CN105080478B - The method that low octane rating component is separated from mixed alkanes - Google Patents
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 18
- 239000003463 adsorbent Substances 0.000 claims abstract description 100
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 76
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 76
- 239000010457 zeolite Substances 0.000 claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 239000010703 silicon Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- -1 solves the problems Chemical class 0.000 claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 82
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 41
- 239000012690 zeolite precursor Substances 0.000 claims description 40
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 abstract description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 35
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 21
- 238000012546 transfer Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical class CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 14
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical class CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 11
- 230000000274 adsorptive effect Effects 0.000 description 11
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 10
- 230000033228 biological regulation Effects 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 10
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 9
- 229940073608 benzyl chloride Drugs 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- LCXAARCEIWRIMU-UHFFFAOYSA-M dibenzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 LCXAARCEIWRIMU-UHFFFAOYSA-M 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical class CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to overall high silicon EUO zeolites, its preparation method, and the method that low octane rating component is separated from mixed alkanes, mainly solves the problems, such as the existing low octane rating component inferior separating effect formed to methylpentane, monomethyl hexane of existing binder free 5A zeolite adsorbents in the prior art, by using overall high silicon EUO zeolites, wherein SiO2/Al2O3Mol ratio is at least 100 technical scheme, preferably solves above-mentioned technical problem, the separation available for low octane rating component in mixed alkanes.
Description
Technical field
The present invention relates to the present invention relates to overall high silicon EUO zeolites, its preparation method, and separate from mixed alkanes low
The method of octane components.
Background technology
Environmental problem has caused world's extensive concern, and this requires that researcher seeks to solve the side for improving efficiency of energy utilization
Method.The end in cheap crude epoch will promote oil refining enterprise to optimize fuel performance, to increase fuel engines efficiency of combustion.With regard to vapour
For oil, its combustibility is evaluated by research octane number (RON) (RON).The high burning of octane number is steady, and detonation will not occur, can be with
Improve the efficiency of fuel engines.
Light straight-run naphtha is a kind of refinery material, is mainly made up of C5-C7 alkane, is fuel for motor vehicles, such as gasoline
Blend component.But the octane number of the organon gasoline of these hydro carbons is relatively low, typically between 68-72.Past octane number can
To be improved by adding alkyl lead compound or aromatic hydrocarbons, with the implementation of new environmental regulation, oil refining enterprise's unrenewable tradition
Method improves octane number.
At present, putting forward high-octane method mainly has：1) octane enhancing additive is added in oil product, it contains in increase gasoline
Outside oxygen amount, cleaning burning is may additionally facilitate, reduces automobile hazardous emission；2) low octane rating component in separating oil, by low octane
Value component is converted into antiknock component through chemical reaction and rejoined in oil product.
In past 20 years, methyl tertiary butyl ether(MTBE) has substituted with serious pollution Organic leadP, as octane enhancer.Methyl- tert
Butyl ether (MTBE) can not only increase the octane number of gasoline, improve efficiency of combustion, reduce CO and some other harmful substance (such as
Ozone, benzene, butadiene etc.) discharge, and uprising dose can be made instead of lead tetraethide, various countries have once started production MTBE wave
Tide.Therefore rapid promote is come, and demand constantly increases, and MTBE suddenly becomes emerging large-tonnage petrochemicals.China
Begin one's study MTBE synthetic technology from beginning of the eighties late 1970s, 1999, and country starts " national air purification work
Journey-cleaning vehicle action ".On January 1st, 2001, start-stop shotpin sold doped fuel.Used with MTBE popularity, to MTBE
Research also deepening continuously.Recent studies have shown that MTBE also has certain toxic action to animal, it may be possible to a kind of potential
Environmental pollutants.
