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 15
In 26.25g modified silicasol, add 50g deionized water, more slowly added by 63.5gMgO, mechanical agitation is even.In above-mentioned solution, add 26g500nm, Si/Al100, middle micropore pore volume ratio be 1.0 ZSM-11 molecular sieve powder, then add 12.5g deionized water dissolving, mechanical agitation is even.In 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the KNO of 8.04g
3(by its oxide mass be 5g calculate), be dissolved in 70g deionized water and stir evenly, make KNO
3the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h.Take the Co (NO of 12.21g again
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes Co (NO
3)
26H
2the aqueous solution of O, impregnated of KNO above-mentioned
3the aqueous solution and dried catalyst floods Co (NO
3)
26H
2the aqueous solution of O.Then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 16
In 44.08g boehmite, add 180g deionized water, machinery stirs evenly, and adds 28.2g hydrochloric acid, stirs 0.5h plastic.In above-mentioned solution, add 30g1700nm, Si/Al65, middle micropore pore volume ratio be 1.5 ZSM-11 and 35g kaolin powder, add 12.5g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the ammonium dihydrogen phosphate (ADP) of 3.79g, be dissolved in 70g deionized water and stir evenly, make ammonium dihydrogen phosphate aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 17
In 44.08g boehmite, add 180g deionized water, machinery stirs evenly, and adds 28.2g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 25g1100nm, Si/Al100, middle micropore pore volume ratio be 1.5 ZSM-11 and 30g kaolin powder, add 37.5g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the CsNO of 6.50g
3, be dissolved in 70g deionized water and stirred evenly, made CsNO
3the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, and 700 DEG C of roasting 2h, for subsequent use.
Embodiment 18
In 29.39g boehmite, add 180g deionized water, machinery stirs evenly, and adds 18.8g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 20g500nm, Si/Al65, middle micropore pore volume ratio be 0.5 ZSM-11 and 50g kaolin powder, add 25.0g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Ba (NO of 8.52g
3)
2, be dissolved in 70g deionized water and stirred evenly, made Ba (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, and 700 DEG C of roasting 2h, for subsequent use.
Embodiment 19
In 51.42g boehmite, add 180g deionized water, machinery stirs evenly, and adds 32.99g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 20g500nm, Si/Al35, middle micropore pore volume ratio be 1.0 ZSM-11 and 35g kaolin powder, add 25.0g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Mg (NO of 20.0
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes dipping Mg (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, and 700 DEG C of roasting 2h, for subsequent use.
Embodiment 20
In 36.73g boehmite, add 180g deionized water, machinery stirs evenly, and adds 37.51g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 25g1100nm, Si/Al100, middle micropore pore volume ratio be 1.0 ZSM-11 and 32.5g kaolin powder, add 43.75g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Sr (NO of 10.21g
3)
2, be dissolved in 70g deionized water and stirred evenly, made Sr (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, and 700 DEG C of roasting 2h, for subsequent use.
Embodiment 21
In 47.75g boehmite, add 180g deionized water, machinery stirs evenly, and adds 23.50g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 40g500nm, Si/Al65, middle micropore pore volume ratio be 2.0 ZSM-11 and 15g kaolin powder, add 31.25g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the KNO of 10.72g
3, be dissolved in 70g deionized water and stirred evenly, made KNO
3the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Embodiment 22
In 22.04g boehmite, add 180g deionized water, machinery stirs evenly, and adds 14.10g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 35g1100nm, Si/Al35, middle micropore pore volume ratio be 2.0 ZSM-11 and 30g kaolin powder, add 50.0g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Co (NO of 12.21g
3)
26H
2o, is dissolved in 70g deionized water and is stirred evenly, and makes Co (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h, and 700 DEG C of roasting 2h, for subsequent use.
Embodiment 23
In 44.08g boehmite, add 180g deionized water, machinery stirs evenly, and adds 28.2g hydrochloric acid, stirs 0.5h plastic.In above-mentioned gel, add 20g1100nm, Si/Al65, middle micropore pore volume ratio be 1.5 ZSM-11 and 35g kaolin powder, add 37.5g modified silicasol and 20g water again, mechanical agitation is even, in 120 DEG C of dry 6-8h, subsequently in 700 DEG C of roasting 2h, pulverize and sieve out 80-200 μm as intermediary form catalyst after cooling.Take the Zn (NO of 11.63g
3)
26H
2o(is that 5g calculates by its oxide mass), be dissolved in 70g deionized water and stir evenly, make Zn (NO
3)
2the aqueous solution, intermediary form catalyst described in 50g floods this solution, then in 140 DEG C of dry 8-10h.Take the NH of 8.46g again
4ce (NO
3)
6, be dissolved in 70g deionized water stirring evenly and made NH
4ce (NO
3)
6the aqueous solution, impregnated of Zn (NO above-mentioned
3)
2the aqueous solution and dried catalyst floods NH
4ce (NO
3)
6the aqueous solution, then in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, for subsequent use.
