CN101798516B - Nano-base carrier synchronous multiple-effect cracking catalyst and preparation method thereof - Google Patents
Nano-base carrier synchronous multiple-effect cracking catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000005336 cracking Methods 0.000 title claims abstract description 31
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- -1 ethene diamine Chemical class 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 239000000571 coke Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 11
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFUAIAKLWWIPTC-UHFFFAOYSA-L magnesium;naphthalene-2-carboxylate Chemical group [Mg+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 OFUAIAKLWWIPTC-UHFFFAOYSA-L 0.000 claims abstract description 4
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- MQHWFIOJQSCFNM-UHFFFAOYSA-L Magnesium salicylate Chemical compound [Mg+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O MQHWFIOJQSCFNM-UHFFFAOYSA-L 0.000 claims abstract description 3
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229940072082 magnesium salicylate Drugs 0.000 claims abstract description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 15
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 14
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002114 nanocomposite Substances 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- WAKHLWOJMHVUJC-SQFISAMPSA-N (2z)-2-hydroxyimino-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(=N/O)/C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-SQFISAMPSA-N 0.000 claims description 8
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 8
- 150000002220 fluorenes Chemical class 0.000 claims description 8
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 241001272567 Hominoidea Species 0.000 claims description 7
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 7
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- HKMTVMBEALTRRR-UHFFFAOYSA-N Benzo[a]fluorene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4C3=CC=C21 HKMTVMBEALTRRR-UHFFFAOYSA-N 0.000 claims description 4
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005770 Eugenol Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 4
- 241000534944 Thia Species 0.000 claims description 4
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 4
- 229960002217 eugenol Drugs 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 150000002475 indoles Chemical class 0.000 claims description 4
- FHFHPENPORXWHG-UHFFFAOYSA-N magnesium;phenol Chemical compound [Mg].OC1=CC=CC=C1 FHFHPENPORXWHG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 4
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 claims description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 2
- 229910052749 magnesium Inorganic materials 0.000 abstract 2
- 239000011777 magnesium Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 30
- 150000003254 radicals Chemical class 0.000 description 23
- 239000002699 waste material Substances 0.000 description 20
- 238000004523 catalytic cracking Methods 0.000 description 15
- 238000007233 catalytic pyrolysis Methods 0.000 description 14
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- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 239000006259 organic additive Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 150000001336 alkenes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a nano-base carrier synchronous multiple-effect cracking catalyst and a preparation method thereof. Nanometer composite inorganic catalyst and additive are mixed to obtain nano-base carrier synchronous multiple-effect cracking catalyst; the inorganic catalyst comprises the components of nanometer SiO2 and Al2O3; the additive comprises as follows: nanometer composite inorganic catalyst surface treating agent which adopts coupling agent, the composition of radical initiator, chain terminator, antiscorching agent and antioxygen, and the additive generating freely flowing granular coke; the additive is selected from magnesium naphthenate, calcium naphthenate and ethene diamine tetraalkoxy alcohol which has high superficial area and contains metal solid, pyridine, calcium salicylate, magnesium salicylate, calcium phenate, magnesium phenate, vulcanizing calcium phenate, vulcanizing magnesium phenate and polyoxypropylene alcohol. Coupling agent is used to combine nanometer composite inorganic catalyst and multiple-effect additive composition to ensure that various kinds of required reactions simultaneously happen at the cracking position, so that the catalyst of the invention has high liquid yield and favorable oil quality, forms coke capable of freely flowing and has high utilization ratio.
Description
Technical field:
The invention belongs to useless heavy oil and waste plastics deep process technology field, be specifically related to a kind of energy and will give up heavy oil and waste plastics through catalytic pyrolysis, catalyst for cracking of the qualified vapour of output, diesel oil and preparation method thereof.
Background technology:
As the important component part of recycling economy, useless heavy oil and waste plastics are through catalytic pyrolysis, and the qualified vapour of output, diesel oil are important industry.
