CN105709817B - Isomerization dewaxing catalyst and preparation method thereof - Google Patents
Isomerization dewaxing catalyst and preparation method thereof Download PDFInfo
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- CN105709817B CN105709817B CN201410716641.7A CN201410716641A CN105709817B CN 105709817 B CN105709817 B CN 105709817B CN 201410716641 A CN201410716641 A CN 201410716641A CN 105709817 B CN105709817 B CN 105709817B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 59
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 239000005416 organic matter Substances 0.000 claims abstract description 20
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 229920002472 Starch Polymers 0.000 claims description 19
- 239000008107 starch Substances 0.000 claims description 19
- 235000019698 starch Nutrition 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- 229940099112 cornstarch Drugs 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims 1
- 235000002678 Ipomoea batatas Nutrition 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 229920001592 potato starch Polymers 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
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- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
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- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- -1 carbonium ion Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The invention discloses a kind of isomerization dewaxing catalyst and preparation method thereof.This method is that the MTT type molecular sieves for loading hydrogenation active component are embedded in organic matter, and then the precursor with high temperature resistant indifferent oxide is well mixed, and through shaping, dries and is calcined, obtain isomerization dewaxing catalyst.During catalyst of the present invention is especially suitable for the isomerization dewaxing of lube cut.Compared with prior art, due in catalyst molecular sieve dosage be greatly lowered, not only Catalyst Production cost significantly declines, it is thus also avoided that the discharge of intractable waste water in sieve synthesis procedure, and with purpose product yield it is high low with pour point the characteristics of.
Description
Technical field
The present invention relates to a kind of isomerization dewaxing catalyst and preparation method thereof.The isomerization dewaxing catalyst is used for waxy feeds
During oily isomerization dewaxing, particularly suitable for producing the process of top-grade lubricating oil base oil.
Background technology
Heretofore described waxy feeds oil mainly includes diesel oil, AGO, VGO, white oil, hydrocracking tail oil and lubrication
Oil distillate etc..Waxy feeds oil, is especially originating from the heavy distillate of paraffinic base crude oil and contains more wax, and condensation point is higher,
Low temperature flow is poor, during storage, transport and use, can make oily retrogradation, or even solidification with the reduction of environment temperature, so as to
Blocking the fuel feeding of petroleum pipeline and interruption engine makes engine breakdown.At present solve content of wax heavy distillate because of solidification and
The method of caused various problems is a lot, wherein main means are dewaxings, including solvent dewaxing, catalytic dewaxing and isomery take off
Wax.
Solvent dewaxing is exactly to be removed using wax solubility property in a solvent, is that solvent selection is tired the shortcomings that this method
It is difficult, waste substantial amounts of organic solvent, it is harmful and pollute that environment, equipment investment and operating cost be high and product quality by
Raw material limits.Catalytic dewaxing is exactly to use the catalyst with shape-selective cracking function, makes the wax component in cut that selection occur and urges
Change cracking, generate the hydro carbons compared with small molecule, such as United States Patent (USP) USP.4247388 and USP.4659311 are exactly de- using catalysis
The method of wax removes the wax in lubricating oil, is due to the macromolecular compound conversion substantial amounts of high value the shortcomings that this method
For the small-molecule substance of low value, make that base oil yield is low, viscosity index (VI) loss is big, accessory substance value is low.Dewaxed with first two
Method is compared, and isomerization dewaxing is to make macromolecular wax generation isomerization reaction generation isoparaffin, and isoparaffin and identical molecule
The wax of amount, which is compared, has lower condensation point and pour point and higher viscosity index (VI), and remains in heavy distillate, from
And cut oil yield is set to be greatly enhanced.
The purpose of isomerization dewaxing is exactly high melting-point wax is converted into the relatively low isoparaffin of fusing point, but isomerisation degree is high
Alkane fusing point it is higher on the contrary, so must just control the isomerisation degree of wax molecule, this just the Acidity to acidic components and
Pore structure and hydrogenation component propose strict requirements.Acidic components will have moderate strength, acid amount more and have in general
There is the pore structure of space restriction effect, and active metal component has quick hydrogenation/dehydrogenation activity, prevents tertiary carbonium ion
Further isomery so that cracking.
