CN103638964A - Molecular sieve catalyst and preparation method thereof, and preparation method of diolefin compounds - Google Patents
Molecular sieve catalyst and preparation method thereof, and preparation method of diolefin compounds Download PDFInfo
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Abstract
The invention provides a molecular sieve catalyst which comprises an active component and a support, wherein the active component is composed of one or more of Type-X molecular sieve, Type-Y molecular sieve, ZSM-5 molecular sieve, beta molecular sieve and SAPO molecular sieve. The molecular sieve catalyst provided by the invention belongs to a solid acid catalyst; the ratio of the B acid active centers to L acid active centers of the molecular sieve catalyst can reach 1.76, so the B acid active centers are more than the L acid active centers; and thus, the molecular sieve catalyst can enhance the selectivity of condensation reaction. The molecular sieve catalyst has higher specific area, and thus, has higher activity. When being used in the reaction for preparing diolefin compounds by an olefin aldehyde condensation one-step process, the molecular sieve catalyst can simultaneously ensure higher conversion rate and higher selectivity of the condensation reaction.
Description
Technical field
The present invention relates to catalyst field, relate in particular to the preparation method of a kind of molecular sieve catalyst, its preparation method and double olefin compound.
Background technology
Rubber has purposes and greatly demand widely in industrial and agricultural production, communications and transportation, national defence and daily life.Rubber can be divided into natural rubber and synthetic rubber, natural rubber yields poorly, price is high, can not meet the demand of production, therefore, people are on the basis of natural rubber structure, developed synthetic rubber, synthetic rubber is not only with low cost, and has good heat resistance, cold resistance and anticorrosive property, but in some properties, synthetic rubber can not substitute natural rubber completely, as poor in elastomeric drawing effect, and tearing toughness and mechanical performance are also all inferior to natural rubber.Structure and the character of isoprene rubber approach natural rubber most, and its resistance to water and electrical insulating property have even surpassed natural rubber.Therefore, research isoprene rubber has great importance to development Rubber Industry.
Isoprene rubber is polymerized by isoprene monomer, along with isoprene rubber industrial expansion, and will be larger to the demand of isoprene.Therefore, the preparation of isoprene monomer is the important foundation of development isoprene rubber industry.
In prior art, isoprene is mainly reacted and is made by olefine aldehyde condensation.Olefine aldehyde condensation reaction can be divided into two-step method and one-step method.Two-step method be formaldehyde and isobutene under 70～100 ℃ of conditions, first reaction generates 4,4-dimethyl-1,3-dioxy six alkane, then 4,4-dimethyl-1,3-dioxy six alkane cracking Isoprene at 250～280 ℃; One-step method is formaldehyde and isobutene Direct Dehydration condensation Isoprene under 200～300 ℃ of conditions.Because one-step method flow process is short, separated simple, side reaction is few, and product quality is high, so this technique has good development prospect.
In one-step method, prepare in the process of isoprene, the conversion ratio that catalyst can improve reaction is efficiently with selective.As US Patent No. 3253051 discloses a kind of Cr, Mn, Ag, Fe, the active component that the metallic compounds such as Mg and phosphorus compound form, described active component obtains catalyst after load, dehydrating condensation process by this catalyst for catalysis formaldehyde and isobutene, one-step method is prepared isoprene.But the disclosed catalyst catalytic performance of this patent is lower, conversion ratio (in formaldehyde) is up to 70%, selectively be up to 75%, and can not guarantee that condensation reaction has higher conversion ratio and higher selective simultaneously, when reaching higher when selective, conversion ratio (in formaldehyde) only has 22%.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of molecular sieve catalyst, its preparation method and double olefin compound, and molecular sieve catalyst provided by the invention can guarantee higher conversion ratio and higher selective when olefine aldehyde condensation one-step method diolefin compounds processed simultaneously.
The invention provides a kind of molecular sieve catalyst, comprise active component and carrier;
Described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.
Preferably, the mass ratio of described active component and carrier is 0.5～15:1.
Preferably, described carrier is Ludox or aluminium-containing substance.
Preferably, also comprise auxiliary agent;
Described auxiliary agent for containing the compound of Na, containing the compound of K, the oxide of the compound of Nd, Mo, MgO, CaO, BaO, Al
2o
3, Bi
2o
3, the oxide of Mn is, the oxide of the oxide of Sb, Ce, ZnO, ZrO
2, CuO, Fe
2o
3, containing compound, the B of Re
2o
3, SiO
2, containing the compound of P, containing the compound of S and one or more in Ag simple substance.
The preparation method who the invention provides a kind of molecular sieve catalyst, comprises the following steps:
A) active component and carrier are mixed, carry out the load of active component, obtain catalyst precursor, described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve;
B) by described steps A) carry out the first roasting after the catalyst precursor that obtains is dry, obtain catalyst intermediate;
C) by described step B) in the catalyst intermediate that obtains mix and carry out ion-exchange reactions with ion-exchanger, obtain ion-exchange reactions product;
D) by described step C) the ion-exchange reactions product that obtains carries out the second roasting and obtains molecular sieve catalyst.
Preferably, described steps A) in, the temperature of load is 20～95 ℃, and the time of load is 0.5～8 hour.
Preferably, described step B), the first sintering temperature is 300～380 ℃;
Described step B) in, the first roasting time is 0.5～8 hour.
Preferably, described step D), the second sintering temperature is 450～550 ℃;
Described step D) in, the second roasting time is 1～10 hour.
The preparation method who the invention provides a kind of diolefin compounds, comprises the following steps:
The carbonyl containing compound with structure shown in formula (1) is carried out to dehydration condensation with the monoolefine compounds with formula (2) structure under the effect of catalyst, obtain diolefin compounds;
Described catalyst is the molecular sieve catalyst that preparation method obtains described in molecular sieve catalyst described in claim 1～4 any one or claim 5～8 any one;
Wherein, R
1, R
2, R
3, R
4independently be selected from hydrogen, alkyl and aromatic radical.
Preferably, described R
1, R
2, R
3, R
4the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that to be independently selected from hydrogen, straight chained alkyl that carbon number is 1～8, branched alkyl, phenyl, carbon number that carbon number is 1～8 be 1～8 replaces or carbon number are 1～8 replaces.
Preferably, described monoolefine compounds is 3～10:1 with the mol ratio containing carbonyl complex.
Preferably, the quality of described catalyst is (1～3) g:1mol with the amount of substance ratio with the compound containing carbonyl of structure shown in formula (I).
Preferably, described dehydration condensation temperature is 250～350 ℃.