In this respect, many companies have carried out effective exploration, and obtain suitable achievement, adopt y-type zeolite molecular sieve and porcelain ball such as patent CN1597848A, the mixture of patent CN1350051A employing ZSM-5 molecular sieve with small crystal grains and inorganic oxide, rare-earth oxide, patent CN1683473A adopts alukalin and natural zeolite mixture, and CN1057408A adopts the modification silica-rich zeolite, a series of similar catalyst are still arranged, do not enumerate one by one at this.
In experimental study and concrete production process, we find these catalysis techniques, have several common problems to have to be solved:
＜1〉existing catalytic cracking catalyst, the light oils effective (productive rate 90%) such as catalysis used oil, and when cracking heavy waste oil, light oil productive rate low (average 50%-60%), coke yield high (average 35%-40%), remaining is dry gas.
Above situation is received light oil as the catalytic pyrolysis industry of main target for producing, can not be satisfactory.
＜2〉in fuel-displaced process, the considerable part oil product is black, though can decolour after filtration, still, filter loss is generally 5%-6%, simultaneously, has strengthened decolorizer expenditure cost, and the technical process benefit is reduced, and useless decolorizer also easily causes secondary pollution.
＜3〉catalytic pyrolysis produces sponge coke, be the chunk shape and stick in the still, during removing, need through drill-over, scrape, high-pressure water jet could remove fully, on the one hand, the removing workload is large, reduces work efficiency, raises the cost, on the other hand, coke through high-pressure water jet takes off has not had value, can only be as cheap fuel and coal multifuel combustion.
As the product of recycling economy, coke should obtain valuable utilization and be only reasonably.
For the first two problem, many mechanisms have proposed solution, such as patent CN1712495A, patent CN1560198A, patent CN1583960A, patent CN192802A, patent CN1448490A, patent US35006223, their common ground use surfactant, radical initiator, stopping of chain agent, antioxidant, and its Main Function is:
1. free radical initiation, catalyst spontaneous formation free radical under the thermal cracking condition, Effective Raise cracking conversion rate, thus improve the light oil productive rate.
2. contain free radical intermediate in the catalyst, produce alkyl diradical under heat condition, the living radical effect with useless heavy oil pyrolysis produces forms deactivated saturated hydrocarbons, improves liquid and receives.
3. antioxidant prevents further oxidation coking and reduces the output of easy oxyalkylene.
Verified, these materials truly have effect, can improve oil quality, reduce filter loss, but in use there is limitation in they: when catalytic pyrolysis, must have comparatively fast and stir, they just can be uniformly dispersed, play a significant role, and in actual production, it is impossible stirring fast.
Under industrial low rate mixing condition, they disperse irregular, can not play one's part to the full, and effect is also not obvious, only effect is arranged just when consumption is large, and is infeasible economically.
For the 3. problem, apparent solution is to form free flowable graininess coke, like this, reactor is easy to cleaning, and coke is easily collected, simultaneously, the graininess coke can be used as industrial chemicals and machined electrode uses, and added value improves, patent CN1954051A, patent CN1954048A discloses several effective additive combinations, similarly, and in use, they also need dispersed with stirring faster just effective, otherwise, will strengthen consumption, this is weak point.
The root that above three problems produce is that the additive dispersion is inhomogeneous, can't play a role synchronously, cause them not form a homogeneous phase with heavy waste oil or waste plastics fused mass, particularly catalytic cracking catalyst mostly is greatly solid, and specific area is little, free settling, cause catalytic activity to reduce, act on inhomogeneously, this is the major reason that the light oil productive rate is low, coke yield is high.
In the catalytic cracking catalyst composition, other additive mostly is greatly organic matter, their distributions in waste oil are inhomogeneous, between solid catalyst and the liquid catalyst, between solid catalyst and the waste oil, not even distribution, synchronously onset of catalyst, this is the bad major reason of effect.
In sum:
(a) present custom catalysts when catalytic pyrolysis, is only considered the cracking function usually, mostly do not cooperate free radical saturated with subtract Jiaozhuo usefulness, cause function singleness, the light oil productive rate is low, oxyalkylene content is high, goes out oil quality low, filter loss is larger.
