CN103301835B - Straight-chain lightweight alkane isomerization catalyst, and preparation method and application thereof - Google Patents
Straight-chain lightweight alkane isomerization catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a straight-chain lightweight alkane isomerization catalyst, and a preparation method and an application thereof. The catalyst comprises a composite macroporous alumina carrier and 0.01-2.0% of platinum by mass calculated with the carrier as a reference. The composite macroporous alumina carrier comprises, by mass, calculated with the carrier as a reference, 5-45% of aluminum sol, 50-90% of macroporous alumina, and hydrochloric acid added according to a mass ratio of Al2O3 in the macroporous alumina to HCl of 15-200; kneading, strip extrusion forming and drying are carried out, and the material is roasted for 0.5-6h under a temperature of 400-700 DEG C; the material is then impregnated for 1-30h by using chloroplatinic acid according to a platinum load; the material is dried, and is roasted for 0.5-6h under a temperature of 400-700 DEG C, such that the catalyst is prepared. An Al/Cl molar ratio of the aluminum sol is 0.9-1.4. The volume of the macroporous alumina is 1.0-1.8ml/g. The catalyst is suitable for a straight-chain lightweight alkane isomerization reaction, and has good mechanical strength and catalytic activity. The catalyst has the advantages of high product liquid yield and high multi-branched alkane selectivity. The catalyst can be used for improving light hydrocarbon component octane number.
Description
Technical field
The present invention relates to a kind of isomerization catalyst and its preparation method and application, more specifically to the low temp isomerizing catalyst of straight chain light paraffins of a kind of platinum group noble metal and compound macropore alumina supporter, and its preparation method and application method.
Background technology
At crude oil once with in secondary processing process, can produce with C
5~ C
6for the light ends fractionation mainly formed, generally as the blend component of gasoline, but wherein contained n-alkane octane number is lower, call in the front-end octane number (FEON) that can reduce gasoline in gasoline in a large number thus affect quality of gasoline, isoparaffin has higher octane number, by small-molecular-weight C contained in blended gasoline
5~ C
6n-alkane changes into isoparaffin, effectively can improve the front-end octane number (FEON) of gasoline, as CN1037111C, described in CN1345914A, CN1521240A, CN1660973A, CN101397230A, along with the strict restriction to arene content in motor petrol, isomerization process to the production improving quality of gasoline and clean fuel all tool be of great significance.A large amount of reports is had, as described in USP4804803, USP4831209, USP5003118, USP5082989, USP5233120, USP5602291, EP256604A2 to light hydrocarbon isomerization process and the technology after improving in prior art.
Hydroisomerization reaction catalyst used is mainly the catalyst having noble metal containing zeolite type, solid ultra strong acid type and halogen-containing alumina type three kinds of supported on carriers.And the catalyst of also mainly zeolite type and the halogen-containing alumina load noble metal of application of industrially succeeding.Early stage catalyst for normal paraffin isomerization is Friedel-Craft (Friedel-Crafts) type catalyst mainly, as AlCl
3/ HCl, AlBr
3the systems such as/HBr, the reactivity of catalyst is high, and reaction temperature is low, be conducive to the concentration improving isoparaffin equilibrium composition like this, its shortcoming has stronger toxicity and corrosivity, is difficult to meet environmental requirement, and require strict to moisture, sulfide, alkene in raw material etc.In recent years gradually eliminate by bifunctional catalyst, bifunctional isomerization catalyst is mainly made with acid carrier supported V III metal, the acid activated centre required for reaction is provided by carrier, there is provided hydrogenation dehydrogenation activity center by group VIII metal, acting in conjunction promotes that alkane isomerization reacts.
