CN101172249A - Normal alkane isomerization catalyst and preparation method thereof - Google Patents
Normal alkane isomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses normal alkane isomerization catalyst and a preparation method thereof. The catalyst comprises a TON molecular sieve, inorganic melt-resistant oxide and hydrogenation component, wherein, the TON molecular sieve contains IB elements, the weight content of the IB elements in the molecular sieve is 0.5 to 10 percent counted by the metal. The preparation process of the catalyst comprises the following steps: firstly, the IB elements are loaded onto the molecular sieve, and then are prepared into the catalyst. The catalyst is used for the isomerization process of the normal alkane, and has the characteristic of high reaction selectivity.
Description
Technical field
The present invention relates to a kind of catalyst for normal paraffin isomerization and preparation method thereof.In particular, relate to a kind of long-chain normal paraffin isomerization catalyst and preparation method thereof, be particularly suitable for the isomerization process of n-dodecane.
Background technology
In the petroleum distillate, especially come from the heavy distillate of paraffinic base crude oil and contain more wax, condensation point is higher, low temperature flow is poor, in storage, transportation and use, reduction with environment temperature can make oily retrogradation, even solidifies, thereby the fuel feeding that stops up petroleum pipeline and interruption engine breaks down engine.It is a lot of because of the method for solidifying the variety of issue that causes to solve content of wax heavy distillate at present, and wherein main means are dewaxings, comprise solvent dewaxing, catalytic dewaxing and isomerization dewaxing.
Solvent dewaxing is exactly to utilize the solubility property of wax in solvent to remove, and the shortcoming of this method is that solvent selects a large amount of organic solvent of difficulty, waste, harmful and contaminated environment, equipment investment and operating cost height and product quality limited by raw material.Catalytic dewaxing just is to use has the catalyst of selecting shape cracking function, make the wax component generation selectivity catalytic cracking in the cut, generate the hydro carbons of less molecule, for example P.4247388 U.S. Pat removes wax in the lubricating oil with USP.4659311 with regard to the method that is to use catalytic dewaxing, the shortcoming of this method is because the macromolecular compound of a large amount of high values is converted into the small-molecule substance of low value, makes that base oil yield is low, the viscosity index (VI) loss is big, accessory substance value is low.Compare with preceding two kinds of process for dewaxing, isomerization dewaxing is to make big molecular wax generation isomerization reaction generate isoparaffin, and isoparaffin condensation point and pour point and the higher viscosity index lower than having with the wax phase of same molecular amount, and still be retained in the heavy distillate, thereby the distillate yield is greatly enhanced.
The purpose of isomerization dewaxing is exactly to make high melting-point wax be converted into the lower isoparaffin of fusing point, but the alkane fusing point that isomerisation degree is high is higher on the contrary, so isomerisation degree that just must control wax molecule, this has just proposed strict requirement to the acid matter of acidic components and pore structure and hydrogenation component.Acidic components will have that intensity is moderate, acid amount is more and have the pore structure of spatial constraints effect in general, and active metal component has hydrogenation/dehydrogenation activity fast, prevent the further isomery and even the cracking of uncle's carbonium ion.
At present a lot of about the report of isomerization dewaxing catalyst, for example, U.S. Pat P5990371,5833,837,5817907,5149421,5135638,5110445,4919788,4419420,4601993,4599162,4518485 etc. all relate to the isomerization dewaxing technology, use therein acidic components mainly contain modenite, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, SSZ-32, Nu-10, KZ-2 and ISI-1 etc.Though above-mentioned these materials can both make paraffin hydrocarbon generation isomerization reaction to a certain extent,, help the performance of normal alkane isomerization performance because the TON structure molecular screen has special pore structure and suitable acid matter.And the at present disclosed catalyst that contains the TON molecular sieve also can be handled by modification and further improve its reactivity worth, especially improves its isomerization selectivity.
Be widely used in the petroleum refining catalyst at present for example the preparing ethylene by selective hydrogenation of acetylene or propine or propylene catalyst, the selective oxidation making formaldehyde catalyst of ethanol etc. with the element modified catalyst of IB.But the element modified molecular sieve of IB is applied to long-chain normal paraffin isomerization reaction aspect also to be had not seen reported.