The invention provides a kind of molecular sieve catalyst, comprise active component and carrier, described active component is molecular sieve, and described molecular sieve is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.Molecular sieve catalyst provided by the invention belongs to solid acid catalyst, solid acid catalyst has two kinds of activated centre: Bronsted acid (being called for short B acid) activated centre and Lewis acid (being called for short L acid) activated centre, in described olefine aldehyde condensation one-step method, prepare in the course of reaction of diolefin compounds, the more many generations that are more conducive to diolefin in B acid activity center, molecular sieve catalyst B acid activity provided by the invention center can reach 1.76 with the ratio at L acid activity center, B acid activity center is in the majority, therefore, molecular sieve catalyst provided by the invention can improve the selective of condensation reaction.Molecular sieve catalyst has high specific area, and molecular sieve catalyst specific area provided by the invention can reach 358m
2/ g, higher specific area makes molecular sieve catalyst have higher activity.Described molecular sieve catalyst is prepared to the reaction of double olefin compound for catalytic olefine condensation one-step method, can guarantee that condensation reaction has higher conversion ratio and higher selective simultaneously.
Described auxiliary agent be described auxiliary agent for the compound containing Na, containing the compound of K, the oxide of the compound of Nd, Mo, MgO, CaO, BaO, Al
2o
3, Bi
2o
3, the oxide of Mn is, the oxide of the oxide of Sb, Ce, ZnO, ZrO
2, CuO, Fe
2o
3, containing compound, the B of Re
2o
3, SiO
2, containing the compound of P, containing the compound of S and one or more in Ag simple substance.
The present invention also provides a kind of preparation method of molecular sieve catalyst, and active component and carrier can be obtained to described molecular sieve catalyst by load and roasting, and method provided by the invention is simple, and easy operating is beneficial to and carries out large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the structural representation of fixed bed used in the embodiment of the present invention;
Fig. 2 is catalyst regeneration life test figure in the embodiment of the present invention 58.
The specific embodiment
The invention provides a kind of molecular sieve catalyst, comprise active component and carrier;
Described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.
Molecular sieve catalyst provided by the invention belongs to solid acid catalyst, solid acid catalyst has two kinds of activated centre: Bronsted acid (being called for short B acid) activated centre and Lewis acid (being called for short L acid) activated centre, in described olefine aldehyde condensation one-step method, prepare in the course of reaction of diolefin compounds, the more many generations that are more conducive to diolefin in B acid activity center, molecular sieve catalyst B acid activity provided by the invention center can reach 1.76 with the ratio at L acid activity center, B acid activity center is in the majority, therefore, molecular sieve catalyst provided by the invention can improve the selective of condensation reaction.Molecular sieve catalyst has high specific area, and molecular sieve catalyst specific area provided by the invention can reach 358m
2/ g, higher specific area makes molecular sieve catalyst have higher activity.
Molecular sieve catalyst provided by the invention comprises active component, and described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.In the present invention, described active component is preferably one or more in Na-ZSM-5 molecular sieve, Na-X molecular sieve, Na-Y molecular sieve, Na-beta-molecular sieve and Na-SAPO molecular sieve, more preferably one or more in Na-ZSM-5 molecular sieve, Na-X molecular sieve and Na-Y molecular sieve, most preferably are Na-ZSM-5 molecular sieve.The present invention does not have special restriction to the source of described molecular sieve, can adopt the commercial goods of described molecular sieve, can adopt the technical scheme of preparing molecular sieve well known to those skilled in the art to prepare voluntarily yet.
Molecular sieve catalyst provided by the invention comprises carrier, and the present invention does not have special restriction to the kind of described carrier, can the above-mentioned active component of load.In the present invention, described carrier is preferably Ludox or aluminium-containing substance, more preferably one or more in boehmite, aluminium colloidal sol, Ludox and titanium aluminium glue, most preferably are one or more in boehmite, aluminium colloidal sol and Ludox, are the most preferably Ludox.
The present invention is to the specific area of described boehmite, Na
2the content of O and using method do not have special restriction, can load described in active component.In the present invention, the specific area of described boehmite is preferably 250～380m
2/ g, more preferably 280～360m
2/ g; Described Na
2the content of O is preferably 0～0.1g, more preferably 0～0.05g; The present invention preferably adds deionized water in boehmite, and the mass ratio of described deionized water and boehmite is preferably 1:1.
The present invention does not have special requirement to the solid masses concentration in described aluminium colloidal sol, solid average grain diameter and pH value, can load described in active component.In the present invention, the solid masses concentration in described aluminium colloidal sol is preferably 20～30%, and more preferably 28%; Solid average grain diameter in described aluminium colloidal sol is preferably 15 μ m～35 μ m, more preferably 20 μ m～30 μ m; The pH value of described aluminium colloidal sol is preferably 4～6, and more preferably 5.
The present invention is to SiO in described Ludox
2the mass concentration of mass concentration, average grain diameter and sodium ion there is no special restriction, can load described in active component.In the present invention, SiO in described Ludox
2mass concentration be preferably 30～50%, more preferably 40%; SiO in described Ludox
2average grain diameter be preferably 15 μ m～30 μ m, more preferably 20 μ m; In described Ludox, the mass concentration of sodium ion is preferably 0～0.1%, and more preferably 0～0.05%.
In the present invention, the mass ratio of described active component and carrier is preferably 0.5～15:1, and more preferably 0.8～10:1, most preferably is 1:1.
Molecular sieve catalyst provided by the invention preferably also comprises auxiliary agent, described auxiliary agent is preferably compound containing Na, containing the compound of K, the oxide of the compound of Nd, Mo, MgO, CaO, BaO, Al
2o
3, Bi
2o
3, the oxide of Mn is, the oxide of the oxide of Sb, Ce, ZnO, ZrO
2, CuO, Fe
2o
3, containing compound, the B of Re
2o
3, SiO
2, containing the compound of P, containing compound and one or more in Ag simple substance, the more preferably HPO of S
3, Al
2o
3, Sb
2o
3, MoO
3, Ag, Fe
2o
3, CuO and NdCl
3in one or more, most preferably be HPO
3, Fe
2o
3with one or more in Ag.The present invention does not have special restriction to the source of described auxiliary agent, after overload, dry, ion-exchange and roasting, can access described auxiliary agent.In the present invention, the source of described auxiliary agent be preferably the oxide of Na, the oxide of K, MgO, CaO, containing the compound of Mo, containing the compound of Ba, containing the compound of Al, containing the compound of Bi, containing the compound of Mn, the oxide of Sb, compound containing Ce, ZnO, containing the compound of Zr, containing the compound of Fe, containing the compound of Cu, containing the compound of Re, containing compound, the SiO of B
2, containing the compound of P, containing the compound of S, containing the compound of Nd with containing one or more in the compound of Ag, more preferably H
3pO
4, P
2o
5, Al (OH)
3, Sb
2o
3, MoO
3, AgNO
3, Fe
2o
3, CuSO
4and NdCl
36H
2one or more in O, most preferably are H
3pO
4, Fe
2o
3and AgNO
3in one or more.