Catalyst performance is tested: the catalytic performance that the catalyst that the embodiment of the present invention provides shows in the reaction of methanol conversion is according to following condition test: be that the pure methyl alcohol of 99% is for raw material with mass fraction, to the catalyst of preparation in embodiment 4 ~ 23, miniature fixed-bed reactor carries out performance evaluation, reaction temperature is 450 DEG C, loaded catalyst is 2g, nitrogen flow rate is 21mL/min, is 6h when quality is empty
-1.The evaluation result product of the continuous feed 10min (distribution) sees attached list 1 ~ 4, selectivity of product with the hydrocarbon amount after methanol dehydration for benchmark.
The pure methyl alcohol of table 1 product on embodiment 4 ~ 8 catalyst is selective, C%(wt)
The pure methyl alcohol of table 4 product on embodiment 19 ~ 23 catalyst is selective, C%(wt)
Can be found out by table 1-4, the reactivity worth evaluation result of the catalyst that embodiment of the present invention 4-23 provides shows, gasoline conversion rate, propylene conversion and P/E be flexibility and changeability within the scope of 26.51-66.31%, 8.54-41.35%, 1.23-5.35 respectively, thus the adjustment achieved to gasoline and propene yield in the reaction of methanol conversion, adapt to the turn of the market of gasoline and propylene, improve the ability that methanol conversion technology resists the market risk.
Comparative example 1
What grade green for a long time is that the aluminium silicophosphate molecular sieve SAPO-34 of template synthesis is used in the reaction of methanol conversion with diethylamine, and propene yield is 39.42%, and yield of gasoline is 0, see table 5.
Comparative example 2
When Cao Yongkun etc. find that HZSM-5 molecular sieve is used for the reaction of methanol conversion, propene yield is 0, and yield of gasoline is 87%, see table 5.
Visible, when SAPO-34 and HZSM-5 molecular sieve is used for the reaction of methanol conversion as catalyst, propylene or a kind of product of gasoline can only be obtained, the adjustment to gasoline and propene yield in the reaction of methanol conversion can not be realized, therefore be difficult to the turn of the market adapting to gasoline and propylene, resist the market risk for methanol conversion technology and bring pressure.
Comparative example 1-2 can bibliography as follows:
What is green for a long time, Liu Zhongmin, Cai Guangyu, etc. take diethylamine as template synthesized silicon phosphor aluminum molecular sieve [P] .CN1096496A.1994-12-21.
Cao Yongkun. preparing gasoline by methanol, methanol-to-olefins technical progress and commercial Application [J]. Coal Chemical Industry, 2010,4:25-27.
The pure methyl alcohol of table 5 product on comparative example catalyst is selective, C%(wt)
The invention described above embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. produce for methanol conversion the catalyst that propene yield taken into account by gasoline for one kind, described catalyst is made up of active component, carrier, modified binder and metal oxide, it is characterized in that, described active component is ZSM-11 molecular sieve, this molecular sieve has step pore structure and the nanometer rods grafting pattern of mesopore and micropore, and mesopore wherein and the volume ratio of micropore are (0.2-3.0): 1, crystal grain is 50-1900nm, silica alumina ratio is 30-300; With the quality of catalyst for benchmark, the quality proportioning of the active component of described catalyst, carrier, modified binder and metal oxide is (3-60): (80-5): (2.0-55): (0.1-50); Described modified binder is made up of modified binder I and modified binder II, described modified binder I adopts metal-modified method to obtain, modified binder II adopts static hydrothermal crystallization method to obtain, and the mass ratio of described modified binder I and modified binder II is 0.1-10:1.
2. catalyst as claimed in claim 1, it is characterized in that, with the quality of catalyst for benchmark, the mass ratio of described active component, carrier, modified binder and metal oxide is (10-35): (20-60): (7.0-35): (1.0-40).
3. catalyst as claimed in claim 1, it is characterized in that, the described mesopore of ZSM-11 molecular sieve and the volume ratio of micropore are (0.5-2.0): 1, crystal grain is 200-1700nm, silica alumina ratio is 30-100.