It is generally acknowledged after the carbon atom number surpasses 8, the mechanism of its isomerization reaction all is to carry out according to key mechanism, the most meaningful to long chain alkane isomerization reaction research at present, obtain maximum progress, and typical case's representative of commercial Application has been exactly an isomerization dewaxing, isomerization dewaxing is exactly optionally paraffinic components to be carried out isomerization reaction to generate isomerization product, so not only make the depression of pour point of product, mobile performance improves, and can improve the yield and the quality of purpose product, be subjected to great attention.Because the structure of waxy oil component is very complicated, paraffinic components itself is exactly some long-chain normal paraffins or the terminal isoparaffin that slight branch is arranged, its reaction mechanism and other C
8Above normal alkane isomerization mechanism is identical, so study at present such catalyst maximum be to be model compound with pure n-alkane, study its isomerization reaction performance, for having more representativeness, what selected model compound was maximum is n-dodecane and hexadecane, and the research with n-dodecane serves as maximum especially.
Summary of the invention
For overcoming the deficiencies in the prior art part, the invention provides a kind of high selectivity catalyst for normal paraffin isomerization and preparation method thereof.Compare with reference catalyst, reaching under the close conversion ratio condition, the selectivity of this catalyst isomerization reaction obviously improves.
Catalyst of the present invention contains TON type molecular sieve, inorganic refractory oxide and hydrogenation component, and wherein TON type molecular sieve contains IB family element, and in metal, the IB family weight of element in molecular sieve consists of 0.5%～10%, is preferably 0.5%～5%.
Catalyst of the present invention, by weight, it is composed as follows:
The TON type molecular sieve that contains IB family element: 10%～90%;
Hydrogenation component is in metal: 0.1%～5.0%;
Inorganic refractory oxide: surplus.
Described TON type molecular sieve is one or more among ZSM-22, Nu-10, KZ-2 and the ISI-1, is preferably the ZSM-22 molecular sieve.The silica alumina ratio of described TON type molecular sieve is 50～200, is preferably 70～150.
Described IB family element is to be selected from copper, silver and the gold one or more, is preferably silver or/and gold, more preferably silver.
The kind of described hydrogenation component is that those of ordinary skills are known, the preferred noble metal hydrogenation component of the present invention, more preferably platinum and/or palladium.In metal, its weight in catalyst consists of 0.1%～5.0%, is preferably 0.2%～3.0%.
Described inorganic refractory oxide is to be selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay one or more, is preferably aluminium oxide and/or silica, more preferably aluminium oxide.Its precursor can be selected from boehmite, boehmite, diaspore, gibbsite and visit in the aluminium stone one or more, is preferably boehmite.
Catalyst property of the present invention is as follows: specific surface is 200～350m
2/ g, pore volume are 0.3～0.5ml/g.The specific surface of catalyst and pore volume are to adopt ASAP 2400 among the present invention, and the low temperature liquid nitrogen absorption method calculates through BET.
Preparation of catalysts method disclosed in this invention comprises:
(1), the IB element is loaded on the TON type molecular sieve, through super-dry, roasting, obtain containing the TON type molecular sieve of IB element.
(2), the TON type molecular sieve that contains the IB element, inorganic refractory oxide, extrusion aid, water, peptizing agent that step (1) is obtained fully mix together and pinch into plastic paste, extruded moulding through super-dry, roasting, obtains catalyst carrier;
(3), load hydrogenation component on the carrier that obtains of step (2), drying and roasting obtain catalyst of the present invention.
The described IB element of step (1) mode of loading can adopt the method for mixing or flooding, and preferably adopts infusion process.The method of mixing will contain the IB element compound exactly and directly mix with molecular sieve, add an amount of water then and mix; The method of dipping is exactly to be prepared into the solution that contains the IB element with containing the IB element compound earlier, the concentration of solution can change in a big way, general its weight percent concentration that contains the IB element is 0.5%～20%, then molecular sieve is fully mixed with prepared solution, ℃ dry 1h～48h through normal temperature～300 again, 400 ℃～800 ℃ roasting 0.5h～10h obtain the TON molecular sieve of the IB of containing element of the present invention.Load IB element preferable methods of the present invention can make the IB element be more evenly distributed on the molecular sieve surface like this, and help the modification to the molecular sieve aperture for the method for dipping.The described IB of containing family metallic compound is the salt that is dissolvable in water water, and for example chloride, nitrate and acetate etc. are preferably nitrate.