Report at present on isomerization dewaxing catalyst is a lot, for example, United States Patent (USP) US5990371, US5833837,
US5817907、US5149421、US5135638、US5110445、US4919788、US4419420、US4601993、
US4599162, US4518485 etc. all relate to Isodewaxing Technology, wherein the acidic components used mainly have modenite,
SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, ZSM-22 molecular sieve etc., although these above-mentioned materials have intensity
Moderate acid centre and the pore structure to match with wax molecule, there is obvious space to limit to highly-branched chain isomerous body, can
Make paraffin hydrocarbon that isomerization reaction occur to a certain extent, but due in catalyst preparation process, most acid can be made
Property center be capped, obtained acidity of catalyst is weaker, and activity and selectivity is relatively low, in addition, the stability of catalyst with its acid
Property it is closely related, acid stronger catalyst resistant to sulfur nitrogen poisoning capability is strong, and stability is good, but is also easier to that the pairs such as cracking occur
Reaction.
CN 103031144A disclose a kind of method that base oil is prepared using metal-modified small crystallite MTT molecular sieve,
The catalyst includes：With MTT matrix topologies and in the longest direction with about 200 ~ 400 nanometers of crystal grain diameter
Molecular sieve, at least one metal selected from Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd and at least one group VIII metal.Should
Method is using conventional hydrothermal crystallizing method synthesis of molecular sieve, using conventional impregnation method carried metal component.Using the method,
The effective rate of utilization of molecular sieve reduces, and activity and diffusion are deteriorated, and influence the selectivity and stability of catalyst.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of isomerization dewaxing catalyst and preparation method thereof.This method
The more active center distributions of catalyst can be made not only the acid centre of catalyst can be avoided to be capped in pore passage structure,
But also acid centre and hydrogenation sites is preferably coordinated, improve the activity and isomerisation selectivity of catalyst
And stability, and reduce the generation of side reaction.
The preparation method of the isomerization dewaxing catalyst of the present invention, including：
（1）Hydrogenation active component is loaded on MTT type molecular sieves, obtains loading the molecular sieve of hydrogenation active component；
（2）By step（1）Obtained molecular sieve is embedded in organic matter, obtains the molecular sieve of organic matter embedding；
（3）By step（2）The molecular sieve of obtained organic matter embedding mixes with the precursor of high temperature resistant indifferent oxide
It is even, through shaping, dry and be calcined, obtain the isomerization dewaxing catalyst of the present invention.
Step（1）The molecular sieve is that topological structure is MTT type small crystal grain molecular sieves, and average grain diameter is 0.1 ~ 1.0
Micron, preferably 0.2 ~ 0.8 micron, SiO2/Al2O3Mol ratio is 10 ~ 50, preferably 20 ~ 40.The MTT types molecular sieve can be with
Selected from various MTT structure molecular screens, including the one or more in ZSM-23, ISI-4, KZ-1 and SSZ-32 in the prior art,
One or more preferably in ZSM-23 and SSZ-32 molecular sieves.The mass content of the MTT types molecular sieve in the catalyst
For 1.0% ~ 20.0%, preferably 2.0% ~ 15.0%, more preferably 2.0% ~ 10.0%.Described hydrogenation active component is selected from member
At least one of VIIIth race's element, preferably platinum or/and palladium in plain periodic table, described hydrogenation active component is in the catalyst
Mass content 0.01% ~ 0.30%, preferably 0.05% ~ 0.10% are calculated as with metal.Described high temperature resistant indifferent oxide can be with
One or more in aluminum oxide, silica, calcium oxide, zinc oxide, magnesia etc., preferably aluminum oxide or/and oxidation
Silicon.The precursor of described high temperature resistant indifferent oxide refers to hydroxide corresponding to the oxide.