(b) present catalyst, even minority has been considered the problems referred to above, but because catalyst for cracking is solid (soil, quartz sand etc.), other compositions of additives mostly is greatly liquid, has so just brought problem: the catalyst heterogeneity distributes very inhomogeneous in cracking stock, act on asynchronous, during reaction, some compositions are inactivation in advance, and some compositions to reaction finishes not yet to play a role, this unbalanced state causes reaction insufficient, imperfect, the W-response poor effect.
(c) therefore, at catalytic cracking reaction occur moment, if timely saturation of olefins and end chain reaction, just can the high-quality light oil of output and reduce coke yield, this is the optimum response state.At present, existing solid-stately have again liquid state, and the catalyst mixture of distribution disconnected from each other obviously can not meet the need.
(d) to reach optimum efficiency in (c), just need to be when the catalytic pyrolysis activated centre reacts, follow the reaction of olefin saturated and stopping of chain, that is to say, the reaction of the saturated and stopping of chain of catalytic cracking reaction and free radical occurs in same position, the best results of this catalytic reaction, this just need to combine catalytic cracking catalyst and other desired additives, forms a kind of firmly composition.
(e) solid-state inorganic matter catalyst and liquid state organics catalyst mutually between can not in conjunction with, effectively combine, need a bridge between them.Therefore, we introduce titanate coupling agent.
Coupling agent claims again surface conditioning agent, it can be two kinds of materials of different nature, and the effect by chemistry or physics combines, and it can combine inorganic matter and two kinds of materials of different nature of organic polymer closely, therefore, coupling agent be inorganic and the organic substance interface between bridge.
Because catalytic cracking catalyst mostly is greatly SiO
2, Al
2O
3Deng inorganic matter, they are hydrophilic polar substances (surface has all attracted water molecule layer), and organic additive mostly is greatly macromolecule organic, mostly belongs to hydrophobic apolar substance, therefore, lacks affinity between them.
With the surface of the above-mentioned inorganic matter of coupling agent treatment, make it become hydrophobicity by hydrophily, just can realize that inorganic matter is combined with organic interface.
We will combine catalytic cracking catalyst (solid-state, inorganic) and the additives (liquid, organic) such as free radical initiation and stopping of chain agent in following the present invention by titanate coupling agent, the composite catalyst that provides a kind of high activity, multiple reaction to occur synchronously, to reach optimum efficiency, improve liquid and receive, improve quality.
Summary of the invention:
The object of the present invention is to provide a kind of solid-liquid catalyst to organically combine, catalyst is combined good nano-base carrier synchronous multiple-effect cracking catalyst and preparation method thereof with heavy waste oil.
The object of the present invention is achieved like this, and the present invention adopts nanometer SiO
2With nanometer Al
2O
3As the catalytic cracking catalyst main body, its advantage is large, lightweight, the easy dispersion of specific area, and the while catalytic activity is higher, consumption reduces.
The present invention adopts titanate coupling agent to nanometer SiO
2With nanometer Al
2O
3The surface carry out preliminary treatment, the SiO after the processing
2And Al
2O
3Can combine veritably with other organic additive, and with heavy waste oil system good knitting.
The present invention adopts pretreated nanometer SiO
2With nanometer Al
2O
3, utilize the supersonic oscillations means to mix, make itself and multiple organic additive coupling, form a kind of well-set multiple-effect composite catalyst.
Particular content of the present invention is as follows:
(1) a kind of nano composite inorganic catalyst is solid catalyst, and as catalytic cracking catalyst, composition is nanometer SiO
2And Al
2O
3(10～900nm), compositely proportional is 50～80: 50～20;
Preferred proportion is: 60～70: 40～30;
Further preferred proportion is: 66: 34.
(2) a kind of nano composite inorganic catalyst surface inorganic agent, adopt coupling agent, it can be selected from: two (phosphorous acid two lauryls) network, four octyloxy titanium coupling agents, β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium coupling agent, a kind of in the triethanolamine titanate coupling agent;
Be preferably: two (phosphorous acid two lauryls) network, four octyloxy titanium coupling agents;
Consumption is: 2%～5% of solid catalyst quality;
Preferable amount is: 3% of solid catalyst quality.