In the present invention, the mass ratio of described auxiliary agent and active component is 0.01～1:1, is preferably 0.03～0.5:1, more preferably 0.04～0.1:1.
The preparation method who the invention provides a kind of molecular sieve catalyst, comprises the following steps:
A) active component and carrier are mixed, carry out the load of active component, obtain catalyst precursor, described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve;
B) by described steps A) carry out the first roasting after the catalyst precursor that obtains is dry, obtain catalyst intermediate;
C) by described step B) in the catalyst intermediate that obtains mix and carry out ion-exchange reactions with ion-exchanger, obtain ion-exchange reactions product;
D) by described step C) the ion-exchange reactions product that obtains carries out the second roasting and obtains molecular sieve catalyst.
The present invention mixes active component and carrier, carries out the load of active component, obtains catalyst precursor.Described active component is consistent with active component and carrier in technique scheme with carrier, does not repeat them here.The present invention does not have special restriction to the charging sequence of described active component and carrier, active component and carrier can be mixed.
The present invention does not have special restriction to the load device of described mixed solution and carrier, adopts load device well known to those skilled in the art to carry out load.In the present invention, the load device of described mixed solution and carrier is preferably mixed sizing device.
In the present invention, the temperature of described active component load is preferably 20～95 ℃, more preferably 40～93 ℃, most preferably is 90 ℃; The time of described active component load is preferably 0.5～8 hour, more preferably 1～6 hour, most preferably is 2 hours.
Obtain after described catalyst precursor, after the present invention is dry by described catalyst precursor, carry out the first roasting, obtain catalyst intermediate.The present invention does not have special restriction to the drying means of described catalyst precursor, adopts dry technical scheme well known to those skilled in the art to be dried.In the present invention, the dry evaporate to dryness that is preferably of described catalyst precursor; The baking temperature of described catalyst precursor is preferably 100～200 ℃, more preferably 130～180 ℃, most preferably is 150 ℃.
After completing described catalyst precursor dry, the present invention carries out the first roasting by the dried catalyst precursor obtaining, and obtains catalyst intermediate.The present invention does not have special restriction to the device of the first described roasting, adopts the device that carries out roasting well known to those skilled in the art.In the present invention, the device of described the first roasting is preferably Muffle furnace; The temperature of described the first roasting is preferably 300～380 ℃, more preferably 330～360 ℃, most preferably is 340～350 ℃; The time of described the first roasting is preferably 0.5～8 hour, more preferably 1～6 hour, most preferably is 4～5 hours.
Obtain after catalyst intermediate, the present invention mixes described catalyst intermediate to carry out ion-exchange reactions with ion-exchanger, obtains ion-exchange reactions product.
The present invention preferably pulverizes the catalyst intermediate obtaining, and the catalyst intermediate particle obtaining is mixed with ion-exchanger and carries out ion-exchange reactions.The present invention does not have special restriction to described for the device of pulverizing, and adopts reducing mechanism well known to those skilled in the art to pulverize.In the present invention, the particle diameter of described pulverizing rear catalyst midbody particle is preferably 20～80 orders, more preferably 25～75 orders.
Complete after the pulverizing of catalyst intermediate, the present invention mixes with ion-exchanger the catalyst intermediate particle obtaining carry out ion-exchange reactions, obtains ion-exchange reactions product.In the present invention, described ion-exchanger is preferably ammonium chloride or hydrochloric acid, and more preferably ammonium chloride solution or hydrochloric acid, most preferably be ammonium chloride solution.In the present invention, the mass concentration of described ammonium chloride solution is preferably 0.5%～3%, and more preferably 0.8%～2%, most preferably be 1%; The present invention does not have special restriction to the consumption of described ammonium chloride solution, can complete described ion-exchange reactions; The present invention does not have special restriction to the number of times of described ion-exchange reactions, adopts ion-exchange reactions number of times well known to those skilled in the art.In the present invention, the number of times of ion-exchange reactions is preferably 2～5 times, more preferably 4 times.
Complete after described ion-exchange reactions, the present invention carries out the second roasting by the ion-exchange reactions product obtaining, and obtains molecular sieve catalyst.Complete after described ion-exchange reactions, the present invention preferably carries out Separation of Solid and Liquid by the ion-exchange reactions product obtaining, and the solid obtaining is washed to laggard row the second roasting, obtains molecular sieve catalyst.The present invention does not have special restriction to the method for described Separation of Solid and Liquid, adopts the technical scheme of Separation of Solid and Liquid well known to those skilled in the art to carry out Separation of Solid and Liquid.In the present invention, the method for described Separation of Solid and Liquid is preferably filtration; In the present invention, described washing times is preferably 1～6 time, more preferably 2～5 times, most preferably is 3 times
Complete after described washing, the solid that the present invention preferably obtains washing is dried, and dried solid is carried out to the second roasting, obtains molecular sieve catalyst.The present invention to described washing after the drying means of solid there is no special restriction, adopt drying means well known to those skilled in the art to be dried.In the present invention, after described washing, the dry method of solid is preferably evaporate to dryness; After described washing, the dry temperature of solid is preferably 100～150 ℃, more preferably 110～120 ℃, most preferably is 125 ℃.
Complete after solid after described washing dry, the present invention carries out the second roasting by dried solid, obtains molecular sieve catalyst.The present invention does not have special restriction to the device of the second described roasting, adopts the device that carries out roasting well known to those skilled in the art to carry out roasting.In the present invention, described the second calciner is preferably Muffle furnace.Described the second sintering temperature is preferably 450～550 ℃, more preferably 480～530 ℃, most preferably is 490～510 ℃; Described the second roasting time is preferably 1～10 hour, more preferably 3～8 hours, most preferably is 4～5 hours.
The present invention also provides a kind of preparation method of diolefin compounds, comprises the following steps:
The carbonyl containing compound with structure shown in formula (1) is carried out to dehydration condensation with the monoolefine compounds with formula (2) structure under the effect of catalyst, obtain diolefin compounds;
Described catalyst is the molecular sieve catalyst described in technique scheme;
Wherein, R
1, R
2, R
3, R
4independently be selected from hydrogen, alkyl and aromatic radical.
In the present invention, the monoolefine compounds that has the carbonyl containing compound of structure shown in formula (1) and have formula (2) structure carries out condensation reaction, during the reaction of described condensation reaction suc as formula shown in (A):
Wherein, cat represents molecular sieve catalyst provided by the invention; R
1, R
2, R
3, R
4with the R described in technique scheme
1, R
2, R
3, R
4unanimously, at this to substituent R
1, R
2, R
3, R
4repeat no more; R
4' compare R
4few one-H.