Step（1）The carrying method can be selected from the one or more in infusion process, kneading method and cladding process, preferably
Infusion process, more preferably supersaturated infusion process, i.e., contain hydrogenation metal component with more than institute's impregnated zeolite saturated extent of adsorption
Solution be sufficiently mixed with molecular sieve, then through drying and calcination process obtaining load hydrogenation active component molecular sieve.
Step（2）Described organic species can be selected from the one or more in starch and polyvinyl alcohol, the polyethylene
The degree of polymerization of alcohol is 1500 ~ 2500, and alcoholysis degree is more than 85%, preferably 90% ~ 99%.Described starch is water soluble starch, its
Molecular weight is 20000 ~ 100000, described starch be precipitated as one kind in cornstarch, tapioca and farina or
It is a variety of, preferably cornstarch.Step（2）The process that can be used with the method for organic matter embedding molecular sieve is as follows：Will be organic
Thing mixes with water, by step（1）The molecular sieve of the load hydrogenation active component of preparation is suspended in wherein, is then granulated, made
The molecular sieve of load hydrogenation active component is embedded in organic matter, and wherein prilling process can be vacuum spray drying method, boiling
Comminution granulation, centrifugal granulation or extrusion―spherozation etc., preferably vacuum spray drying method.In vacuum spray drying method, very
Reciprocal of duty cycle is generally 0.01 ~ 0.05MPa, and drying temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24 hour, i.e., will be obtained above outstanding
Turbid carries out vacuum spray drying, forms small dry particle.Step（2）In the molecular sieve of the organic matter embedding of gained, have
The mass ratio of machine thing and molecular sieve is 20:1~1:1, preferably 10:1~5:1.Step（2）The molecular sieve of the organic matter embedding of gained
Particle diameter be 10 ~ 100 microns.
Step（3）Described shaping, it can be selected according to practical application, such as spherical, strip or other special-shaped particles,
Preferably strip.Step（3）Described drying condition is：80 ~ 150 DEG C of drying temperature, 5 ~ 20 hours drying times, described roasting
Burning is carried out in oxygenous atmosphere, and the condition of roasting is：400 ~ 650 DEG C of sintering temperature, roasting time 5 ~ 20 hours.Purpose is
By organic matter oxidation removal at high temperature, discharge the ducts of needs i.e. reaction channel while, by active metal component grappling
On the inwall of molecular sieve pore passage.
The isomerization dewaxing catalyst of the present invention converts hydrogenation active metal component using preceding needing to be pre-processed
For simple substance, wet reducing or dry reduction, preferably dry reduction can be used.Described dry reduction can use pure hydrogen
Gas or the hydrogen containing inert gas, wherein hydrogen volume content are 5% ~ 100%, preferably 50% ~ 100%；Reduce bar
Part is as follows：Pressure is normal pressure ~ 10MPa, preferably 2 MPa ~ 8MPa；Temperature be 200 DEG C ~ 500 DEG C, preferably 250 DEG C ~ 400
℃；Time be 0.5 hour ~ 24 hours, preferably 1 hour ~ 12 hours, more preferably 2 hours ~ 8 hours, gas agent volume ratio（I.e.
The volume ratio of hydrogen and catalyst）For 500 ~ 1500, preferably 800 ~ 1200.
Isomerization dewaxing catalyst of the present invention can be used for the isomerization dewaxing process of lube cut, and reaction condition is such as
Under：The h of volume space velocity 0.5 during liquid-1~4.0h-1, reaction temperature is 260 DEG C ~ 400 DEG C, and reaction pressure is 2MPa ~ 20MPa, and hydrogen is oily
Volume ratio is 800 ~ 1200.
