CN103638964B - A kind of preparation method of molecular sieve catalyst, its preparation method and double olefin compound - Google Patents
A kind of preparation method of molecular sieve catalyst, its preparation method and double olefin compound Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 209
- 239000003054 catalyst Substances 0.000 title claims abstract description 200
- -1 olefin compound Chemical class 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 157
- 238000009833 condensation Methods 0.000 claims abstract description 55
- 230000005494 condensation Effects 0.000 claims abstract description 55
- 239000000969 carrier Substances 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 21
- 241000269350 Anura Species 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 57
- 238000006297 dehydration reaction Methods 0.000 claims description 47
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 238000011068 load Methods 0.000 claims description 25
- 238000005342 ion exchange Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000012018 catalyst precursor Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 34
- 238000006482 condensation reaction Methods 0.000 abstract description 17
- 239000011973 solid acid Substances 0.000 abstract description 8
- 230000003197 catalytic Effects 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 191
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 70
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 46
- 238000004817 gas chromatography Methods 0.000 description 32
- 239000007788 liquid Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical group ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 240000008528 Hevea brasiliensis Species 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N Silver nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229920001194 natural rubber Polymers 0.000 description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N Bismuth(III) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910052904 quartz Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 229910017544 NdCl3 Inorganic materials 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N MeOtBu Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K Neodymium(III) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 2
- 201000002574 conversion disease Diseases 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WFJQGQNVERCLOQ-AATRIKPKSA-N (3E)-2,5-dimethylhexa-1,3-diene Chemical compound CC(C)\C=C\C(C)=C WFJQGQNVERCLOQ-AATRIKPKSA-N 0.000 description 1
- KFQWHHUZLDASRR-UHFFFAOYSA-N 3,4-dimethylpenta-1,3-diene Chemical compound CC(C)=C(C)C=C KFQWHHUZLDASRR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101710039852 METAP1 Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
Abstract
The present invention provides a kind of molecular sieve catalyst, and including active component and carrier, described active component is one or more in X-type molecular sieve, Y type molecular sieve, ZSM 5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.The molecular sieve catalyst that the present invention provides belongs to solid acid catalyst, and the ratio in molecular sieve catalyst B-acid active center and L acid active center is up to 1.76, and B-acid active center is in the majority, can improve the selectivity of condensation reaction.Described molecular sieve catalyst has higher specific surface area so that molecular sieve catalyst has higher activity.Described molecular sieve catalyst is used in the reaction that catalytic olefine condensation one-step method prepares double olefin compound, it is possible to ensure that condensation reaction has higher conversion ratio and higher selectivity simultaneously.
Description
Technical field
The present invention relates to catalyst field, particularly relate to a kind of molecular sieve catalyst, its preparation method and diolefin chemical combination
The preparation method of thing.
Background technology
Rubber has purposes and greatly demand widely in industrial and agricultural production, transportation, national defence and daily life
Amount.Rubber can be divided into natural rubber and synthetic rubber, and natural rubber yields poorly, price high, can not meet the demand of production, because of
This, people, on the basis of natural rubber structure, have developed synthetic rubber, and synthetic rubber is the most with low cost, and have excellent
Good thermostability, tolerance to cold and anticorrosive property, but in some properties, synthetic rubber can not substitute natural rubber completely,
As poor in elastomeric drawing effect, tearing toughness and mechanical performance are the most all inferior to natural rubber.Isoprene rubber
Structure and character are closest to natural rubber, and its resistance to water and electrical insulating property have been even more than natural rubber.Therefore, research isoamyl rubber
Development Rubber Industry is had great importance by glue.
Isoprene rubber is polymerized by isoprene monomer, along with isoprene rubber industrial expansion, the need to isoprene
The amount of asking will be bigger.Therefore, the preparation of isoprene monomer is the important foundation of development isoprene rubber industry.
In prior art, isoprene is mainly prepared by olefine aldehyde condensation reaction.Olefine aldehyde condensation reaction can be divided into two-step method
And one-step method.Two-step method be formaldehyde and isobutene. under the conditions of 70～100 DEG C, first reaction generation 4,4-dimethyl-1,3-dioxy
Six alkane, then 4,4-dimethyl-1,3-dioxy six alkane is cracked to form isoprene at 250～280 DEG C；One-step method be formaldehyde and
Isobutene. Direct Dehydration condensation under the conditions of 200～300 DEG C generates isoprene.Owing to one-step method flow process is short, separate simple, secondary
Reaction is few, and product quality is high, so, this technique has good development prospect.
During one-step method prepares isoprene, efficient catalyst can improve conversion ratio and the selection of reaction
Property.As United States Patent (USP) US3253051 discloses a kind of Cr, the metallic compound such as Mn, Ag, Fe, Mg and phosphorus compound are formed
Active component, described active component obtains catalyst after load, this catalyst is used for being catalyzed the dehydration of formaldehyde and isobutene.
Condensation course, one-step method prepares isoprene.But catalyst catalytic performance disclosed in this patent is relatively low, conversion ratio (in terms of formaldehyde)
Being up to 70%, selectivity is up to 75%, and can not ensure that condensation reaction has higher conversion ratio and higher choosing simultaneously
Selecting property, when reaching higher selectivity, conversion ratio (in terms of formaldehyde) only has 22%.
Summary of the invention
Present invention aim at providing a kind of molecular sieve catalyst, its preparation method and the preparation side of double olefin compound
Method, the molecular sieve catalyst that the present invention provides can ensure higher when olefine aldehyde condensation one-step method diolefin compounds simultaneously
Conversion ratio and higher selectivity.
The present invention provides a kind of molecular sieve catalyst, including active component and carrier；
Described active component is in X-type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve
One or more.
Preferably, described active component is 0.5～15:1 with the mass ratio of carrier.
Preferably, described carrier is Ludox or aluminium-containing substance.
Preferably, auxiliary agent is also included；
Described auxiliary agent is the compound containing Na, compound containing K, the compound of Nd, the oxide of Mo, MgO, CaO, BaO,
Al2O3、Bi2O3, the oxide of Mn, the oxide of Sb, the oxide of Ce, ZnO, ZrO2、CuO、Fe2O3, compound containing Re,
B2O3、SiO2, the compound containing P, one or more in the compound containing S and Ag simple substance.
The present invention provides the preparation method of a kind of molecular sieve catalyst, comprises the following steps:
A) active component and carrier are mixed, carry out the supported of active component, obtain catalyst precursor, described activity
Composition is one or more in X-type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve；
B) by described step A) catalyst precursor that obtains carries out the first roasting after drying, obtains catalyst intermediate；
C) by described step B) in the catalyst intermediate that obtains mix with ion-exchanger and carry out ion-exchange reactions,
To 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 step A) in the temperature of load be 20～95 DEG C, the time of load is 0.5～8 hour.
Preferably, described step B) in the first sintering temperature be 300～380 DEG C；
Described step B) in the first roasting time be 0.5～8 hour.