The present invention carries out dehydration condensation by the carbonyl containing compound with structure shown in formula (1) with the monoolefine compounds with formula (2) structure under the effect of catalyst, obtains diolefin compounds.
In the present invention, described carbonyl containing compound has structure shown in formula (1):
Wherein, R
1, R
2independently be selected from hydrogen, alkyl and aromatic radical, the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is preferably 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, phenyl, carbon number are 1～8 replaces or carbon number are 1～8 replaces, more preferably the branched alkyl that the straight chained alkyl that is 1～8 independently selected from hydrogen, carbon number or carbon number are 1～8, is most preferably independently selected from hydrogen, methyl or isopropyl.Work as R
1for H, R
2during for H, described in there is formula (1) structure carbonyl containing compound be formaldehyde; Work as R
1for H, R
2during for methyl, described in there is formula (1) structure carbonyl containing compound be acetaldehyde; Work as R
1for H, R
2during for isopropyl, described in there is formula (1) structure carbonyl containing compound be isobutylaldehyde.
The present invention does not have special restriction to the described source with the carbonyl containing compound of structure shown in formula (1), can adopt the commercial goods with the carbonyl containing compound of structure shown in formula (1), the technical scheme that also can have a carbonyl containing compound of structure shown in formula (1) according to preparation well known to those skilled in the art is prepared voluntarily.
In the present invention, described monoolefine compounds has structure shown in formula (2):
Wherein, R
3, R
4independently be selected from hydrogen, alkyl and aromatic radical, the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that the branched alkyl that the straight chained alkyl that is preferably 1～8 independently selected from hydrogen, carbon number, carbon number are 1～8, phenyl, carbon number are 1～8 replaces or carbon number are 1～8 replaces, branched alkyl or phenyl that the straight chained alkyl that more preferably carbon number is 1～8, carbon number are 1～8, most preferably be methyl, phenyl or isopropyl.Concrete, as described R
3for methyl, R
4during for methyl, described in there is formula (2) structure monoolefine be isobutene; As described R
3for methyl, R
4during for phenyl, described in there is formula (2) structure monoolefine be AMS; As described R
3for methyl, R
4during for isopropyl, described in there is formula (2) structure monoolefine be 2,3-dimethyl-1-butylene.
The present invention does not have special restriction to the described source with the monoolefine compounds of structure shown in formula (2), can adopt the commercial goods with the monoolefine compounds of structure shown in formula (2), the technical scheme that also can have a monoolefine compounds of structure shown in formula (2) according to preparation well known to those skilled in the art is prepared voluntarily.The preparation method in the present invention, with the monoolefine compounds of formula (2) structure preferably includes following steps:
The ether compound with structure shown in formula (3) is carried out to cracking reaction, the monoolefine compounds of the structure shown in (2) that obtains thering is formula;
Wherein, R
3, R
4independently selected from hydrogen, alkyl and aromatic radical.
The present invention carries out cracking reaction by the ether compound with structure shown in formula (3), the monoolefine compounds of the structure shown in (2) that obtains having formula.In the present invention, the R in described formula (3)
3and R
4with the R in formula described in technique scheme (2)
3and R
4unanimously, do not repeat them here.Concrete, when R3 is methyl, when R4 is methyl, described in there is formula (3) structure ether compound be methyl tertiary butyl ether(MTBE).
The present invention does not have special restriction to the condition of the monoolefine compounds of structure shown in the ether compound cracking preparation formula (2) of structure shown in described formula (3), adopts the condition of cracking reaction well known to those skilled in the art.In the present invention, the temperature of described cracking reaction is preferably 250～350 ℃, more preferably 280～230 ℃, most preferably is 300 ℃; The described cracking reaction time is preferably 0.1～2 hour, more preferably 0.5～1.5 hour, most preferably is 1 hour.
In the present invention, described in there is formula (2) structure monoolefine compounds with described in there is structure shown in formula (1) the mol ratio containing carbonyl complex be preferably 3～10:1, more preferably 4～6:1, most preferably is 5.5:1.The quality of described catalyst with described in there is structure shown in formula (1) the ratio containing the amount of substance of carbonyl complex be preferably (1～3) g:1mol, more preferably (1.5～2.5) g:1mol, most preferably is 2g:1mol.
In the present invention, described dehydration condensation temperature is preferably 250～350 ℃, more preferably 280～230 ℃, most preferably is 300 ℃; The described dehydration condensation time is preferably 0.1～2 hour, more preferably 0.5～1.5 hour, most preferably is 1 hour; In described dehydration condensation, gas-solid contact time is preferably 0.2～1.0 second, more preferably 0.3～0.8 second, most preferably is 0.4 second.
The present invention does not have special restriction to the device of described dehydration condensation, preferably adopt the fixed-bed reactor with structure shown in Fig. 1, Fig. 1 is the structural representation of fixed bed used in the embodiment of the present invention, and wherein 1 is the first material feeding pump, and 2 is the second material feeding pump, 3 is the first valve, 4 is the second valve, and 5 is reaction tube, and 6 is condenser, 7 is gas-liquid separation and carbonyl containing compound retracting device, and 8 is gas chromatograph.
In the present invention, described fixed-bed reactor comprises the first material feeding pump 1, the outlet of described the first product pump 1 is connected with the import of the first valve 3 by the first material pipe (not marking in figure), the outlet of described the first valve 3 is connected with the charging aperture of described reaction tube 5, described the first valve 3 is for regulating the flow of the first material, the present invention does not have special restriction to the material of the first described material pipe and size, can transport material.The present invention is for the ease of the conveying of material, in an embodiment of the present invention, the fixed bed reactors that the present invention adopts can be provided with the second material pipe (not marking in figure) and mixed material pipeline (not marking in figure) between the first valve 3 and reaction tube 5, and the charging aperture of described the second material pipe is connected with the discharging opening of described the first valve 3; The discharging opening of described the second material pipe is connected with the charging aperture of described mixed material pipeline, the discharging opening of described mixed material pipeline is connected with the charging aperture of described reaction tube, described mixed material pipeline, for by after the first material and the second mixing of materials, is delivered to reaction tube 5.