The isomerization dewaxing catalyst of the present invention is using will first be loaded with the molecular sieve of hydrogenation active metal component with organic
Thing embedding is got up, and is then mixed with catalyst with high temperature resistant inert inorganic oxide again, can so be made catalyst more
Active center distribution not only can avoid the acid centre of catalyst from being capped in pore passage structure, but also make acid centre and
Hydrogenation sites can preferably coordinate, when reactant is by catalyst duct, directly efficiently with urging in its duct
Change active specy contact and react, but because active particle is small, orifice throat length is short, and isomerization product can be diffused out quickly
Come, avoid deep reaction, improve the selectivity of isomerization reaction.Compared with prior art, the inventive method is used for lubricating oil
The isomerization dewaxing process of cut, because molecular sieve usage amount is greatly lowered, not only Catalyst Production cost significantly declines, also
The discharge of intractable waste water in sieve synthesis procedure is avoided, and with the high spy low with pour point of purpose product yield
Point.
Embodiment
The technology of the present invention is described further below by embodiment, but should not be construed as being limited to this scope.This
In invention, wt% is mass fraction.
In the present invention, the grain size of molecular sieve uses SEM（SEM）Mode determine, silica alumina ratio
It is to be measured using chemical analysis.
Evaluation institute is shown in Table 1 using feedstock property.Used fine grain ZSM-5-23 is with reference to Chinese patent
CN101214971A method synthesizes to obtain, and its average grain diameter is 0.5 micron.
The feedstock oil main character of table 1
| Project | Raw material 1 |
| Viscosity（50℃）/mm2.s-1 | 15.14 |
| Viscosity（100℃）/mm2.s-1 | 4.365 |
| Pour point/DEG C | 35 |
| Sulphur/μ g.g-1 | 8.0 |
| Nitrogen/μ g.g-1 | 1.0 |
| Wax content, % | 28.5 |
| Boiling range/DEG C | |
| IBP/10% | 378/390 |
| 30%/50% | 407/423 |
| 70%/90% | 444/483 |
| 95%/EBP | 503/520 |
Embodiment 1
A kind of preparation process of catalyst of the present invention is as follows：
（1）Chloroplatinic acid containing 1 gram of platinum is dissolved in 14 grams of water, by 19 grams of ZSM-23 molecular screens（Particle diameter is 0.5 micron,
SiO2/Al2O3Mol ratio is 35）It is sufficiently mixed with above-mentioned solution, mixture dries roasting 4 in 16 hours and 480 DEG C by 120 DEG C
Hour, obtain the ZSM-23 molecular screen of Supported Pt Nanoparticles；
（2）By 90 grams of water-soluble cornstarch（Molecular weight is 35000）It is dissolved in 300 grams of water, then adds 10 under normal temperature
Gram step（1）Obtained molecular sieve, uniform suspension is sufficiently stirred into, by vacuum spray drying（Vacuum 0.03MPa,
Drying temperature is 60 DEG C, drying time 5h）, obtain the catalytic activity thing for the starch embedding that average particulate diameter is 80 microns
Kind.
（3）Take 25 grams of steps（2）The molecular sieve of the starch embedding of preparation and 118 grams（Butt 76%）Aluminium hydroxide is SB powder
It is sufficiently mixed, then adds the salpeter solution that 85mL concentration is 0.1mol/L, abundant kneading, make paste plastic,
Forming diameter is 1.5mm cylindrical bars on banded extruder, and the cylindrical bars are dried 16 hours at 100 DEG C, then in air atmosphere
550 DEG C of roastings obtain catalyst of the present invention in 4 hours.Catalyst forms, in terms of mass fraction, Pt：0.05%、ZSM-23：2.5%、
Aluminum oxide：Surplus.
10mL catalyst is taken, is packed into after being diluted with 10mL quartz sands in the miniature flow reactor of fixed bed and carries out catalysis work
Property evaluation.Under conditions of pressure 1MPa, 200 DEG C of temperature, with gas agent volume ratio（Into the volume of gas and the dress of catalyst
Fill out volume ratio）800 speed is passed through pure hydrogen, improves temperature to 320 DEG C, the retention time is to carry out activation of catalyst in 4 hours；Then
Constant in pressure and temperature, hydrogen to oil volume ratio is adjusted to 900, using volume space velocity during liquid as 1.0h-1Into raw material shown in table 1, enter
Row catalyst activity is evaluated, and is negated and is answered the product of 4 hours to be analyzed, evaluation result is shown in Table 2.