Preferably, described step D) in the second sintering temperature be 450～550 DEG C；
Described step D) in the second roasting time be 1～10 hour.
The present invention provides the preparation method of a kind of diolefin compounds, comprises the following steps:
The monoolefine compounds having the carbonyl containing compound of structure shown in formula (1) with have formula (2) structure is being urged
Carry out dehydration condensation under the effect of agent, obtain diolefin compounds；
Described catalyst be the molecular sieve catalyst described in Claims 1 to 4 any one or claim 5～8 any
The molecular sieve catalyst that one described preparation method obtains；
Wherein, R1、R2、R3、R4Independent selected from hydrogen, alkyl and aromatic radical.
Preferably, described R1、R2、R3、R4Independent selected from the straight chained alkyl that hydrogen, carbon number are 1～8, carbon number it is
The branched alkyl of 1～8, phenyl, carbon number are the substituted phenyl of straight chained alkyl of 1～8 or side chain that carbon number is 1～8
The substituted phenyl of alkyl.
Preferably, described monoolefine compounds is 3～10:1 with the mol ratio containing carbonyl complex.
Preferably, the amount of the quality of described catalyst and the material of the carbonyl-containing compound with structure shown in formula (I)
Than being (1～3) g:1mol.
Preferably, described dehydration condensation temperature is 250～350 DEG C.
The present invention provides a kind of molecular sieve catalyst, and including active component and carrier, described active component is molecular sieve, institute
Stating molecular sieve is one or more in X-type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.
The molecular sieve catalyst that the present invention provides belongs to solid acid catalyst, and solid acid catalyst has two kinds of active center: Bronsted
Acid (abbreviation B-acid) active center and Lewis acid (abbreviation L acid) active center, prepare diene in described olefine aldehyde condensation one-step method
In the course of reaction of hydrocarbon compound, the most more beneficially diolefin the generations in B-acid active center, the molecular sieve that the present invention provides
The ratio in catalyst B-acid active center and L acid active center is up to 1.76, and B-acid active center is in the majority, and therefore, the present invention provides
Molecular sieve catalyst can improve the selectivity of condensation reaction.Molecular sieve catalyst has high specific surface area, and the present invention provides
Molecular sieve catalyst specific surface area up to 358m2/ g, higher specific surface area makes molecular sieve catalyst have higher work
Property.Described molecular sieve catalyst is used in the reaction that catalytic olefine condensation one-step method prepares double olefin compound, it is possible to
Time ensure that condensation reaction has higher conversion ratio and higher selectivity.
Described auxiliary agent be described auxiliary agent be the compound containing Na, compound containing K, the compound of Nd, the oxide of Mo,
MgO、CaO、BaO、Al2O3、Bi2O3, the oxide of Mn, the oxide of Sb, the oxide of Ce, ZnO, ZrO2、CuO、Fe2O3, contain
The compound of Re, B2O3、SiO2, the compound containing P, one or more in the compound containing S and Ag simple substance.
Present invention also offers the preparation method of a kind of molecular sieve catalyst, active component and carrier by load and are roasted
Burning and i.e. can get described molecular sieve catalyst, the method that the present invention provides is simple, it is easy to operation, is beneficial to carry out heavy industrialization
Produce.
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.
Detailed description of the invention
The invention provides a kind of molecular sieve catalyst, including active component and carrier；
Described active component is in X-type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve
One or more.
The molecular sieve catalyst that the present invention provides belongs to solid acid catalyst, and solid acid catalyst has two kinds of active center:
Bronsted acid (abbreviation B-acid) active center and Lewis acid (abbreviation L acid) active center, in described olefine aldehyde condensation one-step method
Preparing in the course of reaction of diolefin compounds, the most more beneficially diolefin the generations in B-acid active center, the present invention provides
The ratio in molecular sieve catalyst B-acid active center and L acid active center up to 1.76, B-acid active center is in the majority, therefore, this
The molecular sieve catalyst of bright offer can improve the selectivity of condensation reaction.Molecular sieve catalyst has high specific surface area, this
The molecular sieve catalyst specific surface area that invention provides is up to 358m2/ g, higher specific surface area makes molecular sieve catalyst have
Higher activity.
The molecular sieve catalyst that the present invention provides includes that active component, described active component are X-type molecular sieve, Y type molecule
One or more in sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.In the present invention, described active component is preferred
For the one or several in Na-ZSM-5 molecular sieve, Na-X molecular sieve, Na-Y molecular sieve, Na-beta-molecular sieve and Na-SAPO molecular sieve
Kind, one or more in more preferably Na-ZSM-5 molecular sieve, Na-X molecular sieve and Na-Y molecular sieve, most preferably Na-
ZSM-5 molecular sieve.The present invention does not has special restriction to the source of described molecular sieve, can use the commercially available business of described molecular sieve
Product, it is possible to use the technical scheme preparing molecular sieve well known to those skilled in the art to prepare voluntarily.
The molecular sieve catalyst that the present invention provides includes carrier, and the present invention does not has special limit to the kind of described carrier
System, it is possible to load above-mentioned active component.In the present invention, described carrier is preferably Ludox or aluminium-containing substance, more preferably
For one or more in boehmite, Alumina gel, Ludox and titanium aluminium glue, most preferably boehmite, Alumina gel and
One or more in Ludox, the most preferably Ludox.
The present invention is to the specific surface area of described boehmite, Na2The content of O and using method do not have special restriction,
Described active component can be loaded.In the present invention, the specific surface area of described boehmite is preferably 250～380m2/
G, more preferably 280～360m2/g；Described Na2The content of O is preferably 0～0.1g, more preferably 0～0.05g；The present invention is preferred
Adding deionized water in boehmite, described deionized water is preferably 1:1 with the mass ratio of boehmite.
The present invention does not has special requirement to the solid masses concentration in described Alumina gel, solid mean diameter and pH value,
Described active component can be loaded.In the present invention, the solid masses concentration in described Alumina gel is preferably 20～30%,
More preferably 28%；Solid mean diameter in described Alumina gel is preferably 15 μm～35 μm, more preferably 20 μm～30 μm；Institute
The pH value stating Alumina gel is preferably 4～6, more preferably 5.
The present invention is to SiO in described Ludox2The mass concentration of mass concentration, mean diameter and sodium ion the most special
Restriction, it is possible to load described active component.In the present invention, SiO in described Ludox2Mass concentration be preferably 30
～50%, more preferably 40%；SiO in described Ludox2Mean diameter be preferably 15 μm～30 μm, more preferably 20 μm；Institute
State the mass concentration of sodium ion in Ludox and be preferably 0～0.1%, more preferably 0～0.05%.
In the present invention, described active component is preferably 0.5～15:1 with the mass ratio of carrier, more preferably 0.8～10:
1, most preferably 1:1.