Containing the bifunctional catalyst of zeolite type, because technological process is simple, require relatively wide to the impurity content in raw material, industrially be widely applied, it generally carries out hydroisomerization reaction more than 250 DEG C, with crystalline silicate as modenite, Beta zeolite, faujasites etc. are carrier, aluminium oxide or other refractory oxides are binding agent, supporting platinum-group metals, mainly platinum or palladium, prepare the isomerization catalyst with acid function, as USP4232181, GB1039246, GB1189850, USP4665272, EP0552069, described in CN1011695B etc.The shortcoming of zeolite catalyst is that activity is lower, and application of temperature is higher, and under high temperature, the equilibrium concentration of isomerized products can be lower, directly can affect the octane number of product.Therefore in prior art, various modification has been carried out to zeolite, to improving the stereoselectivity of catalyst, as as described in USP3527835, USP5095169, CN87103444A, CN1270990A, CN1345913A, CN1022420C etc., but these methods improving merely zeolite acidity can not make the stereoselectivity of catalyst obtain larger raising.Adopt zeolite and combine and also have report to the research work of carrier improvement, as CN1304793A, CN1305871A, described in CN1672217A, due to the serviceability temperature of catalyst can not be reduced, the stereoselectivity of product also difficulty is greatly improved, therefore there was reported employing in prior art and introduce chlorine or fluorine in the carrier to improve the report of acidity of catalyst, as USP4789655 introduces chlorine by gas phase oxi-chlorination in the mordenite catalyst of year platinum, USP3932554 then adopts fluorine-containing halogenated hydrocarbon to contact with the mordenite catalyst carrying platinum or palladium, make it have good isomerization performance, but in catalyst use procedure, chlorine or fluorine can run off gradually along with the carrying out of reaction, cause catalyst activity reduction and corrosion of equipment.
Solid super-strong acid is owing to having stronger acidity, and isomerization activity is high, thus can carry out isomerization reaction at a lower temperature, obtains higher isomerization rate, is particularly suitable for the catalyst as alkane isomerization, thus comes into one's own.The solid super-strong acid reacted for light hydrocarbon isomerization at present mainly adopts the zirconia carrier of containing sulfate radicals, and the catalyst that load platinum-group noble metals is formed, as described in USP3032599, CN1324392A, CN1840513A, CN1314935A, CN1100613C, CN1185325C, CN100556544C etc.Because solid super-strong acid need use in almost water free environment, in use also need with A type molecular sieve etc. the moisture in raw material is down to 5 micrograms/gram below, in order to avoid affect the activity and selectivity of catalyst.Disclose in CN101172248A and adopt containing sulfate radical, zirconium dioxide be compounded with the catalyst of L zeolite, can at higher reaction temperature 300 ~ 430 DEG C, to the C compared with Long carbon chain
7~ C
20carry out isomerization reaction, to improve liquid yield.CN102107142A discloses C
7~ C
10the isomerization catalyst preparation method containing platinum, phosphorus heteropoly tungstic acid and MCM-41 molecular sieve of n-alkane isomery.CN02132476.X then discloses not containing platinum noble metals, adopts phosphorus tungsten, silicotungstic heteropolyacid catalyst to C
4~ C
12n-alkane carries out the technology of isomerization reaction.Other use as also all disclosed in the prior aries such as USP5510309, USP5719097, USP5648589, USP5422327, CN101052465A, CN1254308C the carriers such as wolframic acid zirconia containing noble metal isomerization catalyst.Because these shortcomings containing the isomerization catalyst of polyacid class carrier are not enough to isomerized catalytic selectivity, as USP5510309, USP5780328, USP5854170, USP6080904, therefore there was reported in prior art and adopt sial etc. to carry out promotion modification technology to containing tungstates Zirconia carrier, as USP5422327, USP5648589, USP5837641, USP6767859, USP6326328, described in CN100528344C, it is generally applied in the isomerization reaction of long chain alkane, and need constantly to supplement halogen auxiliary agent to maintain stable catalytic activity along with the carrying out of course of reaction, as disclosed in CN100425583C, but do like this and can cause certain corrosion to appliance arrangement.For now, solid ultra strong acid type isomerization catalyst also just has the catalyst of applications well prospect, still could not obtain good practical application.
Comparatively close with the present invention is in the prior art traditional low temp isomerizing catalyst, as disclosed in USP4804803, USP5082989, have employed chloride 2 ~ 10%, that platiniferous 0.01 ~ 25% aluminium oxide the is carrier alumina catalyst promoted by hydrogen chloride.And at CN1244570A in its reduction benzene content in gasoline provided and isomerization of paraffinic hydrocarbons method, have employed containing 4 ~ 15% halogens as chlorine and group VIII metal, and the catalyst be made up of as carrier η aluminium oxide and gamma-alumina, its shortcoming is that the chlorine of load very easily runs off along with the carrying out of course of reaction, easy etching apparatus on the one hand, the acidity that on the other hand carrier can not be made to provide stable, have impact on the performance of catalyst catalytic performance, thus limits its application in practice.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, the low temp isomerizing catalyst of straight chain light paraffins of a kind of platinum group noble metal and compound macropore alumina supporter is provided, and methods for making and using same.