4. catalyst as claimed in claim 1, it is characterized in that, described carrier is selected from kaolin, MgO, sepiolite, Al
2o
3, SiO
2with at least one in diatomite.
5. catalyst as claimed in claim 1, it is characterized in that, the preparation method of described modified binder comprises:
Metal-modified process: by binding agent and 2mol/L metal salt solution mix and blend 4h under 60 DEG C of water bath condition, after in left at room temperature 4-6h, obtain modified binder I; Wherein, in metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal, described metal oxide is selected from least one in Zn, W, B, P, Zr, Mg and Mn oxide, and the quality of described metal oxide is the 0.5%-15% of described binding agent quality;
Static hydrothermal crystallization process: binding agent is put into crystallizing kettle, static crystallization 2-8h at 100 DEG C, after in left at room temperature 4-6h, obtain modified binder II;
The ratio of modified binder I and modified binder II 0.1-10:1 is in mass ratio mixed, after stirring, obtains described modified binder.
6. catalyst as claimed in claim 5, it is characterized in that, described binding agent is selected from least one in Ludox, Alumina gel and waterglass.
7. catalyst as claimed in claim 6, it is characterized in that, when described binding agent is Ludox, its quality is in the quality of silica, and wherein the mass fraction of silica in described Ludox is 40.0%; When described binding agent is waterglass, its quality is in the quality of silica, and wherein the mass fraction of silica in described waterglass is 27.5%; When described binding agent is Alumina gel, its quality is in the quality of monohydrate alumina, and wherein the mass fraction of monohydrate alumina in described Alumina gel is 20.0%.
8. catalyst as claimed in claim 1, it is characterized in that, described metal oxide is selected from least one in Zn, Ce, P, Co, B, K, Cs, Ca, Mg, Sr and Ba oxide.
9. prepare a method for catalyst according to claim 1, it is characterized in that, said method comprising the steps of:
Described active component, carrier and modified binder are mixed with deionized water by regulation order, mechanical agitation is even, make catalyst gel;
Metal salt solution is joined in described catalyst gel, in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, sieve out the catalyst granules of 80-200 μm after cooling, in described metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal.
10. prepare a method for catalyst according to claim 1, it is characterized in that, said method comprising the steps of:
Described active component, carrier and modified binder are mixed with deionized water by regulation order, mechanical agitation is even, make catalyst gel; By above-mentioned catalyst gel in 120 DEG C of dry 6-8h, 700 DEG C of roasting 2h, after cooling, sieve out the catalyst granules of the intermediary form of 80-200 μm;
Under normal temperature, impregnating metal salting liquid on the catalyst granules of above-mentioned intermediary form, subsequently in 140 DEG C of dry 8-10h, 700 DEG C of roasting 2h, obtained catalyst granules; In described metal salt solution, the quality of slaine is with the Mass Calculation of the corresponding metal oxide of this metal.
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|---|---|---|---|---|
| CN105056989A (en) * | 2015-07-24 | 2015-11-18 | 麦森能源科技有限公司 | Catalyst for methanol-to-gasoline and preparation method thereof |
| CN113797962A (en) * | 2020-06-17 | 2021-12-17 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method and application thereof |
| CN114605213A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for producing propylene from synthesis gas and dimethyl ether |
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|---|---|---|---|---|
| CN101176849A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof |
| CN102513142A (en) * | 2011-10-25 | 2012-06-27 | 中国海洋石油总公司 | Preparation method for preparing gasoline catalyst with methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176849A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Catalyzer for preparing propylene from methanol or dimethyl ether in high selectivity and preparation method thereof |
| CN102513142A (en) * | 2011-10-25 | 2012-06-27 | 中国海洋石油总公司 | Preparation method for preparing gasoline catalyst with methanol |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105056989A (en) * | 2015-07-24 | 2015-11-18 | 麦森能源科技有限公司 | Catalyst for methanol-to-gasoline and preparation method thereof |
| CN113797962A (en) * | 2020-06-17 | 2021-12-17 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method and application thereof |
| CN113797962B (en) * | 2020-06-17 | 2023-01-13 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method and application thereof |
| CN114605213A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for producing propylene from synthesis gas and dimethyl ether |
| CN114605213B (en) * | 2020-12-09 | 2023-01-31 | 中国科学院大连化学物理研究所 | Method for producing propylene from synthesis gas and dimethyl ether |
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