Embodiment 2
A kind of embodiment of catalyst of the present invention with embodiment 1, difference in each step content of material carry out
Adjustment, SSZ-32（Particle diameter is 0.7 micron, SiO2/Al2O3Mol ratio is 25）Substitute ZSM-23 molecular screen, obtain catalyst group
As Pt：0.02%、SSZ-32：4.0%th, aluminum oxide：Surplus.Evaluation result is shown in Table 2.
Embodiment 3
A kind of embodiment of catalyst of the present invention with embodiment 1, difference in each step content of material carry out
The mass ratio of adjustment, starch and molecular sieve is 5:1, it is prepared into the molecule for the starch embedding that average particulate diameter is 50 microns
Sieve.It is Pt to obtain catalyst composition：0.1%、ZSM-23：8%th, aluminum oxide：Surplus.Evaluation result is shown in Table 2.
Embodiment 4
For a kind of embodiment of catalyst of the present invention with embodiment 1, difference is step（1）It is middle to substitute chlorine with palladium bichloride
Platinic acid, and content of material is adjusted in each step, and the mass ratio of starch and molecular sieve is 10:1, it is prepared into average
The molecular sieve of the starch embedding of a diameter of 100 microns of grain, obtain catalyst composition, in terms of mass fraction, Pd：0.4%、ZSM-23：
5.5%th, aluminum oxide：Surplus.Evaluation result is shown in Table 2.
Embodiment 5
For a kind of embodiment of catalyst of the present invention with embodiment 1, difference is step（1）In be additionally added palladium bichloride,
And content of material is adjusted in each step, the mass ratio of starch and molecular sieve is 2:1, it is prepared into average particulate diameter
For the molecular sieve of 70 microns of starch embedding, catalyst composition, in terms of mass fraction, Pt are obtained：0.07%、Pd：0.15%、ZSM-
23：4.5%th, aluminum oxide：Surplus.Evaluation result is shown in Table 2.
Embodiment 6
For a kind of embodiment of catalyst of the present invention with embodiment 1, difference is step（2）In use polyvinyl alcohol（It is poly-
Right is 1800, alcoholysis degree 92%）Substitute water soluble starch, content of material is adjusted in each step, polyvinyl alcohol with
The mass ratio of molecular sieve is 5:1, the molecular sieve for the polyvinyl alcohol embedding that average particulate diameter is 50 microns is prepared into, is catalyzed
Agent forms, in terms of mass fraction, Pt：0.3%、ZSM-23：8%th, aluminum oxide：Surplus.Evaluation result is shown in Table 2.
Embodiment 7
For a kind of embodiment of catalyst of the present invention with embodiment 1, difference is step（3）It is middle to substitute hydrogen-oxygen with silica gel
Change aluminium, content of material is adjusted in each step, and the mass ratio of starch and molecular sieve is 8:1, it is straight to be prepared into average grain
Footpath is the molecular sieve of 80 microns of starch embedding, obtains catalyst composition in terms of mass fraction, Pt：0.03%、ZSM-23：1.0%、
Silica：Surplus.Evaluation result is shown in Table 2.
Comparative example 1
It is that SB, ZSM-23 molecular screen and sesbania powder are sufficiently mixed by aluminium hydroxide, then adding appropriate concentration is
0.1mol/L salpeter solution, abundant kneading make paste plastic, a diameter of 1.5mm circle are extruded on banded extruder
Column, cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier in 4 hours in air atmosphere.
With containing H2PtCl6Solution saturation impregnates said catalyst carrier, then 100 DEG C of dryings 8 hours again, 500 DEG C in air atmosphere
3h is calcined, it is Pt that catalyst composition, which is made,：0.05%、ZSM-23：55%th, aluminum oxide：Surplus.Appreciation condition is the same as embodiment 1, evaluation
It the results are shown in Table 2.