Make a general survey of prior art, adopting with zeolite is temp isomerizing catalyst in carrier, though what have impurity contents such as the water in feedstock oil and sulphur is less demanding, and to the free from corrosion advantage of consersion unit, but due to the acidity of zeolitic material lower, isomerization reaction need be carried out at a higher temperature, but isomerization reaction is exothermic reaction, and being subject to the restriction of thermodynamical equilibrium, temperature rising can reduce the Equilibrium yield of isoparaffin, and isoparaffin yield when therefore reaching chemical balance is also low.Though the alumina based catalysts of halogenation and solid super acid catalyst have very strong acidity, carry out isomerized reaction temperature lower, the more high outstanding advantages of yield of isoparaffin, but the shortcoming of this type of catalyst has strict demand to the impurity content in feedstock oil, strict restriction is had to the content of the water in feedstock oil and sulphur, the alumina based catalysts of halogenation simultaneously also needs constantly to note chlorine to maintain the acid function of catalyst along with chlorine runs off in course of reaction, thus requires that reaction unit has stronger corrosion resistance.How to provide a kind of sour shape good stability, raw material accommodation wide, little to apparatus corrosivity, the catalyst that straight chain light paraffins low temperature isomerization reaction activity is high just becomes technological difficulties.The invention provides a kind of catalyst being suitable for the isomerization reaction of lightweight linear paraffin low temperature for this reason, have employed a kind of wide to moisture accommodation in raw material, can the acid constituent element of the halogen-containing class of good solidification, and provide the compound macropore alumina supporter of stable acidic function, the low temp isomerizing catalyst made by dip loading VIII noble metal platinum.
Specifically, a kind of straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention and its preparation method and application, it is characterized by described catalyst and comprise compound macropore alumina supporter and the platinum of to take carrier as the content of benchmark be 0.01 ~ 2.0 quality %, platinum content under preferable case is 0.2 ~ 0.8 quality %, adopt chloroplatinic acid to be raw material dip loading platinum on carrier, chloroplatinic acid can by being purchased convenient acquisition.
Compound macropore alumina supporter described in straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention, comprising in the macroporous aluminium oxide of the Alumina gel of 5 ~ 45 quality % of aluminium oxide, 50 ~ 90 quality %, is in the macroporous aluminium oxide of the Alumina gel of 10 ~ 28 quality % of aluminium oxide, 70 ~ 88 quality % under preferable case.Alumina gel and macroporous aluminium oxide can by commercially available, and the Al/Cl mol ratio of wherein said Alumina gel is 0.9 ~ 1.4, and the Al/Cl mol ratio under preferable case is 1.0 ~ 1.3; The pore volume of described macroporous aluminium oxide is 1.0 ~ 1.8 mls/g, and the pore volume under preferable case is 1.1 ~ 1.5 mls/g.
Al in macroporous aluminium oxide is pressed in the preparation method of straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention
2o
3/ HCl be 15 ~ 200 mass ratio add hydrochloric acid, press Al in preferred situation
2o
3/ HCl be 40 ~ 90 mass ratio add hydrochloric acid, hydrochloric acid can by commercially available.The dilute hydrochloric acid water yield used carries out regulable control needed for water during catalyst extrusion/alumina powder ratio, according to the experience of those skilled in the art, water during general control catalyst extrusion/alumina powder ratio is not 0.5: 1 ~ 1.5: 1 etc., the water that major part is added can vapor away in dry run, can not affect the catalytic performance of catalyst.
In the preparation method of straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention, kneading, extruded moulding, drying and method of roasting belong to the operation of chemical field generality, are well known to those skilled in the art.The roasting 0.5 ~ 6 hour at 400 ~ 700 DEG C of carrier after shaping and drying, roasting 1 ~ 4 hour at 450 ~ 600 DEG C under preferable case.Forming method in described preparation process also can adopt rolling ball method, other forming methods such as ball, pressed disc method carry out, and to make difform composite alumina support, these forming methods are known by persons skilled in the art.