The molecular sieve catalyst that the present invention provides the most also includes auxiliary agent, and described auxiliary agent is preferably the compound containing Na, containing K
Compound, the compound of Nd, the oxide of Mo, MgO, CaO, BaO, Al2O3、Bi2O3, the oxide of Mn, the oxide of Sb,
The oxide of Ce, ZnO, ZrO2、CuO、Fe2O3, the compound containing Re, B2O3、SiO2, the compound containing P, the compound containing S and
One or more in Ag simple substance, more preferably HPO3、Al2O3、Sb2O3、MoO3、Ag、Fe2O3, CuO and NdCl3In one or
Several, most preferably HPO3、Fe2O3With one or more in Ag.The present invention does not has special limit to the source of described auxiliary agent
System, can obtain described auxiliary agent after overload, dry, ion exchange and roasting.In the present invention, described auxiliary agent is next
Source be preferably the oxide of Na, the oxide of K, MgO, CaO, the compound containing Mo, the compound containing Ba, compound containing Al,
Compound containing Bi, the compound containing Mn, the oxide of Sb, the compound containing Ce, ZnO, the compound containing Zr, the chemical combination containing Fe
Thing, the compound containing Cu, the compound containing Re, the compound containing B, SiO2, the compound containing P, the compound containing S, containing Nd's
One or more in compound and the compound containing Ag, more preferably H3PO4、P2O5、Al(OH)3、Sb2O3、MoO3、AgNO3、
Fe2O3、CuSO4And NdCl3·6H2One or more in O, most preferably H3PO4、Fe2O3And AgNO3In one or more.
In the present invention, described auxiliary agent is 0.01～1:1 with the mass ratio of active component, preferably 0.03～0.5:1, more
It is preferably 0.04～0.1:1.
The invention provides the preparation method of a kind of molecular sieve catalyst, comprise the following steps:
A) active component and carrier being mixed, carry out the load of active component, obtain catalyst precursor, described activity becomes
It is divided into one or more in X-type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve；
B) by described step A) catalyst precursor that obtains carries out the first roasting after drying, obtains catalyst intermediate；
C) by described step B) in the catalyst intermediate that obtains mix with ion-exchanger and carry out ion-exchange reactions,
To 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.
Active component and carrier are mixed by the present invention, carry out the load of active component, obtain catalyst precursor.Described work
Property composition is consistent with the active component in technique scheme and carrier with carrier, does not repeats them here.The present invention is to described work
The charging sequence of property composition and carrier does not has special restriction, it is possible to active component and carrier are mixed.
The present invention does not has special restriction to the load device of described mixed solution Yu carrier, uses those skilled in the art
Known to load device carry out loading.In the present invention, described mixed solution is preferably slurry with the load device of carrier
Device.
In the present invention, the temperature of described active component load is preferably 20～95 DEG C, more preferably 40～93 DEG C, optimum
Elect 90 DEG C as；The time of described active component load is preferably 0.5～8 hour, and more preferably 1～6 hour, most preferably 2 is little
Time.
After obtaining described catalyst precursor, described catalyst precursor is carried out the first roasting by the present invention after drying,
To catalyst intermediate.The present invention does not has special restriction to the drying means of described catalyst precursor, uses this area skill
The technical scheme being dried known to art personnel is dried.In the present invention, described catalyst precursor is dry preferred
For being evaporated；The baking temperature of described catalyst precursor is preferably 100～200 DEG C, more preferably 130～180 DEG C, most preferably
150℃。
Complete described catalyst precursor be dried after, the dried catalyst precursor obtained is carried out by the present invention
First roasting, obtains catalyst intermediate.The present invention does not has special restriction to the device of the first described roasting, uses ability
The device carrying out roasting known to field technique personnel.In the present invention, the device of described first roasting is preferably Muffle furnace；
The temperature of described first roasting is preferably 300～380 DEG C, more preferably 330～360 DEG C, most preferably 340～350 DEG C；Described
The time of the first roasting is preferably 0.5～8 hour, more preferably 1～6 hour, most preferably 4～5 hours.
After obtaining catalyst intermediate, described catalyst intermediate is mixed with ion-exchanger and carries out ion friendship by the present invention
Change reaction, obtain ion-exchange reactions product.
The catalyst intermediate obtained preferably is pulverized by the present invention, by the catalyst intermediate granule obtained and ion
Exchanger mixing carries out ion-exchange reactions.The present invention does not has special restriction to the described device for pulverizing, and uses ability
Reducing mechanism known to field technique personnel carries out pulverizing.In the present invention, described pulverizing rear catalyst midbody particle
Particle diameter is preferably 20～80 mesh, more preferably 25～75 mesh.
After completing the pulverizing of catalyst intermediate, the catalyst intermediate granule obtained is mixed by the present invention with ion-exchanger
Conjunction carries out ion-exchange reactions, obtains ion-exchange reactions product.In the present invention, described ion-exchanger is preferably ammonium chloride
Or hydrochloric acid, more preferably ammonium chloride solution or hydrochloric acid, most preferably ammonium chloride solution.In the present invention, described ammonium chloride solution
Mass concentration be preferably 0.5%～3%, more preferably 0.8%～2%, most preferably 1%；The present invention is to described ammonium chloride solution
Consumption does not has special restriction, it is possible to complete described ion-exchange reactions；The present invention to described ion-exchange reactions time
Number does not has special restriction, uses ion-exchange reactions number of times well known to those skilled in the art.In the present invention, ion
The number of times of exchange reaction is preferably 2～5 times, more preferably 4 times.
After completing described ion-exchange reactions, the ion-exchange reactions product obtained is carried out the second roasting by the present invention,
To molecular sieve catalyst.After completing described ion-exchange reactions, the ion-exchange reactions product obtained preferably is carried out by the present invention
Solid-liquid separation, washes laggard row the second roasting by the solid obtained, obtains molecular sieve catalyst.The present invention is to described solid-liquid separation
Method there is no special restriction, use the technical scheme of solid-liquid separation well known to those skilled in the art to carry out solid-liquid separation i.e.
Can.In the present invention, the method for described solid-liquid separation is preferably and filters；In the present invention, described washing times be preferably 1～
6 times, more preferably 2～5 times, most preferably 3 times
After completing described washing, the solid that washing obtains preferably is dried by the present invention, is carried out by dried solid
Second roasting, obtains molecular sieve catalyst.The present invention does not has special restriction to the drying means of solid after described washing, adopts
It is dried with drying means well known to those skilled in the art.In the present invention, after described washing solid be dried
Method is preferably evaporated；After described washing, the temperature being dried of solid is preferably 100～150 DEG C, more preferably 110～120 DEG C,
Most preferably 125 DEG C.
Completing the dried of the solid after described washing, dried solid is carried out the second roasting by the present invention, is divided
Sub-sieve catalyst.The present invention does not has special restriction to the device of the second described roasting, uses those skilled in the art to know
The device carrying out roasting carry out roasting.In the present invention, described second calciner is preferably Muffle furnace.Described second
Sintering temperature is preferably 450～550 DEG C, more preferably 480～530 DEG C, most preferably 490～510 DEG C；During described second roasting
Between be preferably 1～10 hour, more preferably 3～8 hours, most preferably 4～5 hours.