(3) a kind of preparation method of nano composite inorganic catalyst colloidal sol: will be an amount of the coupling agent of (account for solid catalyst quality 2%～5%) be dissolved in 200
#In the solvent naphtha, stir the nanometer SiO of rear adding capacity
2With nanometer Al
2O
3, 50 ℃ of lower supersonic oscillations activation 10min, stand for standby use.
(4) a kind of raising light oil quality, reduce the additive of unsaturated olefin and coke yield: they are radical initiators, the stopping of chain agent, antiscorching, the composition of antioxidant, radical initiator wherein, the stopping of chain agent, antiscorching, antioxidant is existing commercially available prod, specifically---tetrahydronaphthalene, alpha-methyl-naphthalene, beta-methylnaphthalene, fluorenes, anthracene, luxuriant and rich with fragrance, benzfluorene, phenol, paracresol, indoles, tetrahydroquinoline, the thia fluorenes, thiophane, 2, the 5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, eugenol, styrenated phenol, DAM, acetoxime, dimethylglyoxime, α-benzoinoxime, triphenylphosphine, triphenyl phosphate, block polyether, the APES sulphonic acid ester, N-phenyl-αnaphthylamine, the sulfenic acids acid amides, azodiisobutyronitrile, several compositions in the carbon tetrachloride, these several compositions can arbitrary ratio make up, generally by being combined into more than 4 kinds or 4 kinds of said components, each composition weight degree summation is 100%.In these several compositions, wherein has a kind of tetrahydronaphthalene that is selected from least, alpha-methyl-naphthalene, beta-methylnaphthalene, fluorenes, anthracene, luxuriant and rich with fragrance, benzfluorene, wherein has a kind of phenol that is selected from least, paracresol, indoles, tetrahydroquinoline, the thia fluorenes, thiophane, 2, the 5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, eugenol, styrenated phenol, wherein has a kind of DAM that is selected from least, acetoxime, dimethylglyoxime, α-benzoinoxime, triphenylphosphine, wherein has a kind of triphenyl phosphate that is selected from least, block polyether, the APES sulphonic acid ester wherein has a kind of N-of being selected from phenyl-αnaphthylamine at least, the sulfenic acids acid amides, azodiisobutyronitrile, carbon tetrachloride.
Its consumption is: the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant and the mass ratio of organic catalyst are 1: 1;
Preferably: tetrahydroquinoline, 2, the composition of 6-di-tert-butyl cresols, α-benzoinoxime, triphenyl phosphate, N-phenyl-αnaphthylamine.
Preferred ingredient and weight percent content: tetrahydroquinoline 27%, 2,6-di-tert-butyl cresols 12%, α-benzoinoxime 25%, triphenyl phosphate 17%, N-phenyl-αnaphthylamine 19%;
Preferred ingredient and weight percent content: tetrahydronaphthalene 23%, paracresol 11%, DAM 17%, triphenylphosphine 21%, APES sulphonic acid ester 15%, carbon tetrachloride 13%;
Preferred ingredient and weight percent content: beta-methylnaphthalene 16%, acetoxime 21%, triphenyl phosphate 13%, styrenated phenol 18%, sulfenic acids acid amides 24%, azodiisobutyronitrile 8%;
(5) a kind of additive that produces free flowing granule shape coke: it is selected from---the composition of the ethylenediamine tetraacetic alcohol alcoxylates of magnesium naphthenate, calcium naphthenate, high surface containing metal solid, pyridine, calcium salicylate, magnesium salicylate, calcium phenoxide, phenol magnesium, sulfuration calcium phenoxide, sulfuration phenol magnesium, polyoxypropylene alcohol.
Its consumption is: account for 5%～20% of organic catalyst quality;
Preferably: calcium salt or the magnesium salts of alkalescence.
(6) a kind of method with the nano composite inorganic catalyst described in () and above-mentioned various organic additive coupling and refinement, homogenize: the additive in through coupling agent surface-treated nano composite inorganic catalyst colloidal sol (three) in the adding (four) and (five), use supersonic oscillations to mix 10min, make organic additive and organic catalyst be combined into nano-base carrier synchronous multiple-effect cracking catalyst colloidal sol.