The noble metal platinum load described in preparation method of straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention is with the load capacity of chloroplatinic acid by platinum in above-mentioned catalyst, compound macropore alumina supporter is flooded 1 ~ 30 hour in platinum acid chloride solution, the volume ratio of carrier and maceration extract is preferably 1: 1.2 ~ 3, and its operating process is known by persons skilled in the art.
The dipping chloroplatinic acid described in preparation method of straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention dried catalyst, at 400 ~ 700 DEG C, roasting is made for 0.5 ~ 6 hour, roasting 1 ~ 4 hour at 450 ~ 600 DEG C under preferable case.
Present invention also offers a kind of straight chain light paraffins low temperature isomerization method, it is characterized by described straight chain light paraffins raw material is C
5~ C
6lighter hydrocarbons, wherein normal paraffin content is 20 ~ 80 quality %; Be applicable to raw material of the present invention comprise light condensate, light straight-run naphtha, gas condensate, gently raise straight run tops or the hydrogasoline that excess oil, light reformate and the end point of distillation are 77 DEG C.
Make straight chain light paraffins raw material and catalyst of the present invention in temperature 130 ~ 170 DEG C, pressure 1.5 ~ 2.0MPa, feed weight air speed 0.6 ~ 2.0 hour in presence of hydrogen
-1with haptoreaction under the condition of hydrogen/hydrocarbon mol ratio 0.5 ~ 3.0.
Straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the invention, the compound macropore alumina supporter cost adopted will be hydrolyzed by the low-carbon alkyl aluminium of costliness the high purity aluminium oxide obtained far below what commonly use in prior art, thus reduce catalyst cost of manufacture, and its acidity not easily runs off along with the carrying out of reaction, little to equipment corrosion, be suitable for the isomerization reaction at low temperatures of straight chain light paraffins, the n-alkane be conducive in raw material generates more isomerization product.Have that mechanical strength is high in reaction use procedure, catalytic activity and good stability, product liquid is received and the selective high plurality of advantages of multibranched paraffin, effectively can improve the octane number of light hydrocarbon component.
Detailed description of the invention
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In embodiments, sample well volume adopts GB/T5816-1995 method to measure; Composition assay adopts x-ray fluorescence analyzer to measure according to GB/T12690.5-90; Crushing strength adopts detector for strength of particles to detect.
Other detects see (" oil and oil product test method national standard " published by China Standards Press 1989).
Embodiment 1
By 100 grams of macroporous aluminium oxide (industrial goods, Sichuan profit and catalysis material company, solid content 63 quality %, pore volume 1.5 mls/g) and 100 ml aluminium colloidal sol (industrial goods, Sichuan profit and catalysis material company, Al/Cl mol ratio 1.2, aluminium oxide 20 quality %) mixing, by 2 milliliters of hydrochloric acid (chemical pures, Beijing chemical reagent company) with after 30 ml distilled water dilutions, add in material and mediate and extruded moulding, 120 degree dry 2 hours, and 550 degree of roastings obtained compound macropore alumina supporter after 4 hours.
Get the compound macropore alumina supporter 100 grams by butt, with the chloroplatinic acid (chemical pure of 45 milliliter of 8.6 mol/L, Beijing chemical reagent company preparation of reagents) solution impregnation 24 hours, 120 degree dry 4 hours, roasting 4 hours in 550 degree of air, the catalyst of the obtained embodiment of the present invention 1, in gained catalyst platinum content be 0.35 quality %, bulk density 0.72 grams per milliliter, crushing strength 75 newton/centimetre.
Comparative example 1
By disclosed in CN1244570A embodiment 1 content preparation, obtain the catalyst of comparative example 1, in gained catalyst platinum content be 0.35 quality %, bulk density 0.70 grams per milliliter, crushing strength 40 newton/centimetre.