Because MTBE has stronger water solubility, soil pollution water body is easily penetrated into.Polluted water body does not only have surface water, also has
Underground water, the drinking water source of serious threat people.Due to structure and the particularity of property, MTBE is difficult degraded, in underground water
There is longer half-life period, longitudinal gradient very little, it is impossible MTBE is largely reduced, and it is ratio that it is extracted from water
More difficult, while also eliminate the feasibility that the method repaired with extraction removes MTBE in soil and groundwater.MTBE into
For second material being detected in urban groundwater, the cry more and more higher of disabling.
The U.S. is former to determine that the 3.65% of gasoline total amount is MTBE, and about 87% reformulated gasoline uses MTBE as oxygen-containing
Compound.In view of pollutions of the MTBE to water quality, California, USA disables MTBE from 2004, Arizona State, the Connecticut State and
New York etc. also disabled MTBE in 2005.MTBE incorporations are also reduced in other states one after another, and add disabling MTBE ranks.
Australia also disabled MTBE in 2004.From 2006, U.S. gasoline disabling MTBE paces are further speeded up.2006
From May, the existing 25 states disabling MTBE in the U.S..U.S.'s MTBE demands are reduced to 2010 from 12,900,000 tons/year of 2001
About 3,500,000 tons/year.Global MTBE demands once reached 22,580,000 tons/year of peak value for 2001, predicted that the demand in future will be further
Decline.If MTBE is not used, must take measures to compensate its octane number, quantity and the loss of other properties.
On the other hand, national legislation is also more next strict to gasoline composition requirement, have high-octane aromatic hydrocarbons, it is nitrogenous, contain
The content of sulphur thing, oxygen-containing compounds in gasoline component is strictly controlled, and content must be greatly lowered.Not doping
Putting forward high-octane main method has catforming to produce high-knock rating gasoline；Normal alkane isomerization improves octane number.
Not doping maintains the method for octane number mainly to increase multibranched paraffin content in gasoline, reduces linear alkanes
With single branched paraffin content., can be by this stock according to isomery temperature using isomerization method by C5~C10 linear alkanes isomerization
The octane number of material is lifted to 78~84.Want naphtha octane number bringing up to more than 90, just must be by isomerization processes with dividing
Separating process is combined.Unconverted linear low octane rating component in isomerization process is removed with adsorbent, to improve its octane number.
Adsorbent of molecular sieve is widely used among many processes of Petrochemical Enterprises.One of them extremely important application
It is exactly to lift field in oil product octane number described above, that is, pentane and hexane is separated into antiknock component and low octane
It is worth component.In general, n-alkane, single branched chain methyl hexane form low octane rating component, multibranched paraffin, cycloalkane and virtue
Hydrocarbon forms antiknock component.
Using conventional method, such as United States Patent (USP) US4709116A (Isomerization process and
Apparatus method used by), i.e., with n-alkane in 5A molecular sieve adsorption naphthas, can largely be lifted
The octane number of oil product, but, 5A molecular sieves can not effectively adsorb low octane rating monomethyl alkane in naphtha, and therefore, it is to stone brain
The further raising of oily octane number is restricted.
Although isoamyl alkyl structure is structurally similar with monomethyl hexane, it is also antiknock component, is being separated
Cheng Zhongying retains.Using overall EUO zeolite adsorbents, using isopentane and monomethylpentanes and monomethyl hexane on the sorbent
The difference of adsorption strength, isopentane can be separated with monomethylpentanes and monomethyl hexane, can so improve raw material utilizes effect
Rate, while the octane number of separation product is not influenceed.
The content of the invention
One of technical problems to be solved by the invention are that existing binder free 5A zeolite adsorbents are existing to methylpent
The problem of low octane rating component inferior separating effect that alkane, monomethyl hexane are formed, there is provided a kind of high silicon EUO zeolites of entirety, it is used
There is the characteristics of good separating effect in low octane rating component described in the adsorbing separation from mixed alkanes in adsorbent.
The two of the technical problems to be solved by the invention are the systems of the high silicon EUO zeolites of one of above-mentioned technical problem entirety
Preparation Method.