In the present invention, described fixed bed reactors comprise the second material feeding pump 2, described the second material feeding delivery side of pump is connected with the import of the second valve 4 by 3 material pipeline (not marking in figure), the outlet of described the second valve 4 is connected with the charging aperture of described reaction tube 5, described the second valve 4 is for regulating the flow of the second material, the present invention does not have special restriction to the material of described 3 material pipeline and size, can transport material.The present invention is for the ease of the conveying of material, in an embodiment of the present invention, the fixed bed reactors that the present invention adopts can be provided with 4 materials pipeline (not marking in figure) and mixed material pipeline (not marking in figure) between the second valve 4 and reaction tube 5, and the charging aperture of described 4 materials pipeline is connected with the discharging opening of described the second valve 4; The discharging opening of described 4 materials pipeline is connected with the charging aperture of described mixed material pipeline, and described mixed material pipeline, for by after the first material and the second mixing of materials, is delivered to reaction tube 5.
In the present invention, described the first material is for having the carbonyl containing compound of structure shown in formula (1), and the second material is the ether compound that has the monoolefine compounds of formula (2) structure and/or have structure shown in formula (3); Or described the first material is the ether compound that has the monoolefine compounds of formula (2) structure and/or have structure shown in formula (3), the second material is for having the carbonyl containing compound of structure shown in formula (1), and the present invention does not have special restriction to this.
In the present invention, described fixed bed reactors comprise reaction tube 5, the discharging opening of described reaction tube 5 is connected with the charging aperture of described condenser 6, in described reaction tube 5, be placed with the molecular sieve catalyst described in technique scheme, the first material and the second material that catalysis transports carry out dehydration condensation, obtain double olefin compound.The present invention does not have special restriction to the material of described reaction tube 5 and size, can provide place for condensation reaction, and in the present invention, described reaction tube 5 is preferably dimensioned to be Φ 10mm～Φ 20mm.
In the present invention, described fixed bed reactors comprise condenser 6, the discharging opening of described condenser 6 is connected with the charging aperture of described gas-liquid separation and carbonyl containing compound retracting device 7, described condenser 6 is condensed into liquid for the gaseous reaction products that reaction tube 5 is obtained, and is conducive to the separated of product and excess raw material.The present invention does not have special restriction to the kind of described condenser 6 and source, can reach the effect of condensation.
In the present invention, described fixed bed reactors comprise gas-liquid separation and carbonyl containing compound retracting device 7, the discharging opening of described gas-liquid separation and formaldehyde retracting device 7 is connected with the charging aperture of described gas chromatograph 8, described gas-liquid separation and formaldehyde retracting device 7 carry out separation for the gas-liquid mixture that condenser 6 is obtained, and unreacted formaldehyde carbonyl containing compound is reclaimed.The present invention does not have special restriction to the kind of described gas-liquid separation and carbonyl containing compound retracting device 7 and source, can realize the recovery of gas-liquid separation and carbonyl containing compound.
In the present invention, described fixed bed reactors comprise gas chromatograph 8, and described gas chromatograph 8 is for the detection of product.The present invention does not have special restriction to the model of described gas chromatograph, can detection reaction product.
Below in conjunction with above-mentioned fixed-bed reactor, illustrate the preparation method of diolefin provided by the invention:
By described in the ether compound that there is the monoolefine compounds of formula (2) structure and/or there is structure shown in formula (3) by the first material feeding pump 1, the first material pipe, the first valve 3 and the second material pipe, be delivered in mixed material pipeline successively, with have structure shown in formula (1) containing after carbonyl complex mixes, be delivered in reaction tube 5;
What will have structure shown in formula (1) is delivered to mixed material pipeline by the second material feeding pump 2,3 material pipeline, the second valve 4 and 4 materials pipeline successively containing carbonyl complex, after mixing with the ether compound that there is the monoolefine compounds of formula (2) structure and/or there is structure shown in formula (3), then be delivered in reaction tube 5;
Mixed material enters in reaction tube 5 and contacts and carry out condensation reaction with pipe inner catalyst, obtain after completion of the reaction mist, described mist is passed into and in condenser 6, carries out condensation, obtain gas-liquid mixture, the gas-liquid mixture obtaining is passed in gas-liquid separation and carbonyl containing compound retracting device 7 and carries out gas-liquid separation, obtain liquid-phase reaction product, and unreacted carbonyl containing compound is reclaimed, described liquid-phase reaction product is passed in gas chromatograph 8 and detected.
The invention provides a kind of molecular sieve catalyst, comprise active component and carrier, described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.Molecular sieve catalyst provided by the invention belongs to solid acid catalyst, solid acid catalyst has two kinds of activated centre: Bronsted acid (being called for short B acid) activated centre and Lewis acid (being called for short L acid) activated centre, in described olefine aldehyde condensation one-step method, prepare in the course of reaction of diolefin compounds, the more many generations that are more conducive to diolefin in B acid activity center, molecular sieve catalyst B acid activity provided by the invention center can reach 1.76 with the ratio at L acid activity center, B acid activity center is in the majority, therefore, molecular sieve catalyst provided by the invention can improve the selective of condensation reaction.Molecular sieve catalyst has high specific area, and molecular sieve catalyst specific area provided by the invention can reach 358m
2/ g, higher specific area makes molecular sieve catalyst have higher activity.
The invention provides a kind of preparation method of molecular sieve catalyst, by load and ion-exchange, can obtain described molecular sieve catalyst, method provided by the invention is simple, and easy operating is beneficial to and carries out large-scale industrial production.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of a kind of molecular sieve catalyst provided by the invention, its preparation method and double olefin compound is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
By 50g Na-ZSM-5 molecular sieve, 1g Ca
3(PO
4)
2add in the round-bottomed flask of 500ml with 50g Ludox, wherein, SiO in Ludox
2for 40wt%, average grain diameter is 20 microns, Na
+concentration is less than 0.1wt%;
Round-bottomed flask is connected in mixed sizing device, carries out the load of active component, molecular sieve is mixed with Ludox, load temperature is 90 ℃, and load time is 2 hours;
Complete after the load of active component, by temperature increase to 150 ℃, evaporating water, proceeds in Muffle furnace roasting at 350 ℃ by the catalyst precursor obtaining and after 4 hours, makes active component in catalyst fix, and obtains catalyst intermediate;
The catalyst intermediate obtaining is pulverized, obtain catalyst intermediate particle, collect 20～80 order particles, the ammonium chloride solution of mass concentration 1% is added in catalyst intermediate particle and carries out ion-exchange reactions 4 times, obtain reaction solution, reaction solution is filtered, the solid washing that filtration is obtained 3 times, is dried temperature increase to 125 ℃ evaporating water to the solid after washing, again dry solid is proceeded in Muffle furnace at 500 ℃ to roasting 4 hours, obtain molecular sieve catalyst.
It is proportional that the present invention has measured the molecular sieve catalyst total acid content, specific area and the acid activity central. set that obtain, and wherein, the total acid content of molecular sieve catalyst is 2.71mmol/g, and specific area is 311m
2/ g, acid activity central. set is proportional is B acid: L acid=1.55:1.