Comparative example 2
For a kind of preparation method of comparative example catalyst with comparative example 1, difference is obtained catalyst composition with real
Apply example 1, i.e. Pt：0.05%、ZSM-23：3.0%th, aluminum oxide：Surplus.The same embodiment of appreciation condition
Comparative example 3
For a kind of preparation method of comparative example catalyst with comparative example 1, difference is obtained catalyst composition with real
Apply example 2, in terms of mass fraction, Pt：0.02%、SSZ-32：4.0%th, aluminum oxide：Surplus.Appreciation condition is the same as embodiment 1, evaluation knot
Fruit is shown in Table 2.
The evaluation result of table 2
| Embodiment is numbered | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| C5 +Liquid is received, wt% | 94.5 | 94.8 | 95.0 | 95.2 | 95.1 |
| Base oil yield, wt% | 81.5 | 81.8 | 82.4 | 82.3 | 81.8 |
| Viscosity index (VI) | 119 | 118 | 120 | 121 | 120 |
| Pour point, DEG C | -22 | -21 | -22 | -22 | -22 |
Continued 2
| Embodiment is numbered | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| C5 +Liquid is received, wt% | 95.3 | 94.8 | 91.5 | 96.2 | 93.7 |
| Base oil yield, wt% | 82.1 | 81.7 | 76.0 | 85.1 | 82.2 |
| Viscosity index (VI) | 120 | 121 | 115 | 108 | 110 |
| Pour point, DEG C | -20 | -21 | -20 | 15 | 17 |
The evaluation result of table 2 is shown, compared with comparative catalyst, using catalyst provided by the invention, for handling wax
In the hydroprocessing processes of the high lube cut of comparision contents, when lube base oil pour point is close, C5 +Liquid, which is received, improves 3%
More than, lube base oil yield improves 7wt% or so, and the viscosity index (VI) of product improves 5 units, and molecular sieve content drops
Low more than 80%, illustrate catalyst of the present invention during crude lube stock is handled, effect, which has, to be significantly improved.
Claims (20)
1. a kind of preparation method of isomerization dewaxing catalyst, including：
（1）Hydrogenation active component is loaded on MTT type molecular sieves, obtains loading the molecular sieve of hydrogenation active component；
（2）By step（1）Obtained molecular sieve is embedded in organic matter, obtains the molecular sieve of organic matter embedding；
（3）By step（2）The molecular sieve of obtained organic matter embedding is well mixed with the predecessor of high temperature resistant indifferent oxide, is passed through
Shaping, dry and be calcined, obtain isomerization dewaxing catalyst；
Wherein, step（2）One or more of the described organic matter in starch and polyvinyl alcohol, the polyvinyl alcohol gather
Right is 1500~2500, and for alcoholysis degree more than 85%, described starch is water soluble starch, its molecular weight is 20000~
100000；
Step（2）The process used with the method for organic matter embedding molecular sieve is as follows：Organic matter is mixed with water, by step（1）
The molecular sieve of the load hydrogenation active component of preparation is suspended in wherein, is then granulated, and makes point of load hydrogenation active component
Son sieve is embedded in organic matter, and wherein prilling process is vacuum spray drying method, boiling granulation method, centrifugal granulation or extrusion rolling
Circle comminution granulation；
Step（2）In the molecular sieve of the organic matter embedding of gained, the mass ratio of organic matter and molecular sieve is 20:1~1:1.
2. in accordance with the method for claim 1, it is characterised in that the MTT types molecular sieve uses small crystallite MTT type molecular sieve,
Average grain diameter is 0.1~1.0 micron.
3. in accordance with the method for claim 2, it is characterised in that the MTT types molecular sieve uses small crystallite MTT type molecular sieve,
Average grain diameter is 0.2~0.8 micron.
4. according to the method described in claim 1 or 2, it is characterised in that the SiO of the MTT types molecular sieve2/Al2O3Mol ratio is
10~50.
5. in accordance with the method for claim 4, it is characterised in that the SiO of the MTT types molecular sieve2/Al2O3Mol ratio is 20
~40.