The three of the technical problems to be solved by the invention are the high silicon EUO zeolite conducts of one of above-mentioned technical problem entirety
Method of the adsorbent in the adsorbing separation low octane rating component from mixed alkanes.
To solve one of above-mentioned technical problem, technical scheme is as follows：Overall high silicon EUO zeolites, wherein SiO2/
Al2O3Mol ratio is at least 100.
In above-mentioned technical proposal, the high silicon EUO zeolite particle sizes of entirety are preferably 16~40 mesh.
In above-mentioned technical proposal, the overall high silicon EUO zeolites of the high preferred Hydrogen of silicon EUO zeolites of entirety.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of the high silicon EUO zeolites of the entirety in case, comprises the following steps：
(1) amorphous Si O needed for containing2With amorphous Al2O3Composite S iO2- Al2O3Article shaped is immersed in pH as 7.5
~14 crystallization in brilliant liquid that turns obtains overall high silicon EUO zeolite precursors 1；
(2) overall high silicon EUO zeolites are obtained by the high silicon EUO zeolite precursors 1 of above-mentioned entirety are fired；
The wherein described brilliant liquid that turns includes template, and the template is selected from template a) or template b) at least
One kind, more preferably template are mixed by template a) and template b), and template a) and template b) weight is than preferred
For 0.3~3, more preferably 0.5~2：
A) mixture of N, N- dimethyl benzylamine and halogenation benzyl；
B) dimethyl dibenzyl ammonium halide.
It is further comprising the steps of in order to prepare Hydrogen integrally high silicon EUO zeolites：
(3) the high silicon EUO zeolites of entirety described in claim 4 are passed through and obtained with the solution progress ion exchange containing ammonium ion
The high silicon entirety EUO zeolites of ammonium type；
(4) the high silicon entirety EUO zeolites of ammonium type are fired obtains Hydrogen integrally high silicon EUO zeolites.
In above-mentioned technical proposal, the mol ratio of halogenation benzyl and N, N- dimethyl benzylamine is preferably 0.2 in the template a)
~4.
In above-mentioned technical proposal, the halogen in template preferably is selected from chlorine or bromine.
In above-mentioned technical proposal, step (1) transfer crystalline substance liquid and composite S iO2- Al2O3The weight ratio preferably 1 of article shaped~
10。
In above-mentioned technical proposal, composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably at least 300.
In above-mentioned technical proposal, it is preferably 0.01~20% by weight percentage to turn template agent concentration in brilliant liquid.
In above-mentioned technical proposal, the temperature that step (1) turns brilliant is preferably 80~200 DEG C；The time for turning brilliant is preferably 4~
100 hours.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Low octane rating is separated from mixed alkanes
The method of component, using overall high silicon EUO zeolites any one of the technical scheme of one of above-mentioned technical problem as absorption
Agent adsorbing separation low octane rating component from mixed alkanes.The low octane rating monomethyl alkane can for example be but not limited to 2-
Methyl-pentane, 3- methyl-pentanes and 2- methyl-hexanes.
According to the record of the present invention, those skilled in the art will be seen that the high silicon EUO zeolites of entirety are as adsorbent
In the application of the adsorbing separation low octane rating component from mixed alkanes, specific method can be：Inhaled using high silicon entirety EUO zeolites
Attached dose is separated off low octane rating monomethyl from the naphtha containing positive structure, monomethyl alkane, multibranched paraffin and cycloalkane
Alkane and n-alkane, adsorbent is in the mesh of granularity 16~40.The preferred room temperature of temperature is to 200 DEG C, solid-liquid weight ratio preferably 1：
(1.5~50).
In the specific embodiment of the invention, in used concept, 2- methyl-pentanes (2-m-C5), 3- methyl-pentanes
(3-m-C5), 2- methyl-hexanes (2-m-C6) are to isopentane (i-C5), n-hexane (n-C6) to 2,3- Dimethyl-butanes (2,3-
M-C4 adsorptive selectivity) is defined as：Concentration (percentage by weight) of the target affinity thing in adsorbent is with it in adsorption liquid
The ratio between concentration (percentage by weight), more than 1, represent adsorbent to the selective suction-operated of target affinity thing.