The described extrusion aid of step (2) is the additive that helps smooth extrusion, and as sesbania powder, starch, graphite etc., addition is a conventional amount used, is generally 2%～10% of carrier (butt) weight.Described peptizing agent is the material that can make the mixture peptization, and for example Ludox, alkali compounds or acid compound are preferably acid compound, inorganic acid more preferably, for example hydrochloric acid, nitric acid etc., its addition is a conventional amount used, is generally 1%～5% of carrier (butt) weight.Described support shapes (cross sectional shape) can also can be the distortion of these shapes for circle, quadrangle, triangle, cloverleaf pattern or bunge bedstraw herb shape etc.
The load of the described hydrogenation component of step (3) can be adopted metal carrying method at present commonly used, and for example dipping or ion-exchange etc. are preferably the method for dipping, more preferably the method for saturated dipping.The method of saturated dipping is exactly the solution that is mixed with the carrier saturated extent of adsorption with a certain amount of hydrogenation component compound, then solution is mixed with carrier.The hydrogenation component compound be for adopting this area salt that is dissolved in water commonly used, for example chloroplatinic acid, palladium bichloride, palladium nitrate or contain the ammino-complex aqueous solution etc. of noble metal.
The drying of catalyst carrier and catalyst and roasting condition can be same as the prior art described in step (2) and (3), for example drying condition is normal temperature～300 ℃ maintenance 1h～48h, the carrier roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that the catalyst roasting condition is 350 ℃～600 ℃ and keeps 1h～8h.
Catalyst of the present invention needs to reduce processing before charging, reducing condition is as follows: in the presence of hydrogen, and 300 ℃～500 ℃ of temperature, pressure 0.5MPa～10MPa, 1 hour～12 hours time.
The present invention adopts the TON structure molecular screen, because this molecular sieve analog has the oval straight hole road that the aperture is 0.53nm * 0.57nm, and its acid matter is based on middle strong acid, can produce tangible restriction to highly-branched chain isomerous body, help long-chain normal paraffin and carry out isomerization reaction according to the key reaction mechanism, isomerization has special effect to long-chain normal paraffin.But because unmodified TON molecular sieve pore passage structure and the reaction of acid confrontation isomerization of long-chain normal paraffin also are not very desirable, cause its reactivity worth to decrease, especially the selectivity of isomerization reaction is lower, after passing through among the present invention to introduce IB family element, an aspect can combine with some highly acid centers on molecular sieve surface, form more stable complex, produce more weak acid center, and strong acid center is the main cause that causes side reactions such as cracking.The another one aspect is the duct that the IB family element of introducing can enter into molecular sieve, the size in aperture is reduced, so just further increased constraint, improved the selectivity of few branched chain isomer, thereby improved the isomerization selectivity of catalyst highly-branched chain isomerous body.
The present invention preferably adopts noble metal as hydrogenation component, be because isomerization reaction and cracking reaction all are consecutive reactions, isomerization process is generally all passed through in cracking for long chain alkane, when the isomers that produces can not be in time from the acid centre desorption, just further isomerization generates highly-branched chain isomerous body, and then generation cracking reaction, improve the isomerization selectivity, the isomers that just need make the reaction generation is timely from the acid centre desorption, avoid side reaction generations such as cracking, this just requires catalyst can have higher hydrogenation activity, and precious metal element obviously is best selection.
Catalyst of the present invention can be used for the isomerization of long-chain normal paraffin reaction, is particularly useful for the isomerization reaction of positive structure dodecane hydrocarbon.
Compared with prior art, catalyst of the present invention has the high advantage of isomerization selectivity.
The specific embodiment
Further specify Preparation of catalysts process of the present invention below by embodiment, but invention should not be deemed limited among the following embodiment.
Catalyst of the present invention is to adopt the 10ml fixed-bed micro-reactor to estimate, with the n-dodecane is model compound, loaded catalyst is 10ml (40～60 order), before the charging catalyst is carried out prereduction, noble metal on the catalyst is changed into go back ortho states, reducing condition is: 480 ℃ of temperature, pressure 6.0MPa, 8 hours time.Product carries out quantitative analysis on the HP5890 gas chromatograph.Analysis condition: capillary column HP-1 (OV-101, non-polar column), internal diameter 0.20mm, long 50m, split ratio 200: 1, temperature programming, FID detects.The selectivity (percentage by weight) of conversion ratio of n-dodecane (percentage by weight) and isomery dodecane calculates with following formula respectively.