When (seven) residual oil carried out conventional catalytic pyrolysis, parallel net reaction occured:
A, conventional catalytic cracking reaction can be described with radical chain reaction mechanism:
(1) chain causes
The hydrocarbon molecules homolysis of being heated generates free radical,
R
1H→R
2·+R
3·
(2) chain development
R
2·+R
1H→R
2H+R
1·
R
3·+R
1H→R
3H+R
1·
(3) free radical decomposes
Free radical resolves into olefin hydrocarbon molecules and new free radical, and this decomposition occurs on the β key position of that carbon atom with unpaired electron.For example:
C-C-C-C-C-C-C·→C-C-C-C-C·+C＝C
Therefore the dry gas yied in the conventional catalytic pyrolysis product is higher.
(4) chain termination
R·→R
1
Add synthetic active polymeric substance, can interact with unpaired electron, make free radical generation homolytic reaction, thereby reduce the generation of cracked gas.
The generation of B, coke is the comprehensive of heat scission reaction and condensation reaction, and its mechanism is:
(1) chain begins
R
1H→R·
(2) chain development
R·+O
2→ROO·
ROO·+RH→ROOH+R·
(3) asphalitine, coke form
Described asphaltic base is that asphalitine is sloughed H
+After material;
C, after adding the compound multiple-effect catalyst of nano based, react as follows:
(1) catalytic cracking reaction occurs fast:
R
1H→R
2·+R
3·
(2) under the effect of coupling multipurpose additive, free radical is saturated by moment, forms liquid saturated hydrocarbons:
R
1H→R
2·+R
3·→R
2+R
3
(3) the antioxygen antiscorching agent stops oxidation reaction to occur, and avoids forming coke.
Advantage of the present invention:
(1) catalyst particle size of the present invention is nanoscale, is the colloidal sol shape, and is scattered in heavy waste oil, contact area is large, reactivity is high, and consumption is few, through on probation, (the present invention is 140 ℃ in the oil outlet temperature reduction, prior art is 180 ℃), simultaneously, (the present invention is 380 ℃ to the reduction of cracking outlet temperature, prior art is 430 ℃), coke reduces.
(2) fuel-displaced quality improvement, filter loss reduces (the present invention is 3%, and prior art is 5%～6%).
(3) nano based catalyst amount few (the present invention is 0.02%, and the prior art consumption is 0.05%) because the nano based catalyst particle size is superfine, is significantly smaller than the catalyst such as carclazyte, quartz sand, has improved the coke quality.
(4) output free flowing granule shape coke of the present invention is easy to collect, and coke quality is high, can be used for processing carbon black and electrode, and added value improves.
(5) introducing of titanate coupling agent has reduced the oil product interfaces free energy, reduces heavy waste oil system viscosity, makes fuel-displaced speed improve that (the present invention is about 8～10h and finishes cracking, prior art 13h consuming time～15h).
(6) catalyst of the present invention is by the coupling agent combination, one end is the nanometer catalyst for cracking, the other end is radical initiator, stopping of chain agent, antioxidant etc., so that the moment of catalytic cracking reaction, unsaturated olefin is by saturated, alkane is in a liquid state, pyrogenetic reaction is prevented from, the fluid receipts thereby improve, (at present, cracking heavy waste oil liquid of the present invention receives 68%～71% to reduce coke yield, the prior art yield is 50%～60%, simultaneously, coke yield of the present invention reduces to 25%, and the prior art productive rate is 30%～40%).
(7) catalyst of the present invention only changes product and distributes, and does not change the quality index such as boiling range, density, hydrocarbon bunch composition, carbon residue of fluid product.
(8) in catalytic pyrolysis, use the present invention, easy and simple to handle, expense is cheap, liquid receive high, economic benefit is high.
(9) the present invention has dissimilar functional group, and the dissimilar free radical that produces in the balance heavy waste oil cracking process is had the effect that adapts, and effect is better than the single type chemicals.
(10) the present invention shortens the time of staying of distillate in tower, reduces the chance that second pyrolysis and hydrocarbon molecules further are condensed into coke.
(11) the present invention can be according to factors such as different feedstock properties, process conditions and product requirements, rationally adjusts prescription, obtaining optimum efficiency, thereby has larger flexibility and wider applicability.
The present invention mainly can be used for the recovery cracking of heavy waste oil, waste plastics.