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts 25g Na-X molecular sieve to replace the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts 750g Na-Y molecular sieve to replace the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts Na-beta-molecular sieve to replace the Na-ZSM-5 molecular sieve in embodiment 1, adopts 20 ℃ active component is carried out to load.
Embodiment 5
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts SAPO molecular sieve to replace the Na-ZSM-5 molecular sieve in embodiment 1, adopts 95 ℃ active component is carried out to load.
In fixed bed shown in the molecular sieve catalyst load map 1 that embodiment 1 is obtained, by the first product pump, the first valve and mixed material transfer pipeline, in reaction tube, pass into isobutene successively, successively by the second product pump, the second valve and mixed material transfer pipeline pass into formaldehyde in reaction tube, molecular sieve catalyst quality is 2g:1mol with the ratio of the amount of substance of formaldehyde, the mol ratio of isobutene and formaldehyde is 5.5:1, reaction temperature is 300 ℃, at gas-solid contact time, be to react 60 minutes under the condition of 0.4 second, obtain admixture of gas, the admixture of gas obtaining is delivered to and in condenser, carries out condensation, obtain gas-liquid mixture, the gas-liquid mixture obtaining is passed into gas-liquid separation and in carbonyl containing compound retracting device, gas carried out separated with liquid, obtain the double olefin compound of liquid phase, and unreacted gas phase carbonyl containing compound is reclaimed.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 1, the experimental result that table 1 obtains for embodiment 6～10.
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that 1g embodiment 2 obtains to replace the 2g molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 1, the experimental result that table 1 obtains for embodiment 6～10.
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that 3g embodiment 3 obtains to replace the 2g molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 1, the experimental result that table 1 obtains for embodiment 6～10.
Embodiment 9
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 4 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 1, the experimental result that table 1 obtains for embodiment 6～10.
Embodiment 10
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 5 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 1, the experimental result that table 1 obtains for the embodiment of the present invention 6～10.
The experimental result that table 1 embodiment of the present invention 6～10 obtains
As can be seen from Table 1, activity of molecular sieve catalysts composition is different, the reaction selectivity (in formaldehyde) of the catalyst formaldehyde obtaining and isobutene dehydration condensation can reach 75.2%, conversion ratio (in formaldehyde) can reach 87.1%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 87.1%.
Embodiment 11
50g Na-ZSM-5 molecular sieve, 2g phosphoric acid (auxiliary agent) and 50g Ludox are added in the round-bottomed flask of 500ml, wherein, SiO in Ludox
2for 40wt%, average grain diameter is 20 microns, Na
+concentration is less than 0.1wt%;
Round-bottomed flask is connected in mixed sizing device, carries out the load of active component, molecular sieve is mixed with Ludox, load temperature is 90 ℃, and load time is 2 hours;
Complete after the load of active component, by temperature increase to 150 ℃, evaporating water, proceeds in Muffle furnace roasting at 350 ℃ by the catalyst precursor obtaining and after 4 hours, makes active component in catalyst fix, and obtains catalyst intermediate;
The catalyst intermediate obtaining is pulverized, obtain catalyst intermediate particle, collect 20～80 order particles, the ammonium chloride solution of mass concentration 1% is added in catalyst intermediate particle and carries out ion-exchange reactions 4 times, obtain reaction solution, reaction solution is filtered, the solid washing that filtration is obtained 3 times, is dried temperature increase to 125 ℃ evaporating water to the solid after washing, again dry solid is proceeded in Muffle furnace at 500 ℃ to roasting 4 hours, obtain molecular sieve catalyst.
It is proportional that the present invention has measured the molecular sieve catalyst total acid content, specific area and the acid activity central. set that obtain, and wherein, the total acid content of molecular sieve catalyst is 2.83mmol/g, and specific area is 358m
2/ g, acid activity central. set is proportional is B acid: L acid=1.76:1.
Embodiment 12
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g P
2o
5replace the 2g phosphoric acid in embodiment 11, adopt within 0.5 hour, to active component, carry out load.Embodiment 13
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g Al (OH)
3replace the 2g phosphoric acid in embodiment 11, adopt within 8 hours, to active component, carry out load.
Embodiment 14
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 0.5g Sb
2o
3replace the 2g phosphoric acid in embodiment 11, adopt 300 ℃ described catalyst precursor is carried out to roasting.
Embodiment 15
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 50g MoO
3replace the 2g phosphoric acid in embodiment 11, adopt 380 ℃ described catalyst precursor is carried out to roasting.
Embodiment 16
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g AgNO
3replace the 2g phosphoric acid in embodiment 11, to described catalyst precursor roasting 0.5 hour.
Embodiment 17
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g Fe
2o
3replace the 2g phosphoric acid in embodiment 11, to described catalyst precursor roasting 8 hours.Embodiment 18
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g CuSO
4replace the 2g phosphoric acid in embodiment 11, adopt 450 ℃ catalyst intermediate is carried out to roasting.
Embodiment 19
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts 2g NdCl
36H
2o replaces the 2g phosphoric acid in embodiment 11, adopts 550 ℃ catalyst intermediate is carried out to roasting.
Embodiment 20
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 11 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 21
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 12 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 22
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 13 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 23
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 14 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 24
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 15 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 25
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 16 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 26
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 17 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 27
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 18 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for embodiment 20～28.
Embodiment 28
Adopt the technical scheme of embodiment 6 to obtain double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 19 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 2, the experimental result that table 2 obtains for the embodiment of the present invention 20～28.
The experimental result that table 2 embodiment of the present invention 20～28 obtains
As can be seen from Table 2, the auxiliary agent adding is different, the reaction selectivity (in formaldehyde) of the molecular sieve catalyst catalysis formaldehyde obtaining and isobutene dehydration condensation can reach 73.7%, conversion ratio (in formaldehyde) can reach 77.8%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 77.8%.
Embodiment 29
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the hydrochloric acid solution of the present embodiment employing 5% replaced the ammonium chloride solution of 1% in embodiment 1, to described catalyst intermediate roasting 1 hour.
Embodiment 30
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 29 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 3, the experimental result that table 3 obtains for the embodiment of the present invention 30.
The experimental result that table 3 embodiment of the present invention 30 obtains
As can be seen from Table 3, ion-exchanger is changed to after 5% hydrochloric acid solution, the reaction selectivity (take methyl alcohol) that obtains molecular sieve catalyst catalysis formaldehyde and isobutene dehydrating condensation is 74.8%, the conversion ratio (take methyl alcohol) of reaction is 67.4%, illustrates that molecular sieve catalyst provided by the invention can guarantee higher conversion ratio and selective simultaneously.
