CN103769076A - Method for preparing olefin-removal catalyst by taking clay as raw materials - Google Patents
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Abstract
The invention discloses a method for preparing an olefin-removal catalyst by taking clay as raw materials, relating to a method for preparing a catalyst by loading active components on a mesoporous material prepared by the clay. The catalyst is used for removing trace olefin in reformate oil. The preparation method comprises the following steps: mixing clay with sodium carbonate and calcining at high temperature, adding water and fully dissolving, then adding a tetrabutyl titanate solution, filtering, washing to be neutral, drying, calcining, and synthesizing the mesoporous material with Si and Ti structure; adding the prepared mesoporous material into quantitative rare earth solution, stirring, carrying out ultrasonic treatment, drying and calcining to obtain a rare-earth-modified mesoporous material; preparing the rare-earth-modified material, other active components and deionized water into an aqueous solution, carrying out ultrasonic stirring and soaking, drying and then adding extrusion aids and binders, extrusion-molding through an banded extruder or roll-molding through a bowl machine, and then drying and finally calcining and molding to obtain the catalyst. The catalyst is environmentally friendly, low in cost and simple in technique, has excellent catalytic activity and stability, and can be repeatedly utilized after being reproduced.
Description
Technical field
The present invention relates to a kind of mesoporous material of being prepared by clay, and prepare a kind of method of catalyst with this material load active component, this catalyst is for removing the trace amounts of olefin of reformed oil.
Background technology
Aromatic hydrocarbons is petrochemical industry important foundation raw material, and production development nearly three, aromatic hydrocarbons over 40 years is very fast.Aromatic hydrocarbons comprises various ingredients, wherein the most important thing is benzene,toluene,xylene." triphen " occupies extremely important status in oil product, and it is mainly to produce by the technique such as naphtha reforming and steam cracking.But all contain a certain amount of olefin impurity in the BTX product of these explained hereafter; the mass fraction of general content in product composition is less than 1%; these olefin impurity character are very active; being easy to polymerization formation colloid affects the quality of aromatic hydrocarbon product; some follow-up chemical processes are produced to harmful effect, affect the further processing and utilization of aromatic hydrocarbons.In order to obtain qualified industrial chemicals and to guarantee carrying out smoothly of subsequent technique, trace amounts of olefin hydrocarbon in arene must be removed, to improve the economic benefit of aromatic hydrocarbons processing technology.
At present, petrochemical enterprise extensively adopts the method for olefin impurity in Arene removal reformed oil to mainly contain clay-filtered and Hydrobon method both at home and abroad.
Clay-filtered is the process using the earliest, this technique all has good removal effect to benzene to the alkene in dimethylbenzene long distillate, clay-filtered is under certain condition, thereby the acid activated centre on carclazyte can impel alkene generation polymerization and alkylated reaction by trace amounts of olefin deep removal, but the deactivation rate of carclazyte is fast, and the operation cycle is short, change frequent, and a large amount of spent bleaching clays can only process by the mode of landfill, serious environment pollution.
Hydrofinishing is to make olefine reaction generate corresponding paraffins by hydrogenation, reaches the method that removes trace amounts of olefin impurity.Be typically and on aluminium oxide, make catalyst by precious metal palladium or platinum even load, as CN85100215A, CN101157031A, CN1448474A patent report, unifining process can only be concerning single narrow fraction effect better, and for the long distillate that contains multiple aromatic hydrocarbons simultaneously, the degree of depth of hydrogenation reaction is difficult to take into account comprehensively, can cause the loss of aromatic hydrocarbons larger, and noble metal is on the high side, seriously polluted, process route complexity, equipment investment expense is too high, affects further commercial Application.
Patent CN102728394A has introduced a kind of Concave-convex clay rod catalyst of sour modification, and its main method is at attapulgite clay loaded SO
4 2-, uniform temperature is dry after persulfuric acid activation, then roasting at a certain temperature.Though catalyst preparation is simple, it is active and the life-span is on the low side.
Patent CN102091648A has introduced a kind of preparation method of full white-clay type olefinic hydrocarbon expelling catalyzer, to turn brilliant atlapulgite and solid caustic soda mixes, add dispersant, extrusion aid and peptizing agent to mediate evenly, extruded moulding, after formed body drying, roasting, under the existence conditions such as sodium metasilicate, NaOH, deionized water, directed agents, carry out hydrothermal crystallizing reaction, again by this crystallization product through ion-exchange and the super steady modification of hydro-thermal, will be through repeatedly exchange and roasting in preparation process, complex process, cost is also high.