The specific embodiment:
The present invention is described in detail below in conjunction with embodiment:
Embodiment 1:
1. take by weighing the nanometer SiO of 1 weight portion
2And Al
2O
3(wherein: SiO accounts for 66%, Al to mixture
2O
3Account for 34%) for subsequent use.
2. two (phosphorous acid two laurate) network, the four octyloxy titanium coupling agents that take by weighing 0.03 weight portion are dissolved in 1 weight portion 200
#In the solvent naphtha, stir.
3. 1. step is taken by weighing thing adding step and 2. obtain in the thing, be warming up to 50 ℃, supersonic oscillations activation 10min obtains nano composite inorganic catalyst colloidal sol (2.03 weight portion).
4. prepare the composition of 1 weight portion radical initiator, stopping of chain agent, antiscorching, antioxidant (wherein: tetrahydroquinoline 27%, 2,6-di-tert-butyl cresols 12%, α-benzoinoxime 25%, triphenyl phosphate 17%, N-phenyl-αnaphthylamine 19%), and stir.
5. take by weighing 0.1 weight portion bigcatkin willow acid calcium for subsequent use.
6. 4. step is obtained thing and step and 5. obtain thing and add step and 3. obtain in the thing, under the normal temperature, use supersonic oscillations to mix 10min, make abundant combination, obtain multiple-effect catalyst for cracking colloidal sol (about 3.13 weight portions), code name K-1.
Embodiment 2:
1. take by weighing the nanometer SiO of 1 weight portion
2And Al
2O
3Mixture (wherein: SiO
2Account for 72%, Al
2O
3Account for 28%) for subsequent use.
2. take by weighing the β of 0.03 weight portion-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium coupling agent and be dissolved in 1 weight portion 200
#In the solvent naphtha, stir.
3. 1. step is taken by weighing thing adding step and 2. obtain in the thing, be warming up to 50 ℃, supersonic oscillations activation 10min obtains nano composite inorganic catalyst colloidal sol (2.03 weight portion).
4. prepare the composition (wherein: tetrahydronaphthalene 23%, paracresol 11%, DAM 17%, triphenylphosphine 21%, APES sulphonic acid ester 15%, carbon tetrachloride 13%) of 1 weight portion radical initiator, stopping of chain agent, antiscorching, antioxidant, and stir.
5. take by weighing 0.1 weight portion magnesium naphthenate for subsequent use.
6. 4. step is obtained thing and step and 5. obtain thing and add step and 3. obtain in the thing, under the normal temperature, use supersonic oscillations to mix 10min, make abundant combination, obtain multiple-effect catalyst for cracking colloidal sol (about 3.13 weight portions), code name K-2.
Embodiment 3:
1. take by weighing the nanometer SiO of 1 weight portion
2And Al
2O
3Mixture (wherein: SiO
2Account for 85%, Al
2O
3Account for 15%) for subsequent use.
2. the triethanolamine titanate coupling agent that takes by weighing 0.03 weight portion is dissolved in 1 weight portion 200
#In the solvent naphtha, stir.
3. 1. step is taken by weighing thing adding step and 2. obtain in the thing, be warming up to 50 ℃, supersonic oscillations activation 10min obtains nano composite inorganic catalyst colloidal sol (2.03 weight portion).
4. prepare the composition (wherein: beta-methylnaphthalene 16%, acetoxime 21%, triphenyl phosphate 13%, styrenated phenol 18%, sulfenic acids acid amides 24%, azodiisobutyronitrile 8%) of 1 weight portion radical initiator, stopping of chain agent, antiscorching, antioxidant, and stir.
5. take by weighing 0.1 weight portion sulfuration calcium phenoxide for subsequent use.
6. 4. step is obtained thing and step and 5. obtain thing and add step and 3. obtain in the thing, under the normal temperature, use supersonic oscillations to mix 10min, make abundant combination, obtain multiple-effect catalyst for cracking colloidal sol (about 3.13 weight portions), code name K-3.
Embodiment 4:
This example is that the nano based bearer synchronization multiple-effect composite catalyst colloidal sol that embodiments of the invention 1 make is used for the catalytic pyrolysis result of the test that residual oil is reclaimed in heavy oil storage device bottom.