Wherein：S2C5/iC5Represent that 2-m-C5 to i-C5 adsorptive selectivity, represents adsorbent to 2-m- more than 1 in mixture
C5 preferences adsorb, and bigger adsorbent is stronger to 2-m-C5 selectivity；
C2-m-C5sThe weight percent concentration of 2- methyl-pentanes (2-m-C5) in-solid absorbent；
Ci-C5sThe weight percent concentration of isopentane (i-C5) in-solid absorbent；
C2-m-C5lThe weight percent concentration of 2- methyl-pentanes (2-m-C5) in-liquid；
Ci-C5lThe weight percent concentration of isopentane (i-C5) in-liquid.
S3C5/iC5Represent that 3-m-C5 to i-C5 adsorptive selectivity, represents that adsorbent is excellent to 3-m-C5 more than 1 in mixture
First selective absorption, bigger adsorbent are stronger to 3-m-C5 selectivity；
C3-m-C5sThe weight percent concentration of 3- methyl-pentanes (3-m-C5) in-solid absorbent；
Ci-C5sThe weight percent concentration of isopentane (i-C5) in-solid absorbent；
C3-m-C5lThe weight percent concentration of 3- methyl-pentanes (3-m-C5) in-liquid；
Ci-C5lThe weight percent concentration of isopentane (i-C5) in-liquid.
S2C5/iC5Represent that 2-m-C6 to i-C5 adsorptive selectivity, represents that adsorbent is excellent to 2-m-C6 more than 1 in mixture
First selective absorption, bigger adsorbent are stronger to 2-m-C6 selectivity.
C2-m-C6sThe weight percent concentration of 2- methyl-hexanes (2-m-C6) in-solid absorbent；
Ci-C5sThe weight percent concentration of isopentane (i-C5) in-solid absorbent；
C2-m-C6lThe weight percent concentration of 2- methyl-hexanes (2-m-C6) in-liquid；
Ci-C5lThe weight percent concentration of isopentane (i-C5) in-liquid.
SnC6/2,3C4Represent that n-C6 to 2,3m-C4 adsorptive selectivity, represents that adsorbent is excellent to n-C6 more than 1 in mixture
First selective absorption, bigger adsorbent are stronger to 2,3m-C4 selectivity；
CnC6sThe weight percent concentration of n-hexane (n-C6) in-solid absorbent；
C2,3-m-C4sThe weight percent concentration of 2,3- Dimethyl-butanes (2,3-m-C4) in-solid absorbent；
CnC6lThe weight percent concentration of n-hexane (n-C6) in-liquid；
C2,3-m-C4lThe weight percent concentration of 2,3- Dimethyl-butanes (2,3-m-C4) in-liquid.
The high silicon EUO zeolites of entirety of the present invention are low pungent to n-alkane, methylpentane, monomethyl hexane etc. as adsorbent
Alkane value component has preferable adsorptive selectivity, and has relatively low adsorptive selectivity to high-octane isopentane, does not adsorb height
More methyl alkanes of octane number, and prior art uses adhesive-free 5A zeolite adsorbents, does not adsorb monomethyl alkane, achieve compared with
Good technique effect.
Below by embodiment, the present invention is further elaborated, but these embodiments are not the limits to the scope of the invention
System.
Embodiment
【Embodiment 1】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:1) water is dissolved in, described turn of crystalline substance is obtained for 9 with sodium hydroxide regulation pH
Liquid.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites in 3 hours through 550 DEG C of roastings and produce adsorbent；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
2nd, adsorbent evaluation
To be activated 1 hour at 400 DEG C before all adsorbent evaluations
1) measure of n-hexane saturated adsorption capacity, it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity, accurately weigh with
Percentage by weight meter contains 5 grams of the isooctane solution of 10% n-hexane, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, constantly
Stirring, measurement temperature are room temperature, and adsorption time is 60 minutes, and the adsorbance of measure is its saturated adsorption capacity.