The present invention also provides for the preparation method of a kind of diolefin compounds, comprises the following steps:
The monoolefine compounds having the carbonyl containing compound of structure shown in formula (1) with have formula (2) structure is being urged
Carry out dehydration condensation under the effect of agent, obtain diolefin compounds；
Described catalyst is the molecular sieve catalyst described in technique scheme；
Wherein, R1、R2、R3、R4Independent selected from hydrogen, alkyl and aromatic radical.
In the present invention, there is the carbonyl containing compound of structure shown in formula (1) and there is the monoene hydro carbons of formula (2) structure
Compound carries out condensation reaction, during the reaction of described condensation reaction as shown in formula (A):
Wherein, cat represents the molecular sieve catalyst that the present invention provides；R1、R2、R3、R4With the R described in technique scheme1、
R2、R3、R4Unanimously, at this to substituent R1、R2、R3、R4Repeat no more；R4' compare R4A few-H.
The present invention will have the carbonyl containing compound of structure shown in formula (1) and has the monoene hydrocarbon of formula (2) structure
Thing carries out dehydration condensation under the effect of catalyst, obtains diolefin compounds.
In the present invention, described carbonyl containing compound has a structure shown in formula (1):
Wherein, R1、R2Independent selected from hydrogen, alkyl and aromatic radical, preferably independently selected from hydrogen, carbon number be 1～8
The substituted phenyl of straight chained alkyl or the carbon that branched alkyl that straight chained alkyl, carbon number are 1～8, phenyl, carbon number are 1～8
Atomic number is the substituted phenyl of branched alkyl of 1～8, more preferably independently selected from the straight chained alkyl that hydrogen, carbon number are 1～8
Or the branched alkyl that carbon number is 1～8, the most independent selected from hydrogen, methyl or isopropyl.Work as R1For H, R2During for H, institute
State that to have the carbonyl containing compound of formula (1) structure be formaldehyde；Work as R1For H, R2During for methyl, described in have formula (1) structure containing carbonyl
Based compound is acetaldehyde；Work as R1For H, R2During for isopropyl, described in have the carbonyl containing compound of formula (1) structure be isobutylaldehyde.
The present invention has the source of the carbonyl containing compound of structure shown in formula (1) do not have special restriction to described, permissible
Employing has the commercial goods of the carbonyl containing compound of structure shown in formula (1), it is possible to according to system well known to those skilled in the art
Shown in formula of getting everything ready (1), the technical scheme of the carbonyl containing compound of structure is prepared voluntarily.
In the present invention, described monoolefine compounds has a structure shown in formula (2):
Wherein, R3、R4Independent selected from hydrogen, alkyl and aromatic radical, preferably independently selected from hydrogen, carbon number be 1～8
The substituted phenyl of straight chained alkyl or the carbon that branched alkyl that straight chained alkyl, carbon number are 1～8, phenyl, carbon number are 1～8
Atomic number be the substituted phenyl of branched alkyl of 1～8, more preferably carbon number be 1～8 straight chained alkyl, carbon number be 1
～the branched alkyl of 8 or phenyl, most preferably methyl, phenyl or isopropyl.Concrete, as described R3For methyl, R4For methyl
Time, described in have the monoolefine of formula (2) structure be isobutene.；As described R3For methyl, R4During for phenyl, described in have formula (2) knot
The monoolefine of structure is α-methyl styrene；As described R3For methyl, R4During for isopropyl, described in there is the monoolefine of formula (2) structure
For 2,3-dimethyl-1-butylene.
The present invention has the source of the monoolefine compounds of structure shown in formula (2) do not have special restriction to described, can
To use, there is the commercial goods of the monoolefine compounds of structure shown in formula (2), it is possible to know according to those skilled in the art
Preparation there is the technical scheme of the monoolefine compounds of structure shown in formula (2) prepare voluntarily.In the present invention, have described in
The preparation method of the monoolefine compounds of formula (2) structure preferably includes following steps:
Carry out cracking reaction by having the ether compound of structure shown in formula (3), obtain having the list of structure shown in formula (2)
Alkenes compounds；
Wherein, R3、R4Independently selected from hydrogen, alkyl and aromatic radical.
The present invention carries out cracking reaction by having the ether compound of structure shown in formula (3), obtains having knot shown in formula (2)
The monoolefine compounds of structure.In the present invention, the R in described formula (3)3And R4With the R in formula described in technique scheme (2)3
And R4Unanimously, do not repeat them here.Concrete, when R3 is methyl, and R4 is methyl, described in there is the ethers of formula (3) structure
Compound is methyl tertiary butyl ether(MTBE).
The present invention cracks the monoene hydro carbons of structure shown in formula (2) to the ether compound of structure shown in described formula (3)
The condition of compound does not has special restriction, uses the condition of cracking reaction well known to those skilled in the art.At this
In bright, the temperature of described cracking reaction is preferably 250～350 DEG C, more preferably 280～230 DEG C, most preferably 300 DEG C；Described
The cracking reaction time is preferably 0.1～2 hour, more preferably 0.5～1.5 hour, most preferably 1 hour.
In the present invention, the monoolefine compounds described in formula (2) structure has structure shown in formula (1) with described
Mol ratio containing carbonyl complex is preferably 3～10:1, more preferably 4～6:1, most preferably 5.5:1.Described catalyst
Quality has preferably (1～the 3) g:1mol of the ratio of the amount of the material containing carbonyl complex of structure shown in formula (1) with described,
More preferably (1.5～2.5) g:1mol, most preferably 2g:1mol.
In the present invention, described dehydration condensation temperature is preferably 250～350 DEG C, more preferably 280～230 DEG C,
It is preferably 300 DEG C；The described dehydration condensation time is preferably 0.1～2 hour, more preferably 0.5～1.5 hour, most preferably
It it 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,
It is preferably 0.4 second.
The present invention does not has special restriction to the device of described dehydration condensation, it is preferred to use have structure shown in Fig. 1
Fixed-bed reactor, Fig. 1 is the structural representation of fixed bed used in the embodiment of the present invention, and wherein 1 is the first material
Feed pump, 2 is the second material feed pump, and 3 is the first valve, and 4 is the second valve, and 5 is reaction tube, and 6 is condenser, and 7 is gas-liquid
Separating and carbonyl containing compound retracting device, 8 is gas chromatograph.