Table 1: catalytically cracked material (recovery residual oil) character
Table 2: FCC tests result
| Project | K-1 | Typical catalyst |
| Material name | Reclaim residual oil | Reclaim residual oil |
| Catalyst addition μ g/g | 200 | 500 |
| Reactor pressure MPa | 0.1 | 0.1 |
| Catalytic pyrolysis temperature ℃ | 150～375 | 220～430 |
| Liquid yield m% | 68.1 | 52.3 |
As shown in Table 1, reclaim residual oil resin and asphalt content high, carbon residue is up to 19.2%, table 2 result of the test shows, is under the condition of 200 μ g/g in the nano based bearer synchronization multiple-effect composite catalyst addition that embodiments of the invention 1 make, and goes out liquid temp lower, liquid yield is high, reaches 68.1%.(annotate: typical catalyst adopts commercially available aluminium oxide, silica).
Embodiment 5
This example is the catalytic pyrolysis result of the test that the nano based bearer synchronization multiple-effect composite catalyst colloidal sol that makes of embodiments of the invention 3 is used for the catalytic cracking waste-plastic fused mass.
Table 3: FCC tests result
| Project | K-3 | Typical catalyst |
| Material name | The waste plastics fused mass | The waste plastics fused mass |
| Catalyst addition μ g/g | 300 | 600 |
| Reactor pressure MPa | 0.1 | 0.1 |
| Catalytic pyrolysis temperature ℃ | 270～360 | 300～350 |
| Liquid yield m% | 75 | 67 |
As shown in Table 3, the present invention is used for the catalytic cracking waste-plastic fused mass, and boiling range broadens, and liquid is received obviously and improved.(annotate: typical catalyst adopts commercially available aluminium oxide, silica; The waste plastics fused mass is taken from the fused mass of the waste plastics at garbage reclamation station).
Claims (7)
1. nano-base carrier synchronous multiple-effect cracking catalyst is characterized in that: with the catalyst for cracking colloidal sol that nano composite inorganic catalyst and additive are mixed to get, and described nano composite inorganic catalyst, constituent is nanometer SiO
2, and Al
2O
3SiO
2, and Al
2O
3Weight ratio be 50～80: 50～20; Described additive is: 1) nano composite inorganic catalyst surface inorganic agent, adopt coupling agent, and its consumption is: coupling agent accounts for 2%～5% of organic catalyst quality; Coupling agent is two (phosphorous acid two lauryls) network, four octyloxy titanium coupling agents, a kind of in β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium coupling agents and the triethanolamine titanate coupling agent;
2) composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, its consumption is: the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant and the mass ratio of organic catalyst are 1: 1; Radical initiator, the stopping of chain agent, antiscorching, the composition of antioxidant is by tetrahydronaphthalene, alpha-methyl-naphthalene, beta-methylnaphthalene, fluorenes, anthracene, luxuriant and rich with fragrance, benzfluorene, phenol, paracresol, indoles, tetrahydroquinoline, the thia fluorenes, thiophane, 2, the 5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, eugenol, DAM, acetoxime, dimethylglyoxime, α-benzoinoxime, triphenylphosphine, triphenyl phosphate, styrenated phenol, the sulfenic acids acid amides, block polyether, the APES sulphonic acid ester, N-phenyl-αnaphthylamine, azodiisobutyronitrile, in the carbon tetrachloride more than 4 kinds or 4 kinds;
3) additive of generation free flowing granule shape coke: additive wherein has a kind of ethylenediamine tetraacetic alcohol alcoxylates that is selected from magnesium naphthenate, calcium naphthenate, pyridine, calcium salicylate, magnesium salicylate, calcium phenoxide, phenol magnesium, sulfuration calcium phenoxide, sulfuration phenol magnesium, polyoxypropylene alcohol at least, and its consumption is: account for 5%～20% of organic catalyst quality.
2. a kind of nano-base carrier synchronous multiple-effect cracking catalyst according to claim 1 is characterized in that: nanometer SiO in the nano composite inorganic catalyst
2, and Al
2O
3Weight ratio is 60～70: 40～30.