Embodiment 2
By (the same for 100 grams of macroporous aluminium oxides, solid content 65 quality %, pore volume 1.2 mls/g) and 100 ml aluminium colloidal sols (the same, Al/Cl mol ratio 1.3, aluminium oxide 24 quality %) mixing, by 3 milliliters of hydrochloric acid (the same) with after 30 ml distilled water dilutions, add in material and mediate and extruded moulding, 110 degree dry 4 hours, and 600 degree roastings obtained compound macropore alumina supporter after 2 hours.
Get the compound macropore alumina supporter 100 grams by butt, by chloroplatinic acid (the same) solution impregnation 20 hours of 50 milliliter of 7.5 mol/L, 120 degree dry 3 hours, roasting 6 hours in 500 degree of air, the catalyst of the obtained embodiment of the present invention 2, in gained catalyst platinum content be 0.35 quality %, bulk density 0.73 grams per milliliter, crushing strength 80 newton/centimetre.
Embodiment 3
By (the same for 150 grams of macroporous aluminium oxides, solid content 67 quality %, pore volume 1.4 mls/g) and 100 ml aluminium colloidal sols (the same, Al/Cl mol ratio 1.1, aluminium oxide 21 quality %) mixing, by 4 milliliters of hydrochloric acid (the same) with after 50 ml distilled water dilutions, add in material and mediate and extruded moulding, 110 degree dry 4 hours, and 500 degree roastings obtained compound macropore alumina supporter after 6 hours.
Get the compound macropore alumina supporter 100 grams by butt, by chloroplatinic acid (the same) solution impregnation 16 hours of 50 milliliter of 7.0 mol/L, 120 degree dry 2 hours, roasting 3 hours in 580 degree of air, the catalyst of the obtained embodiment of the present invention 3, in gained catalyst platinum content be 0.34 quality %, bulk density 0.71 grams per milliliter, crushing strength 70 newton/centimetre.
Embodiment 4
The isomerization activity evaluation of embodiment 1 ~ 3 and comparative example 1 catalyst is carried out on small-sized continuous micro-trans-chromatogram arrangement, capillary chromatographic column column length 60 meters, OV-101 Stationary liquid, and nitrogen is as carrier gas, and product is detected by hydrogen flame ion detector.Catalyst activates 3 hours before the reaction in the air atmosphere of 450 DEG C of flowings, is cooled to 250 DEG C of reductase 12s hour under the nitrogen atmosphere of flowing.
Reaction condition is: reaction raw materials is n-hexane, reaction temperature 170 DEG C, reaction pressure 2.0MPa, air speed 2.0 hours
-1, hydrogen/n-hexane mol ratio 3.0, catalyst sample-loading amount 1.0 grams, successive reaction 12 hours post analysis reaction results.
Conversion ratio=[the n-hexane quality transformed in reaction/react initial n-hexane quality] × 100%
Selective=[the n-hexane quality transformed in the isoparaffin quality/reaction of generation] × 100%
Isoparaffin productive rate=isoparaffin the quality of the generation [/ react initial n-hexane quality] × 100%
The isomerization reaction evaluation result of table 1, embodiment 1 ~ 3 and comparative example 1:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Conversion ratio % | 83.9 | 84.6 | 84.0 | 78.4 |
| Selective % | 97.6 | 95.4 | 96.8 | 82.2 |
| Isoparaffin productive rate % | 81.9 | 80.7 | 81.3 | 64.4 |
From the n-hexane low temperature isomerization reaction evaluation result explanation of table 1, get continuous 12 hours reacted stable product distribution results, straight chain Performance of Isomerization Catalysts for Light n-Paraffin provided by the present invention can obtain better stable catalytic activity and isomerized products selective.
Finally it should be noted that, above embodiment is only unrestricted for illustration of technical scheme of the present invention, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not depart from the spirit and scope of technical solution of the present invention.