In the present invention, described fixed-bed reactor includes the first material feed pump 1, going out of described first product pump 1
Mouth is connected with the import of the first valve 3 by the first material pipe (not marking in figure), and the outlet of described first valve 3 is with described
The charging aperture of reaction tube 5 is connected, and described first valve 3 is for the flow of regulation the first material, and the present invention is to the first described thing
The material of pipe material and size do not have special restriction, it is possible to transport material.The present invention for the ease of the conveying of material,
In embodiments of the invention, the fixed bed reactors that the present invention uses can be provided with the between the first valve 3 and reaction tube 5
Two material pipes (not marking in figure) and mixed material pipeline (not marking in figure), the charging aperture of described second material pipe and institute
The discharging opening stating the first valve 3 is connected；The charging aperture phase of the discharging opening of described second material pipe and described mixed material pipeline
Even, the discharging opening of described mixed material pipeline is connected with the charging aperture of described reaction tube, and described mixed material pipeline is used for the
After one material and the mixing of the second material, it is delivered to reaction tube 5.
In the present invention, described fixed bed reactors include the second material feed pump 2, going out of described second material feed pump
Mouth is connected with the import of the second valve 4 by 3 material pipeline (not marking in figure), and the outlet of described second valve 4 is with described
The charging aperture of reaction tube 5 is connected, and described second valve 4 is for the flow of regulation the second material, and the present invention is to the 3rd described thing
The material of pipe material and size do not have special restriction, it is possible to transport material.The present invention for the ease of the conveying of material,
In embodiments of the invention, the fixed bed reactors that the present invention uses can be provided with the between the second valve 4 and reaction tube 5
4 materials pipeline (not marking in figure) and mixed material pipeline (not marking in figure), the charging aperture of described 4 materials pipeline and institute
The discharging opening stating the second valve 4 is connected；The charging aperture phase of the discharging opening of described 4 materials pipeline and described mixed material pipeline
Even, described mixed material pipeline, after the first material and the second material being mixed, is delivered to reaction tube 5.
In the present invention, described first material is for having the carbonyl containing compound of structure shown in formula (1), and the second material is tool
There is the monoolefine compounds of formula (2) structure and/or there is the ether compound of structure shown in formula (3)；Or described first thing
Material is for having the monoolefine compounds of formula (2) structure and/or having the ether compound of structure, the second material shown in formula (3)
For having the carbonyl containing compound of structure shown in formula (1), the present invention does not has special restriction to this.
In the present invention, described fixed bed reactors include reaction tube 5, the discharging opening of described reaction tube 5 and described condensation
The charging aperture of device 6 is connected, and is placed with the molecular sieve catalyst described in technique scheme, catalysis conveying in described reaction tube 5
The first material and the second material that come carry out dehydration condensation, obtain double olefin compound.The present invention is to described reaction tube 5
Material and size do not have special restriction, it is possible to provide place, in the present invention, described reaction tube 5 for condensation reaction
It is preferably dimensioned to be Φ 10mm～Φ 20mm.
In the present invention, described fixed bed reactors include condenser 6, the discharging opening of described condenser 6 and described gas-liquid
Separating and the charging aperture of carbonyl containing compound retracting device 7 is connected, described condenser 6 is for the gaseous state that will obtain in reaction tube 5
Product is condensed into liquid, and beneficially product separates with excess raw material.The present invention is to the kind of described condenser 6 and source
There is no special restriction, it is possible to reach the effect of condensation.
In the present invention, described fixed bed reactors include gas-liquid separation and carbonyl containing compound retracting device 7, described gas
Liquid separates and the discharging opening of formaldehyde retracting device 7 is connected with the charging aperture of described gas chromatograph 8, described gas-liquid separation and formaldehyde
Retracting device 7 is for separating the gas-liquid mixture that condenser 6 obtains, and enters unreacted formaldehyde carbonyl containing compound
Row reclaims.The present invention does not has special restriction to kind and the source of described gas-liquid separation and carbonyl containing compound retracting device 7,
It is capable of the recovery of gas-liquid separation and carbonyl containing compound.
In the present invention, described fixed bed reactors include that gas chromatograph 8, described gas chromatograph 8 are used for reacting product
The detection of thing.The present invention does not has special restriction to the model of described gas chromatograph, it is possible to detection product.
Below in conjunction with above-mentioned fixed-bed reactor, illustrate the preparation method of the diolefin that the present invention provides:
By the described monoolefine compounds with formula (2) structure and/or have the ether compound of structure shown in formula (3)
Pass sequentially through first material feed pump the 1, first material pipe, the first valve 3 and the second material pipe and be delivered to mixed material pipe
In road, with there is structure shown in formula (1) mix containing carbonyl complex after, be delivered in reaction tube 5；
To have structure shown in formula (1) passes sequentially through the second material feed pump 2,3 material pipe containing carbonyl complex
Road, the second valve 4 and 4 materials pipeline are delivered to mixed material pipeline, with the monoolefine compounds with formula (2) structure
And/or after there is the ether compound mixing of structure shown in formula (3), then it is delivered in reaction tube 5；
Mixed material enters to contact with pipe inner catalyst in reaction tube 5 and carries out condensation reaction, is mixed after completion of the reaction
Gas, is passed through described mixed gas in condenser 6 and condenses, obtain gas-liquid mixture, led to by the gas-liquid mixture obtained
Enter in gas-liquid separation and carbonyl containing compound retracting device 7 and carry out gas-liquid separation, obtain liquid-phase reaction product, and to unreacted
Carbonyl containing compound reclaims, and is passed through in gas chromatograph 8 by described liquid-phase reaction product and detects.
The invention provides a kind of molecular sieve catalyst, including active component and carrier, described active component is X-type molecule
One or more in sieve, Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve and SAPO molecular sieve.The molecular sieve that the present invention provides
Catalyst belongs to solid acid catalyst, and solid acid catalyst has two kinds of active center: Bronsted acid (abbreviation B-acid) active center
With Lewis acid (abbreviation L acid) active center, prepare the course of reaction of diolefin compounds in described olefine aldehyde condensation one-step method
In, the most more beneficially diolefin the generations in B-acid active center, the molecular sieve catalyst B-acid active center of present invention offer and L
The ratio at acid activity center is up to 1.76, and B-acid active center is in the majority, and therefore, the molecular sieve catalyst that the present invention provides can improve contracting
Close the selectivity of reaction.Molecular sieve catalyst has high specific surface area, the molecular sieve catalyst specific surface that the present invention provides
Long-pending up to 358m2/ g, higher specific surface area makes molecular sieve catalyst have higher activity.
The invention provides the preparation method of a kind of molecular sieve catalyst, i.e. available described by load and ion exchange
Molecular sieve catalyst, the method that the present invention provides is simple, it is easy to operation, is beneficial to carry out large-scale industrial production.
In order to further illustrate the present invention, a kind of molecular sieve catalyst of the present invention being provided below in conjunction with embodiment, its
The preparation method of preparation method and double olefin compound is described in detail, but can not be understood as scope
Restriction.