2) measure of 2- methyl-pentanes (2-m-C5) saturated adsorption capacity, it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, 5 grams of the isooctane solution by weight percentage containing 10% 2- methyl-pentanes (2-m-C5) is accurately weighed, solid-to-liquid ratio is
3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorption time is 60 minutes, the absorption of measure
Amount is its saturated adsorption capacity.
3) measure of 3- methyl-pentanes (3-m-C5) saturated adsorption capacity, it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, 5 grams of the isooctane solution by weight percentage containing 10% 3- methyl-pentanes (3-m-C5) is accurately weighed, solid-to-liquid ratio is
3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorption time is 60 minutes, the absorption of measure
Amount is its saturated adsorption capacity.
4) measure of 2- methyl-hexanes (2-m-C6) saturated adsorption capacity, it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, 5 grams of the isooctane solution by weight percentage containing 10% 2- methyl-hexanes (2-m-C6) is accurately weighed, solid-to-liquid ratio is
3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorption time is 60 minutes, the absorption of measure
Amount is its saturated adsorption capacity.
5) measure of the n-hexane rate of adsorption, it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity, and adsorption liquid is with weight
Percentages contain 5 grams of the isooctane adsorption liquid of 10% n-hexane, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, constantly stirs
Mix, measurement temperature is room temperature, and adsorbent is as initial 3 points to the adsorbance of n-hexane, the adsorbance divided by 3 when adsorbing 3 minutes
The clock rate of adsorption.
6) measure of 2- methyl-pentanes (2-m-C5) rate of adsorption, it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity,
Adsorption liquid for by weight percentage containing 10% 2- methyl-pentanes (2-m-C5) 5 grams of isooctane adsorption liquid, solid-to-liquid ratio 3:
5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorbent is to 2- methyl-pentanes when adsorbing 3 minutes
The adsorbance of (2-m-C5), the adsorbance divided by 3, as initial 3 minutes rates of adsorption.
7) measure of 3- methyl-pentanes (3-m-C5) rate of adsorption, it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity,
Adsorption liquid for by weight percentage containing 10% 3- methyl-pentanes (3-m-C5) 5 grams of isooctane adsorption liquid, solid-to-liquid ratio 3:
5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorbent is to 3- methyl-pentanes when adsorbing 3 minutes
The adsorbance of (3-m-C5), the adsorbance divided by 3, as initial 3 minutes rates of adsorption.
8) measure of 2- methyl-hexanes (2-m-C6) rate of adsorption, it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity,
Adsorption liquid for by weight percentage containing 10% 2- methyl-hexanes (2-m-C6) 5 grams of isooctane adsorption liquid, solid-to-liquid ratio 3:
5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, and adsorbent is to 2- methyl-hexanes when adsorbing 3 minutes
The adsorbance of (2-m-C6), the adsorbance divided by 3, as initial 3 minutes rates of adsorption.
9) the adsorptive selectivity measure of 2- methyl-pentanes (2-m-C5), it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, accurately weigh by weight percentage containing 10% 2- methyl-pentanes (2-m-C5), the isooctane of 10% isopentane (i-C5)
5 grams of solution, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, adsorption time 45
Minute, selectivity of the measure adsorbent to 2- methyl-pentanes (2-m-C5).
10) the adsorptive selectivity measure of 3- methyl-pentanes (3-m-C5), it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, accurately weigh by weight percentage containing 10% 3- methyl-pentanes (3-m-C5), the isooctane of 10% isopentane (i-C5)
5 grams of solution, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, adsorption time 45
Minute, the selectivity of the adsorbent of measure to 3- methyl-pentanes (3-m-C5).