Claims (9)
1. a straight chain Performance of Isomerization Catalysts for Light n-Paraffin, it is characterized by described catalyst and comprise compound macropore alumina supporter and the platinum of to take carrier as the content of benchmark be 0.01 ~ 2.0 quality %, described compound macropore alumina supporter comprises in the macroporous aluminium oxide of the Alumina gel of 5 ~ 45 quality % of aluminium oxide, 50 ~ 90 quality % and by Al in macroporous aluminium oxide
2o
3/ HCl is the hydrochloric acid that adds of mass ratio of 15 ~ 200, after kneading, extruded moulding and drying, roasting 0.5 ~ 6 hour at 400 ~ 700 DEG C, then flood 1 ~ 30 hour with chloroplatinic acid by described platinum load capacity, after drying, at 400 ~ 700 DEG C, roasting is made for 0.5 ~ 6 hour; The Al/Cl mol ratio of wherein said Alumina gel is 0.9 ~ 1.4, and the pore volume of described macroporous aluminium oxide is 1.0 ~ 1.8 mls/g; This catalyst is suitable for the low temperature isomerization reaction of straight chain light paraffins.
2. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, is characterized in that described isomerization catalyst take carrier as the platinum content of benchmark is 0.2 ~ 0.8 quality %.
3. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, is characterized in that described compound macropore alumina supporter comprises in the macroporous aluminium oxide of the Alumina gel of 10 ~ 28 quality % of aluminium oxide, 70 ~ 88 quality % and by Al in macroporous aluminium oxide
2o
3/ HCl is the hydrochloric acid that adds of mass ratio of 40 ~ 90.
4. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, after it is characterized in that described compound macropore alumina supporter shaping and drying, roasting 1 ~ 4 hour at 450 ~ 600 DEG C.
5. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, is characterized in that the catalyst after described dipping chloroplatinic acid, roasting 1 ~ 4 hour at 450 ~ 600 DEG C after drying.
6. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, is characterized in that the Al/Cl mol ratio of described Alumina gel is 1.0 ~ 1.3.
7. straight chain Performance of Isomerization Catalysts for Light n-Paraffin according to claim 1, is characterized in that the pore volume of described macroporous aluminium oxide is 1.1 ~ 1.5 mls/g.
8. a straight chain light paraffins low temperature isomerization method, is characterized by and make straight chain light paraffins raw material and catalyst according to claim 1 in temperature 130 ~ 170 DEG C, pressure 1.5 ~ 2.0MPa, feed weight air speed 0.6 ~ 2.0 hour in presence of hydrogen
-1with haptoreaction under the condition of hydrogen/hydrocarbon mol ratio 0.5 ~ 3.0.
9. a kind of straight chain light paraffins low temperature isomerization method according to claim 8, it is characterized by described straight chain light paraffins raw material is C
5~ C
6lighter hydrocarbons, wherein normal paraffin content is 20 ~ 80 quality %.
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| CN104117369B (en) * | 2014-06-26 | 2017-04-12 | 江苏扬子催化剂有限公司 | Normal-paraffin isomerization catalyst, preparation method and application thereof |
| CN105080578B (en) * | 2015-08-14 | 2017-05-17 | 北京赛诺时飞石化科技有限公司 | N-alkane low-temperature isomerization catalyst as well as preparation method and application thereof |
| CN108786860B (en) * | 2017-05-03 | 2021-03-12 | 中国石油化工股份有限公司 | Light alkane isomerization catalyst, preparation method and application |
| CN108786861B (en) * | 2017-05-03 | 2021-03-12 | 中国石油化工股份有限公司 | Light alkane isomerization catalyst and preparation method and application thereof |
| CN109482205B (en) * | 2017-09-12 | 2021-10-08 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN112295593A (en) * | 2019-07-26 | 2021-02-02 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and its preparation and application |
| CN113289673B (en) * | 2021-06-02 | 2022-10-04 | 润和科华催化剂(上海)有限公司 | Isomerization catalyst and preparation method and application thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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Effective date of registration: 20170215 Address after: The three group of Jin Su Zhen Miao Er Cun, Wutongqiao District of Leshan City, Sichuan province 614800 Patentee after: Sichuan run and catalyze new materials Limited by Share Ltd Address before: 266500 Shandong City, Qingdao Province Economic and Technological Development Zone, Jiangshan Road, Jiangshan Rui garden, building 4, room 1, unit 401, room Patentee before: Zhuo Runsheng |
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| CP03 | Change of name, title or address |
Address after: 614000 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Runhe catalyst Co.,Ltd. Address before: 614800 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee before: SICHUAN REZEL CATALYSTS NEW MATERIAL Co.,Ltd. |
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| CP03 | Change of name, title or address |