Embodiment 1
By 50g Na-ZSM-5 molecular sieve, 1g Ca3(PO4)2With 50g Ludox add 500ml round-bottomed flask in, its
In, SiO in Ludox2For 40wt%, mean diameter is 20 microns, Na+Concentration is less than 0.1wt%；
Round-bottomed flask is connected in slurry device, carries out the load of active component, make molecular sieve mix all with Ludox
Even, load temperature is 90 DEG C, and load time is 2 hours；
After completing the load of active component, temperature is promoted to 150 DEG C, evaporating water, the catalyst precursor that will obtain
Proceeding in Muffle furnace roasting at 350 DEG C makes active component in catalyst fix after 4 hours, obtain catalyst intermediate；
The catalyst intermediate obtained is pulverized, obtains catalyst intermediate granule, collect 20～80 mesh granules, by quality
The ammonium chloride solution addition catalyst intermediate granule of concentration 1% carries out ion-exchange reactions 4 times, obtains reaction solution, will be anti-
Answer solution to filter, the solid being filtrated to get is washed 3 times, temperature is promoted to 125 DEG C the solid after washing is done
Dry, evaporating water, drier solid is proceeded in Muffle furnace roasting 4 hours at 500 DEG C, obtain molecular sieve catalyst.
It is proportional that the present invention determines molecular sieve catalyst total acid content, specific surface area and the acid activity central. set obtained, its
In, the total acid content of molecular sieve catalyst is 2.71mmol/g, and specific surface area is 311m2/ g, acid activity central. set is proportional for B
Acid: L acid=1.55:1.
Embodiment 2
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 25g
Na-X molecular sieve replaces the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 3
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 750g
Na-Y molecular sieve replaces the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 4
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses Na-β to divide
Son sieve replaces the Na-ZSM-5 molecular sieve in embodiment 1, uses 20 DEG C and loads active component.
Embodiment 5
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses SAPO to divide
Son sieve replaces the Na-ZSM-5 molecular sieve in embodiment 1, uses 95 DEG C and loads active component.
Embodiment 6
In the fixed bed shown in molecular sieve catalyst load map 1 that embodiment 1 is obtained, pass sequentially through the first product pump,
First valve and mixed material transfer pipeline are passed through isobutene. in reaction tube；Pass sequentially through the second product pump, the second valve and
Mixed material transfer pipeline is passed through formaldehyde in reaction tube, and molecular sieve catalyst quality is 2g with the ratio of the amount of the material of formaldehyde:
1mol, isobutene. is 5.5:1 with the mol ratio of formaldehyde, and reaction temperature is 300 DEG C, in the condition that gas-solid contact time is 0.4 second
Lower reaction 60 minutes, obtains admixture of gas, is delivered in condenser condense by the admixture of gas obtained, obtains gas-liquid
Mixture, is passed through the gas-liquid mixture obtained in gas-liquid separation and carbonyl containing compound retracting device and gas and liquid is carried out
Separate, obtain the double olefin compound of liquid phase, and unreacted gas phase carbonyl containing compound is reclaimed.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 1 institute
Showing, table 1 is the experimental result that embodiment 6～10 obtains.
Embodiment 7
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses 1g embodiment 2
The molecular sieve catalyst obtained replaces the 2g molecular sieve catalyst used in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 1 institute
Showing, table 1 is the experimental result that embodiment 6～10 obtains.
Embodiment 8
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses 3g embodiment 3
The molecular sieve catalyst obtained replaces the 2g molecular sieve catalyst used in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 1 institute
Showing, table 1 is the experimental result that embodiment 6～10 obtains.
Embodiment 9
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 4 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6,.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 1 institute
Showing, table 1 is the experimental result that embodiment 6～10 obtains.
Embodiment 10
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 5 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6,.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 1 institute
Showing, table 1 is the experimental result that the embodiment of the present invention 6～10 obtains.
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, and the catalyst formaldehyde obtained and isobutene. take off
The reaction selectivity (in terms of formaldehyde) of water condensation reaction can reach 75.2%, and conversion ratio (in terms of formaldehyde) can reach
87.1%, when reaction selectivity (in terms of formaldehyde) is the highest, conversion ratio (in terms of 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, its
In, SiO in Ludox2For 40wt%, mean diameter is 20 microns, Na+Concentration is less than 0.1wt%；
Round-bottomed flask is connected in slurry device, carries out the load of active component, make molecular sieve mix all with Ludox
Even, load temperature is 90 DEG C, and load time is 2 hours；
After completing the load of active component, temperature is promoted to 150 DEG C, evaporating water, the catalyst precursor that will obtain
Proceeding in Muffle furnace roasting at 350 DEG C makes active component in catalyst fix after 4 hours, obtain catalyst intermediate；
The catalyst intermediate obtained is pulverized, obtains catalyst intermediate granule, collect 20～80 mesh granules, by quality
The ammonium chloride solution addition catalyst intermediate granule of concentration 1% carries out ion-exchange reactions 4 times, obtains reaction solution, will be anti-
Answer solution to filter, the solid being filtrated to get is washed 3 times, temperature is promoted to 125 DEG C the solid after washing is done
Dry, evaporating water, drier solid is proceeded in Muffle furnace roasting 4 hours at 500 DEG C, obtain molecular sieve catalyst.
It is proportional that the present invention determines molecular sieve catalyst total acid content, specific surface area and the acid activity central. set obtained, its
In, the total acid content of molecular sieve catalyst is 2.83mmol/g, and specific surface area is 358m2/ g, acid activity central. set is proportional for B
Acid: L acid=1.76:1.
Embodiment 12
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g
P2O5Replace the 2g phosphoric acid in embodiment 11, use and active component was loaded in 0.5 hour.Embodiment 13
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g Al
(OH)3Replace the 2g phosphoric acid in embodiment 11, use and active component was loaded in 8 hours.
Embodiment 14
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 0.5g
Sb2O3Replace the 2g phosphoric acid in embodiment 11, use 300 DEG C and described catalyst precursor is carried out roasting.
Embodiment 15
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 50g
MoO3Replace the 2g phosphoric acid in embodiment 11, use 380 DEG C and described catalyst precursor is carried out roasting.
Embodiment 16
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g
AgNO3Replace the 2g phosphoric acid in embodiment 11, to described catalyst precursor roasting 0.5 hour.
Embodiment 17
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g
Fe2O3Replace the 2g phosphoric acid in embodiment 11, to described catalyst precursor roasting 8 hours.Embodiment 18
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g
CuSO4Replace the 2g phosphoric acid in embodiment 11, use 450 DEG C and catalyst intermediate is carried out roasting.
Embodiment 19
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 2g
NdCl3·6H2O replaces the 2g phosphoric acid in embodiment 11, uses 550 DEG C and catalyst intermediate is carried out roasting.
Embodiment 20
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 11 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 21
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 12 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 22
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 13 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 23
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 14 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 24
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 15 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 25
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 16 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 26
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 17 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 27
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 18 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that embodiment 20～28 obtains.
Embodiment 28
The technical scheme using embodiment 6 obtains double olefin compound, and except for the difference that, the present embodiment uses embodiment 19 to obtain
To molecular sieve catalyst replace the molecular sieve catalyst that uses in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 2 institute
Showing, table 2 is the experimental result that the embodiment of the present invention 20～28 obtains.