11) the adsorptive selectivity measure of 2- methyl-hexanes (2-m-C6), it is 16~40 mesh adsorbents 3 accurately to weigh granularity
Gram, accurately weigh by weight percentage containing 10% 2- methyl-hexanes (2-m-C6), the isooctane of 10% isopentane (i-C5)
5 grams of solution, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, adsorption time 45
Minute, the adsorbent of measure is to 2- methyl-hexanes (2-m-C6)) selectivity.
12) the adsorptive selectivity measure of n-hexane (n-C6), it is 3 grams of 16~40 mesh adsorbent accurately to weigh granularity, accurately
Weigh by weight percentage containing 10% n-hexane (2-m-C6), 10% 2,3- Dimethyl-butanes (2,3-m-C4) it is different
5 grams of octane solution, solid-to-liquid ratio 3:5, it is mixed in 25 milliliters of triangular flasks, is stirred continuously, measurement temperature is room temperature, adsorption time
For 45 minutes, the selectivity of the adsorbent of measure to n-hexane (n-C6).
The main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 2】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum dimethyl dibenzyl ammonium chloride
Water is dissolved in, described turn of brilliant liquid is obtained for 9 with sodium hydroxide regulation pH.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 3】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:And dimethyl dibenzyl ammonium chloride in molar ratio 1 1):1 is dissolved in water,
With sodium hydroxide regulation pH described turn of brilliant liquid is obtained for 9.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 4】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:And dimethyl dibenzyl ammonium chloride in molar ratio 1 1):0.5 is dissolved in
Water, described turn of brilliant liquid is obtained for 9 with sodium hydroxide regulation pH.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 5】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:And dimethyl dibenzyl ammonium chloride in molar ratio 1 1):2 are dissolved in water,
With sodium hydroxide regulation pH described turn of brilliant liquid is obtained for 9.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 6】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:0.2) water is dissolved in, described turn is obtained for 9 with sodium hydroxide regulation pH
Brilliant liquid.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites in 3 hours through 550 DEG C of roastings and produce adsorbent；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 7】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 5w% containing template；Turn brilliant liquid and composite S iO2- Al2O3Into
The weight of type thing is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 300；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:4) water is dissolved in, described turn of crystalline substance is obtained for 9 with sodium hydroxide regulation pH
Liquid.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites in 3 hours through 550 DEG C of roastings and produce adsorbent；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 8】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 20w% containing template；Turn brilliant liquid and composite S iO2- Al2O3
The weight of article shaped is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 100；The temperature for turning brilliant is preferred
160℃；The time for turning brilliant is preferably 60 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines and chlorine
Changing benzyl, (N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio:And dimethyl dibenzyl ammonium chloride in molar ratio 1 1):1 is dissolved in water,
With sodium hydroxide regulation pH described turn of brilliant liquid is obtained for 14.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Embodiment 9】
1st, prepared by adsorbent
(1) amorphous Si O will be contained2With amorphous Al2O3The spherical composite S iO of the purpose of granularity 16~402- Al2O3Article shaped
200 grams are immersed in turn brilliant liquid that pH is 9, and crystallization obtains Hydrogen entirety EUO zeolite precursors 1；Wherein composite S iO2- Al2O3Into
SiO in type thing2/Al2O3Mol ratio is 5~300；Its transfer crystalline substance liquid 0.01w% containing template；Turn brilliant liquid and composite S iO2-
Al2O3The weight of article shaped is than 5；Composite S iO2- Al2O3The SiO of article shaped2/Al2O3Mol ratio is preferably 800；Turn brilliant temperature
It is preferred that 200 DEG C；The time for turning brilliant is preferably 4 hours.The manner of formulation of its transfer crystalline substance liquid is by aequum N, N- dimethyl benzylamines
(N, N- dimethyl benzylamine are 1 with benzyl chloride mol ratio with benzyl chloride:And dimethyl dibenzyl ammonium chloride in molar ratio 1 1):1 is molten
Yu Shui, described turn of brilliant liquid is obtained for 7.5 with sodium hydroxide regulation pH.