3. a kind of nano-base carrier synchronous multiple-effect cracking catalyst according to claim 2, it is characterized in that: in the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, have a kind of tetrahydronaphthalene, alpha-methyl-naphthalene, beta-methylnaphthalene, fluorenes, anthracene, phenanthrene, benzfluorene of being selected from least
In the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, have a kind of phenol, paracresol, indoles, tetrahydroquinoline, thia fluorenes, thiophane, 2 of being selected from least, 5-di-tert-butylphenol, 2,6-di-tert-butyl cresols, eugenol, styrenated phenol
In the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, have a kind of DAM, acetoxime, dimethylglyoxime, α-benzoinoxime, triphenylphosphine of being selected from least,
In the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, have a kind of triphenyl phosphate, block polyether, APES sulphonic acid ester of being selected from least,
In the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant, have a kind of N-of being selected from phenyl-αnaphthylamine, sulfenic acids acid amides, azodiisobutyronitrile, carbon tetrachloride at least.
4. a kind of nano-base carrier synchronous multiple-effect cracking catalyst according to claim 3, it is characterized in that: the composite formula of radical initiator, stopping of chain agent, antiscorching, antioxidant is tetrahydroquinoline 27%, 2,6-di-tert-butyl cresols 12%, α-benzoinoxime 25%, triphenyl phosphate 17%, N-phenyl-αnaphthylamine 19% by weight percentage.
5. a kind of nano-base carrier synchronous multiple-effect cracking catalyst according to claim 3 is characterized in that: the composite formula of radical initiator, stopping of chain agent, antiscorching, antioxidant is tetrahydronaphthalene 23%, paracresol 11%, DAM 17%, triphenylphosphine 21%, APES sulphonic acid ester 15%, carbon tetrachloride 13% by weight percentage.
6. a kind of nano-base carrier synchronous multiple-effect cracking catalyst according to claim 3 is characterized in that: the composite formula of radical initiator, stopping of chain agent, antiscorching, antioxidant is beta-methylnaphthalene 16%, acetoxime 21%, triphenyl phosphate 13%, styrenated phenol 18%, sulfenic acids acid amides 21%, azodiisobutyronitrile 8% by weight percentage.
7. according to claim 1, the preparation method of 2,3,4,5 or 6 described a kind of nano-base carrier synchronous multiple-effect cracking catalysts, comprise the steps:
1), an amount of titanate coupling agent is dissolved in the solvent naphtha nanometer SiO of the rear adding capacity that stirs
2With nanometer Al
2O
3, obtain nano composite inorganic catalyst colloidal sol through the supersonic oscillations activation;
2), in nano composite inorganic catalyst colloidal sol, add the composition of radical initiator, stopping of chain agent, antiscorching, antioxidant and the additive of generation free flowing granule shape coke, the use supersonic oscillations are mixed, and make additive and organic catalyst fully be combined into nano-base carrier synchronous multiple-effect cracking catalyst colloidal sol.
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|---|---|---|---|---|
| CN1740093A (en) * | 2005-07-28 | 2006-03-01 | 华中师范大学 | Zinc-containing alkane cracking catalyst and its prepn and application in the synthesis of single-wall carbon nanotube |
| CN1743420A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN1916116A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN1935380A (en) * | 2006-09-30 | 2007-03-28 | 中国科学院广州能源研究所 | Method for preparing integral biomass gasified tarcracking catalyst |
| WO2007082629A1 (en) * | 2005-12-22 | 2007-07-26 | Albemarle Netherlands Bv | Novel cracking catalytic compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743420A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN1740093A (en) * | 2005-07-28 | 2006-03-01 | 华中师范大学 | Zinc-containing alkane cracking catalyst and its prepn and application in the synthesis of single-wall carbon nanotube |
| CN1916116A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| WO2007082629A1 (en) * | 2005-12-22 | 2007-07-26 | Albemarle Netherlands Bv | Novel cracking catalytic compositions |
| CN1935380A (en) * | 2006-09-30 | 2007-03-28 | 中国科学院广州能源研究所 | Method for preparing integral biomass gasified tarcracking catalyst |
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