The experimental result that table 2 embodiment of the present invention 20～28 obtains
As can be seen from Table 2, the auxiliary agent added is different, the molecular sieve catalyst catalysis formaldehyde obtained and isobutene. dehydration
The reaction selectivity (in terms of formaldehyde) of condensation reaction can reach 73.7%, and conversion ratio (in terms of formaldehyde) can reach
77.8%, when reaction selectivity (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 77.8%.
Embodiment 29
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses the salt of 5%
Acid solution replaced the ammonium chloride solution of 1% in embodiment 1, to described catalyst intermediate roasting 1 hour.
Embodiment 30
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 29 obtain replaces the molecular sieve catalyst used in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 3 institute
Showing, table 3 is the experimental result that the embodiment of the present invention 30 obtains.
The experimental result that table 3 embodiment of the present invention 30 obtains
As can be seen from Table 3, after ion-exchanger is changed to the hydrochloric acid solution of 5%, obtain molecular sieve catalyst catalysis formaldehyde
Being 74.8% with the reaction selectivity (in terms of methanol) of isobutene. dehydrating condensation, the conversion ratio (in terms of methanol) of reaction is 67.4%,
Illustrate that the molecular sieve catalyst that the present invention provides can ensure higher conversion ratio and selectivity simultaneously.
Embodiment 31
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses plan thin
Diaspore replaced the Ludox in embodiment 11, to described catalyst intermediate roasting 10 hours.
Embodiment 32
The technical scheme using embodiment 11 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses aluminum molten
Glue replaces the Ludox in embodiment 11.
Embodiment 33
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 31 obtain replaces the molecular sieve catalyst used in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 4 institute
Showing, table 4 is the experimental result that embodiment 33～34 obtains.
Embodiment 34
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 32 obtain replaces the molecular sieve catalyst used in embodiment 6.
The double olefin compound of the liquid phase obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment
The double olefin compound obtained is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 4 institute
Showing, table 4 is the experimental result that the embodiment of the present invention 33～34 obtains.
The experimental result that table 4 embodiment of the present invention 33～34 obtains
As can be seen from Table 4, the carrier used is different, obtains molecular sieve catalyst catalysis formaldehyde and isobutene. dehydration contracting
Closing reaction, selectivity (in terms of formaldehyde) can reach 82.0%, and conversion ratio (in terms of formaldehyde) can reach 71.8%, when instead
When answering selectivity (in terms of formaldehyde) the highest, conversion ratio (in terms of formaldehyde) can reach 71.8%.
Embodiment 35
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses acetaldehyde generation
For the formaldehyde in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is 2-methyl-1,3-pentylene；
The present invention has investigated acetaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 5 institute
Showing, table 5 is the experimental result that embodiment 35～36 obtains.
Embodiment 36
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses isobutylaldehyde
Replace the formaldehyde in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is 2,5-dimethyl-1,3-hexadiene；
The present invention has investigated isobutylaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 5
Shown in, table 5 is the experimental result that the embodiment of the present invention 35～36 obtains.
The experimental result that table 5 embodiment of the present invention 35～36 obtains
As can be seen from Table 5, different aldehyde compounds is taked to react as reactant, the yield of reaction, selection
Property and conversion ratio difference, selectivity (in terms of formaldehyde) can reach 78.4%, and conversion ratio (in terms of formaldehyde) can reach
63.0%, when reaction selectivity (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 63.0%.
Embodiment 37
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses Alpha-Methyl
Styrene replaces the isobutene. in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is 2-phenyl-1,3-butadiene；
The present invention has investigated formaldehyde and the yield of α-methyl styrene dehydration condensation, selectivity and conversion ratio, result
As shown in table 6, table 6 is the experimental result that embodiment 37～39 obtains.
Embodiment 38
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses 2,3-bis-
Methyl isophthalic acid-butylene replaces the isobutene. in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is 3,4-dimethyl-1,3-pentadiene；
The present invention has investigated formaldehyde and the yield of α-methyl styrene dehydration condensation, selectivity and conversion ratio, result
As shown in table 6, table 6 is the experimental result that embodiment 37～39 obtains.
Embodiment 39
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses Alpha-Methyl
Styrene replaces the isobutene. in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is 2-phenyl-1,3-butadiene；
The present invention has investigated formaldehyde and the yield of α-methyl styrene dehydration condensation, selectivity and conversion ratio, result
As shown in table 6, table 6 is the experimental result that the embodiment of the present invention 37～39 obtains.
The experimental result that table 6 embodiment of the present invention 37～39 obtains
As can be seen from Table 6, different alkene (ether) compounds is used to react as reactant, the yield of reaction,
Selectivity and conversion ratio difference, selectivity (in terms of formaldehyde) can reach 76.4%, and conversion ratio (in terms of formaldehyde) is the highest can
Reaching 53.6%, when reaction selectivity (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 51.4%.
Embodiment 40
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses Φ 20mm
Lab scale fluid bed replace the fixed bed in embodiment 11.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 7 institute
Showing, table 7 is the experimental result that the embodiment of the present invention 40 obtains.
The experimental result that table 7 embodiment of the present invention 40 obtains
As can be seen from Table 7, use fluid bed as reaction unit, the reaction choosing of formaldehyde and isobutene. dehydration condensation
Selecting property (in terms of formaldehyde) is 62.5%, and conversion ratio (in terms of formaldehyde) is 55.0%.
Embodiment 41
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 10g
Na-ZSM-5 molecular sieve replaces the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 42
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 25g
Na-ZSM-5 molecular sieve replaces the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 43
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment uses 100g
Na-ZSM-5 molecular sieve replaces the 50g Na-ZSM-5 molecular sieve in embodiment 1.
Embodiment 44
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 41 prepare replaces the molecular sieve catalyst in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 8 institute
Showing, table 8 is the experimental result that embodiment 44～46 obtains.
Embodiment 45
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 42 prepare replaces the molecular sieve catalyst in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 8 institute
Showing, table 8 is the experimental result that embodiment 44～46 obtains.
Embodiment 46
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 43 prepare replaces the molecular sieve catalyst in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 8 institute
Showing, table 8 is the experimental result that the embodiment of the present invention 44～46 obtains.
The experimental result that table 8 embodiment of the present invention 44～46 obtains
As can be seen from Table 8, different catalyst active component content, the yield of reaction, selectivity and conversion ratio are used
Difference, selectivity (in terms of formaldehyde) can reach 75.4%, and conversion ratio (in terms of formaldehyde) can reach 61.3%, when instead
When answering selectivity (in terms of formaldehyde) the highest, conversion ratio (in terms of formaldehyde) can reach 47.8%.
Embodiment 47～49
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses gas-liquid to connect
Touch time 0.2s, 0.8s and 1.0s and replace the gas-liquid contact time 0.4s in embodiment 11 respectively.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 9 institute
Showing, table 9 is the experimental result that the embodiment of the present invention 47～49 obtains.