(2) above-mentioned Hydrogen entirety EUO zeolite precursors 1 are obtained into Hydrogen entirety EUO zeolite precursors in 3 hours through 550 DEG C of roastings
2；
(3) by 60 grams of above-mentioned Hydrogen entirety EUO zeolite precursors 2 through being mixed with 300 grams of concentration for 8w% aqueous ammonium nitrate solution
Close, ammonium type entirety EUO zeolites are obtained within 3 hours in 80 DEG C of ion exchanges；
(4) ammonium type entirety EUO zeolites obtain Hydrogen entirety EUO zeolites, i.e. adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Comparative example 1】
(1) EUO (SiO are weighed2/Al2O3=300) 800 grams of zeolite powder, add Ludox (to contain by weight percentage
SiO240%) 50 grams, suitable quantity of water roller forming is added, the mesh of granularity 16~40 shaping bead is chosen in sieving, by shaping bead in 120 DEG C
Dry 4 hours, then produce adsorbent precursors 2 after 550 DEG C of roastings；
(2) 60 grams of above-mentioned adsorbent precursors are mixed with the aqueous ammonium nitrate solution that 300 grams of concentration are 8w%, in 80 DEG C of ions
Exchange 3 hours and obtain adsorbent precursors 1；
(3) adsorbent precursors 1 obtain adsorbent in 3 hours through 550 DEG C of roastings；
Adsorbent preparation condition is shown in Table 1, table 2, table 3.
The evaluation method and condition of adsorbent are same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
【Comparative example 2】
Choose 16-40 binder free 5A adsorbent of molecular sieve, evaluate the performance of adsorbent, the evaluation method of adsorbent and
Condition is same【Embodiment 1】, the main performance index of adsorbent is shown in Table 4, table 5, table 6.
Table 1
Table 2
* the ratio between EUO zeolite powder XRD intensities that crystallinity synthesizes for turn brilliant product with comparative example.
Table 3
Table 4
Table 5
Table 6
Claims (8)
1. overall high silicon EUO zeolites, wherein SiO2/Al2O3Mol ratio is at least 100, and the high silicon EUO zeolites of entirety are hydrogen
The overall high silicon EUO zeolites of type；
The preparation method of the high silicon EUO zeolites of entirety, comprises the following steps：
(1) amorphous Si O needed for containing2With amorphous Al2O3Composite S iO2-Al2O3It is 7.5~14 that article shaped, which is immersed in pH,
Turn crystallization in brilliant liquid and obtain overall high silicon EUO zeolite precursors 1；
(2) overall high silicon EUO zeolites are obtained by the high silicon EUO zeolite precursors 1 of above-mentioned entirety are fired；
The wherein described brilliant liquid that turns includes template, and the template is selected from least one in template a) or template b)
Kind：
A) mixture of N, N- dimethyl benzylamine and halogenation benzyl；
B) dimethyl dibenzyl ammonium halide.
2. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that the high silicon EUO zeolite particle sizes of the entirety are 16
~40 mesh.
3. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that halogenation benzyl and N, N- bis- in the template a)
The mol ratio of methylbenzylamine is 0.2~4.
4. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that the halogen in template is selected from chlorine or bromine.
5. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that composite S iO2-Al2O3The SiO of article shaped2/
Al2O3Mol ratio is at least 300.
6. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that template agent concentration is with weight percent in turn brilliant liquid
Than being calculated as 0.01~20%.
7. the high silicon EUO zeolites of entirety according to claim 1, it is characterized in that 80~200 DEG C of the temperature of step (1) crystallization；
The time of crystallization is 4~100 hours.
8. the method for low octane rating component is separated from mixed alkanes, it is characterized in that using any one of claim 1-7
Overall high silicon EUO zeolites adsorbing separation low octane rating component from mixed alkanes as adsorbent.
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