The conversion ratio of n-dodecane=(n-dodecane weight content in the 1-product) * 100%
The selectivity of isomery dodecane=(conversion ratio of the weight content/n-dodecane of isomery dodecane in the product) * 100%
Embodiment 1
The preparation method of catalyst of the present invention (E-1) is as follows:
(1) the used ZSM-22 of the present invention is the method preparation according to Chinese patent CN1565969A embodiment 1, and the molecular sieve silica alumina ratio that obtains is 92, specific area 223m
2/ g, pore volume 0.21mL/g.
(2) with silver nitrate (Tianjin chemical reagent factory, analyze pure) to be mixed with the argentiferous weight percent concentration be 3.0% the aqueous solution, molecular sieve 4850 grams that step (1) is obtained fully mix with the above-mentioned silver-containing solution of 5000 grams, in 110 ℃ of following constant temperature 6 hours, 450 ℃ of following constant temperature 6 hours, the weight percent content that obtains silver is 3.0% ZSM-22, and the ZSM-22 that contains the IB element here is called modified molecular screen (down together).
(3) get the modified molecular screen (dry basis that 1500 gram steps (2) obtain, together following) and 500 gram (dry basises, down together) (Germany produces the SB alumina powder, trade names are SB) fully mix, adding 100 gram weight concentration then is 40% rare nitric acid and an amount of water, mix and pinch into plastic paste, it is the cylindrical bar of 1.2mm that extrusion becomes diameter, with this article shaped in 110 ℃ of constant temperature 8 hours, again 550 ℃ of following constant temperature 4 hours, obtain catalyst carrier, it consists of: 75wt% modified molecular screen and 25wt% aluminium oxide.
(4) with containing H
2PtCl
6The aqueous solution, the method that adopts saturated dipping loads to platinum on the carrier that step (3) obtains, in 130 ℃ of following constant temperature 6 hours, 550 ℃ of following constant temperature 3 hours obtained catalyst of the present invention, is numbered E-1, the weight content of platinum is 0.66wt% in the catalyst.
Embodiment 2
The preparation method of catalyst of the present invention (E-2) is as follows:
The Preparation of catalysts method is with embodiment 1, difference is that the weight content of silver in the molecular sieve is 5%, catalyst carrier consist of 20wt% modified ZSM-5-22 and 80wt% aluminium oxide, the content of platinum is 0.80wt% in the catalyst, the drying of catalyst and roasting condition are: 110 ℃ of following constant temperature 4 hours, and 420 ℃ of following constant temperature 6 hours obtains catalyst of the present invention and is numbered E-2, its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Embodiment 3
The preparation method of catalyst of the present invention (E-3) is as follows:
The Preparation of catalysts method is with embodiment 1, difference is that employed solution is 12wt% for the concentration of silver, the content that obtains silver in the molecular sieve is 11.8wt%, hydrogenation component is a palladium, and used maceration extract is a palladium nitrate solution, and wherein palladium is in metal, solution concentration is 5wt%, obtain catalyst E-3 of the present invention, its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Embodiment 4
The preparation method of catalyst of the present invention (E-4) is as follows:
The Preparation of catalysts method is with embodiment 1, difference is that molecular sieve is with containing golden solution impregnation, obtain containing the ZSM-22 of gold, used gold-containing compound is a gold chloride, and the concentration of gold is 3.5wt% in the gold-containing solution, the content of gold is 3.5wt% in the modified molecular screen that obtains, the modified molecular screen weight content is 90% in the carrier, and hydrogenation component is a platinum, obtains catalyst E-4 of the present invention, its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Embodiment 5
The preparation method of catalyst of the present invention (E-5) is as follows:
The Preparation of catalysts method is with embodiment 1, difference is that molecular sieve is with containing silver and golden solution impregnation, in metal, its silver-colored weight percent concentration is 1.2% in the maceration extract, and the weight percent concentration of gold is 2.8%, obtain the ZSM-22 of argentiferous and gold, the modified molecular screen weight content is 50% in the catalyst carrier, and hydrogenation component is a platinum, obtains catalyst E-5 of the present invention, its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Embodiment 6
The preparation method of catalyst of the present invention (E-6) is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that hydrogenation component is platinum and palladium bimetallic, obtains catalyst E-6 of the present invention, and its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Embodiment 7
The preparation method of catalyst of the present invention (E-7) is as follows:
Get 236 gram silver nitrates (silver content is 63.5wt%) and mix back adding 2800 gram water with 4850 gram ZSM-22 molecular sieves, after said mixture fully stirs, in 110 ℃ of following constant temperature 6 hours, 450 ℃ of following constant temperature 6 hours, the weight percent content that obtains silver is 3.0% ZSM-22.Other processes obtain catalyst E-7 of the present invention with embodiment 1, and its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Comparative Examples 1
Comparative catalyst's (C-1) preparation method is as follows:
The Preparation of catalysts method is with embodiment 1, and difference is that used molecular sieve handles without Ag-containing solution, obtains comparative catalyst C-1, and its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Comparative Examples 2
Comparative catalyst's (C-2) preparation method is as follows:
The Preparation of catalysts method is with embodiment 6, and difference is in the catalyst not argentiferous, obtains comparative catalyst C-2, and its composition and physico-chemical property see Table 1, and evaluation result sees Table 2.