Embodiment 31
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopted boehmite to replace the Ludox in embodiment 11, to described catalyst intermediate roasting 10 hours.
Embodiment 32
Adopt the technical scheme of embodiment 11 to prepare molecular sieve catalyst, different, the present embodiment adopts aluminium colloidal sol to replace the Ludox in embodiment 11.
Embodiment 33
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 31 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 4, the experimental result that table 4 obtains for embodiment 33～34.
Embodiment 34
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 32 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound of the liquid phase obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 4, the experimental result that table 4 obtains for the embodiment of the present invention 33～34.
The experimental result that table 4 embodiment of the present invention 33～34 obtains
As can be seen from Table 4, the carrier adopting is different, obtain molecular sieve catalyst catalysis formaldehyde and isobutene dehydration condensation, selectively (in formaldehyde) can reach 82.0%, conversion ratio (in formaldehyde) can reach 71.8%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 71.8%.
Embodiment 35
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts acetaldehyde to replace the formaldehyde in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is 2-methyl isophthalic acid, 3-pentadiene;
The present invention has investigated the yield of acetaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 5, the experimental result that table 5 obtains for embodiment 35～36.
Embodiment 36
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts isobutylaldehyde to replace the formaldehyde in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is 2,5-dimethyl-1,3-hexadiene;
The present invention has investigated the yield of isobutylaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 5, the experimental result that table 5 obtains for the embodiment of the present invention 35～36.
The experimental result that table 5 embodiment of the present invention 35～36 obtains
As can be seen from Table 5, take different aldehyde compounds to react as reactant, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 78.4%, conversion ratio (in formaldehyde) can reach 63.0%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 63.0%.
Embodiment 37
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts AMS to replace the isobutene in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is 2-phenyl-1,3-butadiene;
The present invention has investigated the yield of formaldehyde and AMS dehydration condensation, selective and conversion ratio, and result is as shown in table 6, the experimental result that table 6 obtains for embodiment 37～39.
Embodiment 38
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts 2,3-dimethyl-1-butylene to replace the isobutene in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is 3,4-dimethyl-1,3-pentadiene;
The present invention has investigated the yield of formaldehyde and AMS dehydration condensation, selective and conversion ratio, and result is as shown in table 6, the experimental result that table 6 obtains for embodiment 37～39.
Embodiment 39
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts AMS to replace the isobutene in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is 2-phenyl-1,3-butadiene;
The present invention has investigated the yield of formaldehyde and AMS dehydration condensation, selective and conversion ratio, and result is as shown in table 6, the experimental result that table 6 obtains for the embodiment of the present invention 37～39.
The experimental result that table 6 embodiment of the present invention 37～39 obtains
As can be seen from Table 6, adopt different alkene (ether) compounds to react as reactant, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 76.4%, conversion ratio (in formaldehyde) can reach 53.6%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 51.4%.
Embodiment 40
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the lab scale fluid bed of Φ 20mm to replace the fixed bed in embodiment 11.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 7, the experimental result that table 7 obtains for the embodiment of the present invention 40.
The experimental result that table 7 embodiment of the present invention 40 obtains
As can be seen from Table 7, adopt fluid bed as reaction unit, the reaction selectivity of formaldehyde and isobutene dehydration condensation (take formaldehyde) is 62.5%, and conversion ratio (take formaldehyde) is 55.0%.
Embodiment 41
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts 10g Na-ZSM-5 molecular sieve to replace the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 42
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts 25g Na-ZSM-5 molecular sieve to replace the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 43
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment adopts 100g Na-ZSM-5 molecular sieve to replace the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 44
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 41 prepares to replace the molecular sieve catalyst in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 8, the experimental result that table 8 obtains for embodiment 44～46.
Embodiment 45
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 42 prepares to replace the molecular sieve catalyst in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 8, the experimental result that table 8 obtains for embodiment 44～46.
Embodiment 46
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 43 prepares to replace the molecular sieve catalyst in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 8, the experimental result that table 8 obtains for the embodiment of the present invention 44～46.
The experimental result that table 8 embodiment of the present invention 44～46 obtains
As can be seen from Table 8, adopt different catalyst activity component contents, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 75.4%, conversion ratio (in formaldehyde) can reach 61.3%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 47.8%.
Embodiment 47～49
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts gas-liquid contact time 0.2s, 0.8s and 1.0s to replace respectively the gas-liquid contact time 0.4s in embodiment 11.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 9, the experimental result that table 9 obtains for the embodiment of the present invention 47～49.
The experimental result that table 9 embodiment of the present invention 47～49 obtains
As can be seen from Table 9, adopt different gas-solid contact times, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 70.6%, conversion ratio (in formaldehyde) can reach 60.2%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 53.4%.
Embodiment 50～52
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts 250 ℃, 280 ℃ and 350 ℃ of reaction temperatures to replace respectively 300 ℃ of reaction temperatures in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 10, and table 10 the present invention is the experimental result that embodiment 50～52 obtains.
The experimental result that table 10 embodiment of the present invention 50～52 obtains
As can be seen from Table 10, the reaction temperature adopting is different, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 77.4%, conversion ratio (in formaldehyde) can reach 59.0%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 47.8%.
Embodiment 53～55
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, it is that 3:1,4:1 and 10:1 replace respectively isobutene in embodiment 11 and the mol ratio 5.5:1 of formaldehyde that the present embodiment adopts the mol ratio of isobutene and formaldehyde.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 11, the experimental result that table 11 obtains for the embodiment of the present invention 53～55.
The experimental result that table 11 embodiment of the present invention 53～55 obtains
As can be seen from Table 11, the formaldehyde adopting is different with the mol ratio of isobutene, the yield of reaction, selective and conversion ratio be difference to some extent, selectively (in formaldehyde) can reach 84.2%, conversion ratio (in formaldehyde) can reach 63.3%, when reaction selectivity (in formaldehyde) is the highest, conversion ratio (in formaldehyde) can reach 42.2%.
Embodiment 56
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, the present embodiment amplifies 10 times by the catalyst preparation process equal proportion in embodiment 1.
Embodiment 57
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 56 obtains to replace the molecular sieve catalyst in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 12, the experimental result that table 12 obtains for the embodiment of the present invention 57.
The experimental result that table 12 embodiment of the present invention 57 obtains
As can be seen from Table 12, after catalyst preparation process amplifies 10 times, the selective and conversion ratio of reaction is still higher, and selectively (take formaldehyde) is 69.5%, and conversion ratio (take formaldehyde) is 56.8%.Embodiment 58
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, the present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene.