6. according to the method described in claim 1 or 2, it is characterised in that the MTT types molecular sieve be selected from ZSM-23, ISI-4,
One or more in KZ-1 and SSZ-32.
7. in accordance with the method for claim 6, it is characterised in that the MTT types molecular sieve is in ZSM-23 and SSZ-32
It is one or more.
8. in accordance with the method for claim 1, it is characterised in that the mass content of the MTT types molecular sieve in the catalyst is
1.0%~20.0%.
9. in accordance with the method for claim 8, it is characterised in that the mass content of the MTT types molecular sieve in the catalyst is
2.0%~15.0%.
10. in accordance with the method for claim 1, it is characterised in that described hydrogenation active component is selected from platinum or/and palladium, described
Hydrogenation active component mass content in the catalyst be calculated as 0.01%~0.30% with metal.
11. in accordance with the method for claim 1, it is characterised in that described high temperature resistant indifferent oxide be selected from aluminum oxide or/
And silica.
12. in accordance with the method for claim 1, it is characterised in that described starch is cornstarch, tapioca and Ma Ling
One or more in sweet potato starch.
13. in accordance with the method for claim 1, it is characterised in that step（2）Prilling process is vacuum spray drying method, vacuum
It is 50~150 DEG C to spend for 0.01~0.05MPa, drying temperature, and drying time is 1~24 hour.
14. in accordance with the method for claim 1, it is characterised in that step（2）In the molecular sieve of the organic matter embedding of gained, have
The mass ratio of machine thing and molecular sieve is 10:1~5:1.
15. according to the method described in claim 1 or 10, it is characterised in that step（2）The molecular sieve of the organic matter embedding of gained
Particle diameter be 10~100 microns.
16. in accordance with the method for claim 1, it is characterised in that step（3）Described drying condition is：Drying temperature 80~
150 DEG C, 5~20 hours drying times, described roasting is carried out in oxygenous atmosphere, and the condition of roasting is：Sintering temperature
400~650 DEG C, roasting time 5~20 hours.
17. a kind of isomerization dewaxing catalyst, it is characterised in that prepared using any methods described of claim 1~16.
18. a kind of isomerization dewaxing method of waxy feeds, it is characterised in that using the catalyst described in claim 17.
19. in accordance with the method for claim 18, it is characterised in that described isomerization dewaxing catalyst using preceding need into
Row reduction, using dry reduction, described dry reduction is using the pure hydrogen either hydrogen containing inert gas；Reducing condition
It is as follows：Pressure is normal pressure~10MPa, and temperature is 200 DEG C~500 DEG C, and the time is 0.5 hour~24 hours, and gas agent volume ratio is
500~1500.
20. according to the method described in claim 18 or 19, it is characterised in that described isomerization dewaxing catalyst is used for lubricating oil
The isomerization dewaxing process of cut, reaction condition are as follows：The h of volume space velocity 0.5 during liquid-1~4.0h-1, reaction temperature be 260 DEG C~
400 DEG C, reaction pressure is 2MPa~20MPa, and hydrogen to oil volume ratio is 800~1200.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246566A (en) * | 1989-02-17 | 1993-09-21 | Chevron Research And Technology Company | Wax isomerization using catalyst of specific pore geometry |
| CN1204683A (en) * | 1997-03-05 | 1999-01-13 | 法国石油公司 | Process for selective hydroisomerization of paraffins |
| CN103657713A (en) * | 2012-08-29 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application of catalyst and hydroisomerization method |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
-
2014
- 2014-12-02 CN CN201410716641.7A patent/CN105709817B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246566A (en) * | 1989-02-17 | 1993-09-21 | Chevron Research And Technology Company | Wax isomerization using catalyst of specific pore geometry |
| CN1204683A (en) * | 1997-03-05 | 1999-01-13 | 法国石油公司 | Process for selective hydroisomerization of paraffins |
| CN103657713A (en) * | 2012-08-29 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application of catalyst and hydroisomerization method |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
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