Each implements the main physico-chemical property of (comparison) example preparation catalyst table 1
| Catalyst | Pt，wt％① | Pd，wt％① | Ag，wt％② | Au，wt％② | Modified ZSM-5-22, % are 1. | S，m 2/g | V，ml/g |
| E-1 | 0.66 | - | 3.0 | - | 75 | 255 | 0.35 |
| E-2 | 0.80 | - | 5.0 | - | 20 | 272 | 0.43 |
| E-3 | - | 3.7 | 12 | - | 75 | 237 | 0.30 |
| E-4 | 1.20 | - | - | 3.5 | 90 | 242 | 0.33 |
| E-5 | 0.38 | - | 1.2 | 2.8 | 50 | 246 | 0.33 |
| E-6 | 0.42 | 1.3 | 3.0 | - | 75 | 240 | 0.34 |
| E-7 | 0.66 | - | 3.0 | - | 75 | 251 | 0.35 |
| C-1 | 0.66 | - | - | - | 75 | 258 | 0.36 |
| C-2 | 0.42 | 1.3 | - | - | 75 | 251 | 0.35 |
Annotate: 1. be benchmark with the catalyst; 2. with the molecular sieve benchmark; S is the specific surface of catalyst, and V is the pore volume of catalyst.
The reaction result of table 2 catalyst
The evaluation result of table 2 shows, compares with the comparative catalyst, adopts catalyst provided by the invention, in the isomerization reaction for n-dodecane, during near (about 80%), the selectivity of isomery dodecane improves 8%～16% at conversion ratio, and isomerization selectivity effect significantly improves.
In addition, the reaction result of embodiment 1 and embodiment 7 as can be seen from last table, the Preparation of catalysts method also influences its reactivity worth, method with the liquor argenti nitratis ophthalmicus dipping is better than the effect that silver loads on the molecular sieve molecular sieve to be handled with the method for mixing, form when identical at catalyst, under approaching n-dodecane conversion ratio condition, with the catalyst isomerization selectivity raising 3.5% of the method preparation of flooding.
Catalyst of the present invention can also be applied to the processing procedure of waxy feeds such as paraffin, lubricating oil, white oil, VGO, AGO, is particularly suitable for lubricating oil isomerization dewaxing process.
Claims (13)
1. a catalyst for normal paraffin isomerization contains TON type molecular sieve, inorganic refractory oxide and hydrogenation component, it is characterized in that containing IB family element in the described TON type molecular sieve, and in metal, its weight content in molecular sieve is 0.5%～10%.
2. according to the described catalyst of claim 1, it is characterized in that in the described TON type molecular sieve, IB family element is 0.5%～5% in the weight content of metal.
3. according to the described catalyst of claim 1, it is characterized in that described IB family element is selected from one or more in copper, silver and the gold.
4. according to the described catalyst of claim 1, it is characterized in that described IB family element is silver.
5. according to the described catalyst of claim 1, it is characterized in that the composition of described catalyst is as follows by weight:
The TON type molecular sieve that contains IB family element: 10%～90%;
Hydrogenation component is in metal: 0.1%～5.0%;
Inorganic refractory oxide: surplus.