After reaction finishes, the present invention, to molecular sieve catalyst roasting 50 minutes at 500 ℃, passes into air in roasting process, and air velocity is 20L/hr, carries out the regeneration of molecular sieve catalyst.After regeneration, be cooled to experimental temperature and proceed the condensation reaction of formaldehyde and isobutene.Obtain the life assessment to molecular sieve catalyst, as shown in Figure 2, Fig. 2 is catalyst regeneration life test figure in the embodiment of the present invention 58.Wherein, curve 1 for reaction selectivity (in formaldehyde) over time; Curve 2 for reaction conversion ratio (in formaldehyde) over time; The yield (in formaldehyde) that curve 3 is reaction over time.As seen from Figure 2, catalyst regeneration is effective, and after regeneration, the activity of catalyst has obtained larger recovery.
Embodiment 59
Adopt the technical scheme of embodiment 1 to prepare molecular sieve catalyst, different, in the present embodiment, adopt industrial raw material to replace the SILVER REAGENT raw material in embodiment 1.
Embodiment 60
Adopt the technical scheme of embodiment 6 to prepare double olefin compound, different, the present embodiment adopts the molecular sieve catalyst that embodiment 59 obtains to replace the molecular sieve catalyst adopting in embodiment 6.
The present invention carries out gas chromatography determination by the double olefin compound obtaining, and result shows, the double olefin compound that the present embodiment obtains is isoprene;
The present invention has investigated the yield of formaldehyde and isobutene dehydration condensation, selective and conversion ratio, and result is as shown in table 13, the experimental result that table 13 obtains for the embodiment of the present invention 59.
The experimental result that table 13 embodiment of the present invention 59 obtains
As can be seen from Table 13, the solid acid catalyst that adopt to adopt industrial raw material to prepare, the selective and conversion ratio of reaction is higher, and selectively (take formaldehyde) is 70.3%, and conversion ratio (take formaldehyde) is 57.4%.
Meanwhile, in experiment, we have carried out the amplification test of fixed bed and fluid bed to the present invention middle part divided catalyst, and experimental result and little test result differ and be no more than 2%.
As can be seen from the above embodiments, molecular sieve catalyst catalytic activity provided by the invention and selectively higher, favorable regeneration effect, preparation process is simple.The molecular sieve catalyst that adopts industrial raw material to prepare still has higher activity.Described molecular sieve catalyst is prepared to the reaction of diolefin compounds for catalytic olefine condensation one-step method, make condensation reaction there is higher conversion ratio and higher selective simultaneously.After catalyst preparation process equal proportion is amplified to 10 times, the conversion ratio of condensation reaction and selectively higher.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (13)
1. a molecular sieve catalyst, comprises active component and carrier;
Described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.
2. molecular sieve catalyst according to claim 1, is characterized in that, the mass ratio of described active component and carrier is 0.5～15:1.
3. molecular sieve catalyst according to claim 1, is characterized in that, described carrier is Ludox or aluminium-containing substance.
4. molecular sieve catalyst according to claim 1, is characterized in that, also comprises auxiliary agent;
Described auxiliary agent for containing the compound of Na, containing the compound of K, the oxide of the compound of Nd, Mo, MgO, CaO, BaO, Al
2o
3, Bi
2o
3, the oxide of Mn is, the oxide of the oxide of Sb, Ce, ZnO, ZrO
2, CuO, Fe
2o
3, containing compound, the B of Re
2o
3, SiO
2, containing the compound of P, containing the compound of S and one or more in Ag simple substance.
5. a preparation method for molecular sieve catalyst, comprises the following steps:
A) active component and carrier are mixed, carry out the load of active component, obtain catalyst precursor, described active component is one or more in X-type molecular sieve, Y zeolite, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve;
B) by described steps A) carry out the first roasting after the catalyst precursor that obtains is dry, obtain catalyst intermediate;
C) by described step B) in the catalyst intermediate that obtains mix and carry out ion-exchange reactions with ion-exchanger, obtain ion-exchange reactions product;
D) by described step C) the ion-exchange reactions product that obtains carries out the second roasting and obtains molecular sieve catalyst.
6. preparation method according to claim 5, is characterized in that, described steps A) in the temperature of load be 20～95 ℃;
Described steps A) in, the time of load is 0.5～8 hour.
7. preparation method according to claim 5, is characterized in that, described step B) in the first sintering temperature be 300～380 ℃;
Described step B) in, the first roasting time is 0.5～8 hour.
8. according to the method described in claim 5, it is characterized in that described step D) in the second sintering temperature be 450～550 ℃;
Described step D) in, the second roasting time is 1～10 hour.
9. a preparation method for diolefin compounds, comprises the following steps:
The carbonyl containing compound with structure shown in formula (1) is carried out to dehydration condensation with the monoolefine compounds with formula (2) structure under the effect of catalyst, obtain diolefin compounds;
Described catalyst is the molecular sieve catalyst that preparation method obtains described in molecular sieve catalyst described in claim 1～4 any one or claim 5～8 any one;
Wherein, R
1, R
2, R
3, R
4independently be selected from hydrogen, alkyl and aromatic radical.
10. preparation method according to claim 9, is characterized in that, described R
1, R
2, R
3, R
4the phenyl that the branched alkyl that the phenyl that the straight chained alkyl that to be independently selected from hydrogen, straight chained alkyl that carbon number is 1～8, branched alkyl, phenyl, carbon number that carbon number is 1～8 be 1～8 replaces or carbon number are 1～8 replaces.
11. preparation methods according to claim 9, is characterized in that, described monoolefine compounds is 3～10:1 with the mol ratio containing carbonyl complex.
12. preparation methods according to claim 9, is characterized in that, the quality of described catalyst is (1～3) g:1mol with the amount of substance ratio with the compound containing carbonyl of structure shown in formula (I).
13. preparation methods according to claim 9, is characterized in that, described dehydration condensation temperature is 250～350 ℃.
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| CN107930686A (en) * | 2017-11-22 | 2018-04-20 | 山东玉皇化工有限公司 | The synthetic method of 3 methyl, 3 butylene, 1 alcohol, catalyst and preparation method thereof |
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| CN107930686B (en) * | 2017-11-22 | 2020-09-08 | 山东玉皇化工有限公司 | Synthetic method of 3-methyl-3-butene-1-ol, catalyst and preparation method thereof |
| CN107961812A (en) * | 2017-11-24 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of preparation method of metal-modified ZSM-5 molecular sieve of self-supporting and its application in isoprene is synthesized |
| CN107961812B (en) * | 2017-11-24 | 2020-07-28 | 中国科学院长春应用化学研究所 | Preparation method of self-supporting metal modified ZSM-5 molecular sieve and application thereof in synthesis of isoprene |
| CN110420658A (en) * | 2019-08-08 | 2019-11-08 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the bifunctional catalyst with core-shell structure |
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