The experimental result that table 9 embodiment of the present invention 47～49 obtains
As can be seen from Table 9, using different gas-solid contact times, the yield of reaction, selectivity and conversion ratio are the poorest
Different, selectivity (in terms of formaldehyde) can reach 70.6%, and conversion ratio (in terms of formaldehyde) can reach 60.2%, works as selecting response
When property (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 53.4%.
Embodiment 50～52
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses reaction temperature
Spend 250 DEG C, 280 DEG C and 350 DEG C and replace the reaction temperature 300 DEG C in embodiment 6 respectively.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 10
Shown in, table 10 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 of employing is different, the yield of reaction, selectivity and conversion ratio difference,
Selectivity (in terms of formaldehyde) can reach 77.4%, and conversion ratio (in terms of formaldehyde) can reach 59.0%, works as reaction selectivity
When (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 47.8%.
Embodiment 53～55
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses isobutene.
It is mol ratio 5.5:1 that 3:1,4:1 and 10:1 replace the isobutene. in embodiment 11 and formaldehyde respectively with the mol ratio of formaldehyde.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 11
Shown in, table 11 is the experimental result that the embodiment of the present invention 53～55 obtains.
The experimental result that table 11 embodiment of the present invention 53～55 obtains
As can be seen from Table 11, the formaldehyde of employing is different with the mol ratio of isobutene., the yield of reaction, selectivity and conversion
Rate difference, selectivity (in terms of formaldehyde) can reach 84.2%, and conversion ratio (in terms of formaldehyde) can reach 63.3%, when
When reaction selectivity (in terms of formaldehyde) is the highest, conversion ratio (in terms of formaldehyde) can reach 42.2%.
Embodiment 56
The technical scheme using embodiment 1 prepares molecular sieve catalyst, and except for the difference that, the present embodiment is by embodiment 1
In catalyst preparation process equal proportion amplify 10 times.
Embodiment 57
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 56 obtain replaces the molecular sieve catalyst in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 12
Shown in, table 12 is the experimental result that the embodiment of the present invention 57 obtains.
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, selectivity and the conversion ratio of reaction are the highest,
Selectivity (in terms of formaldehyde) is 69.5%, and conversion ratio (in terms of formaldehyde) is 56.8%.Embodiment 58
The technical scheme using embodiment 6 prepares double olefin compound, the double olefin compound that the present invention will obtain
Carrying out gas chromatography determination, result shows, the double olefin compound that the present embodiment obtains is isoprene.
After reaction terminates, the present invention, to molecular sieve catalyst roasting 50 minutes at 500 DEG C, is passed through sky in roasting process
Gas, air velocity is 20L/hr, carries out the regeneration of molecular sieve catalyst.It is cooled to experimental temperature after regeneration and proceeds first
Aldehyde and the condensation reaction of isobutene..Obtain the life assessment to molecular sieve catalyst, as in figure 2 it is shown, Fig. 2 is the embodiment of the present invention
Catalyst regeneration life test figure in 58.Wherein, curve 1 is for reaction selectivity (in terms of formaldehyde) over time；Curve 2 is
Reaction conversion ratio (in terms of formaldehyde) is over time；Curve 3 be reaction yield (in terms of formaldehyde) over time.By scheming
2 it can be seen that catalyst favorable regeneration effect, and after regeneration, the activity of catalyst has obtained bigger recovery.
Embodiment 59
The technical scheme using embodiment 1 prepares molecular sieve catalyst, except for the difference that, uses industry in the present embodiment
Level raw material replaces the reagent grade materials in embodiment 1.
Embodiment 60
The technical scheme using embodiment 6 prepares double olefin compound, and except for the difference that, the present embodiment uses embodiment
The molecular sieve catalyst that 59 obtain replaces the molecular sieve catalyst used in embodiment 6.
The double olefin compound obtained is carried out gas chromatography determination by the present invention, and result shows, the present embodiment obtains
Double olefin compound is isoprene；
The present invention has investigated formaldehyde and the yield of isobutene. dehydration condensation, selectivity and conversion ratio, result such as table 13
Shown in, table 13 is the experimental result that the embodiment of the present invention 59 obtains.
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 industrial raw material prepares, the selectivity of reaction are used
Higher with conversion ratio, selectivity (in terms of formaldehyde) is 70.3%, and conversion ratio (in terms of formaldehyde) is 57.4%.
Meanwhile, in experiment, we have carried out the amplification test of fixed bed and fluid bed to partial catalyst in the present invention, real
Test result to differ with pilot run less than 2%.
As can be seen from the above embodiments, the molecular sieve catalyst catalysis activity and selectivity that the present invention provides is higher, then
Raw effective, preparation process is simple.The molecular sieve catalyst using industrial raw material to prepare still has higher activity.
Described molecular sieve catalyst is used for catalytic olefine condensation one-step method and prepares the reaction of diolefin compounds so that condensation reaction
There is higher conversion ratio and higher selectivity simultaneously.After catalyst preparation process equal proportion is amplified 10 times, condensation reaction
Conversion ratio and selectivity higher.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (3)
1. a preparation method for diolefin compounds, comprises the following steps:
To there is the carbonyl containing compound of structure shown in formula (1) and there is the monoolefine compounds of formula (2) structure at catalyst
Effect under carry out dehydration condensation, obtain diolefin compounds；
Described monoolefine compounds is 3～10:1 with the mol ratio containing carbonyl complex；
The quality of described catalyst and the amount with the material of the carbonyl-containing compound of structure shown in formula (1) compare for (1～3) g:
1mol；
Described catalyst is the molecular sieve catalyst prepared by the following method；
The preparation method of described molecular sieve catalyst, comprises the following steps:
A) active component and carrier being mixed, carry out the load of active component, obtain catalyst precursor, described active component is
One or more in Na-X type molecular sieve, Na-Y type molecular sieve and SAPO molecular sieve, described carrier is aluminium-containing substance；
B) by described step A) catalyst precursor that obtains carries out the first roasting after drying, obtains catalyst intermediate；
C) by described step B) in the catalyst intermediate that obtains mix with ion-exchanger and carry out ion-exchange reactions, obtain from
Sub-exchange reaction product；
D) by described step C) the ion-exchange reactions product that obtains carries out the second roasting and obtains molecular sieve catalyst；
Wherein, R1、R2、R3、R4Independent selected from hydrogen, alkyl and aromatic radical.
Preparation method the most according to claim 1, it is characterised in that described R1、R2、R3、R4Independent selected from hydrogen, carbon atom
Branched alkyl that straight chained alkyl that number is 1～8, carbon number are 1～8, phenyl, carbon number be 1～8 straight chained alkyl replace
Phenyl or the substituted phenyl of branched alkyl that carbon number is 1～8.
Preparation method the most according to claim 1, it is characterised in that described dehydration condensation temperature is 250～350
℃。
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