6. according to the described catalyst of claim 1, it is characterized in that described TON type molecular sieve is the ZSM-22 molecular sieve, its silica alumina ratio is 50～200.
7. according to the described catalyst of claim 1, it is characterized in that described hydrogenation component is to be selected from palladium, platinum, ruthenium and the rhodium one or more; Described inorganic refractory oxide is to be selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, zirconia and the clay one or more.
8. according to the arbitrary described catalyst of claim 1～7, it is characterized in that described hydrogenation metal is platinum and/or palladium, accounts for 0.2%～3.0% of catalyst weight; Described inorganic refractory oxide is an aluminium oxide, and its precursor can be selected from boehmite, boehmite, diaspore, gibbsite and visit in the aluminium stone one or more.
9. according to the described catalyst of claim 1, it is characterized in that described catalyst property is as follows: specific surface is 200～350m
2/ g, pore volume are 0.3～0.5ml/g.
10. the arbitrary described Preparation of catalysts method of claim 1～9 is characterized in that comprising the steps:
(1), the IB element is loaded on the TON type molecular sieve, through super-dry, roasting, obtain containing the TON type molecular sieve of IB element.
(2), the TON type molecular sieve that contains the IB element, inorganic refractory oxide, extrusion aid, water, peptizing agent that step (1) is obtained fully mix together and pinch into plastic paste, extruded moulding through super-dry, roasting, obtains catalyst carrier;
(3), load hydrogenation component on the carrier that obtains of step (2), drying and roasting obtain catalyst of the present invention.
11. in accordance with the method for claim 10, it is characterized in that the described IB element of step (1) carrying method is an infusion process, the solution that is about to contain the IB element fully mixes with TON type molecular sieve, the weight percent concentration that wherein contains IB element in the solution of IB element is 0.5%～20%, behind the dipping through normal temperature～300 ℃ dry 1h～48h, 400 ℃～800 ℃ roasting 0.5h～10h obtain containing the TON type molecular sieve of IB element.
12. in accordance with the method for claim 10, the drying condition that it is characterized in that catalyst carrier described in described step (2) and (3) and catalyst is normal temperature～300 ℃ maintenance 1h～48h, the carrier roasting condition is 400 ℃～800 ℃ and keeps 0.5h～10h that the catalyst roasting condition is 350 ℃～600 ℃ and keeps 1h～8h.
13. the application of the arbitrary described catalyst of claim 1～9 in the isomerization of long-chain normal paraffin reaction.
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| CN101934237A (en) * | 2010-08-03 | 2011-01-05 | 仇文杰 | Lubricating oil catalyst and preparation method thereof |
| CN106540738A (en) * | 2016-09-27 | 2017-03-29 | 江苏大学 | The method that metal Ag modified molecular screens are catalyzed 2,5 dichlorotoleune isomerization |
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- 2006-11-01 CN CN200610134165A patent/CN100594063C/en active Active
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| CN101934237A (en) * | 2010-08-03 | 2011-01-05 | 仇文杰 | Lubricating oil catalyst and preparation method thereof |
| CN101934237B (en) * | 2010-08-03 | 2013-01-09 | 仇文杰 | Lubricating oil catalyst and preparation method thereof |
| CN106540738A (en) * | 2016-09-27 | 2017-03-29 | 江苏大学 | The method that metal Ag modified molecular screens are catalyzed 2,5 dichlorotoleune isomerization |
| CN107876084A (en) * | 2017-10-23 | 2018-04-06 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of the molecular sieve catalysts of integrated nano hetero atom ZSM 22 |
| CN112705220A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for carbon-tetra-alkyl hydrocarbon skeleton isomerization reaction and preparation method and application thereof |
| CN111804330A (en) * | 2020-07-09 | 2020-10-23 | 中国石油大学(北京) | Sulfate/zirconia @ SAPO-11 composite material, hydrocarbon isomerization catalyst and application |
| CN111804330B (en) * | 2020-07-09 | 2023-04-25 | 中国石油大学(北京) | Sulfate radical/zirconia@SAPO-11 composite material, hydrocarbon isomerization catalyst and application |
| CN112226210A (en) * | 2020-11-08 | 2021-01-15 | 盘锦北方沥青股份有限公司 | Heat conduction oil with low oil sludge tendency and preparation method thereof |
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