Patent CN102658196A has introduced a kind of modified argil method for preparing catalyst, just simply atlapulgite, lewis acid catalyst, molecular sieve, rare earth chloride is mixed.Exist dispersion inhomogeneous, and there is no the problems such as activation, active component can not play one's part to the full.
There is preparation method's complexity in above patent, technological process is long, and noble metal dosage is large, some problems during initial activity and life-span are on the low side etc.
Summary of the invention
For the deficiency of above-mentioned technology, the object of this invention is to provide a kind of catalyst of preparing take clay with low cost as raw material, this catalyst is environmentally friendly, and it has good catalytic activity and stability, to reach the object that removes trace amounts of olefin in reformed oil, after regeneration activating, can be repeatedly used, use cost is low.
The present invention is achieved through the following technical solutions above-mentioned purpose:
Prepare a method for olefinic hydrocarbon expelling catalyzer take clay as raw material, comprise that step is following rapid:
(1) be that 1:0.5～2 clay and sodium carbonate mix by mass ratio, mixture roasting 1～3 hour at 700 ℃～900 ℃, packs the material after roasting with in the container stirring into, adds deionized water, and it is fully mixed; Butyl titanate and deionized water are fully mixed and made into butyl titanate solution with the volume ratio of 1:1～2, and described butyl titanate and above-mentioned clay mass ratio are 1:2～5; Under the condition of rapid stirring, butyl titanate solution is joined in said vesse, continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 8～10, stir and stop after 1～2 hour, filter, washing is to neutral, dry, under 300 ℃～700 ℃ conditions, roasting obtains mesoporous material for 1～4 hour;
(2) get the mesoporous material that step (1) prepares, joined in the earth solution preparing, ultrasonic 1～4 hour, leave standstill post-drying, obtain rare earth modified mesoporous material 400 ℃～600 ℃ roastings; Described earth solution is one or more in oxide, chloride, nitrate, sulfate or the carbonate solution of rare earth, and the rare earth element quality in earth solution accounts for 0.1～5% of described mesoporous material quality;
(3) get by mass 5～30 parts of active components and deionized water and be made into the aqueous solution, the mass ratio of active component and deionized water is 1:5～20, active component is the one in chloride, sulfate or heteropoly acid, getting by mass the rare earth modified mesoporous material of 70～95 parts of steps (2) puts into the aqueous solution and stirs, ultrasonic 4～6 hours, flood 8～16 hours, after oven dry, add extrusion aid and binding agent, extrusion molding or the moulding of rolling on bowling machine on banded extruder, then through super-dry, finally obtain catalyst 150 ℃～450 ℃ roasting moulding.
Further improve, the described clay of step (1) is the one in Concave-convex clay rod, bentonite, kaolin, illite, sepiolite, galapectite, rectorite or diatomite; Preferred 1:1～1.2 of mass ratio of clay and sodium carbonate; Preferably 500 ℃～600 ℃ of the temperature of roasting after drying.
Further improve chloride or the nitrate of the preferred rare earth of earth solution of preparation in step (2), further preferably nitrate; Rare earth element is La, Ce, in Nd one or several.
Further improve, described in step (3), active component is one or more in aluminium chloride, zinc chloride, gallium chloride, aluminum sulfate or phosphotungstic acid, further preferred aluminium chloride, gallium chloride or aluminum sulfate; Preferably 200～300 ℃ of sintering temperatures after drying; Described extrusion aid is sesbania powder, and addition is gross mass 1～5%; Described binding agent is inorganic acid, preferably nitric acid, and the mass concentration of salpeter solution is 2.0%～4.0%.
Beneficial effect, advantage of the present invention is:
1, the mesoporous material that prepared by step (1) has very high specific surface, and large aperture is structurally ordered, has good stability.And catalyst formation Ti-O-Si key, make the active component of load below be difficult for removing.
2, add a small amount of rare earth element, although the cost of catalyst is increased a little, due to adding of rare earth element, make material be able to modification, make structure more stable on the one hand, make more stable the loading on material of active component.Rare earth element can act on the B acid position of catalyst on the other hand, can make like this acid strength of catalyst reduce, and produce more acid position, when providing more active sites for catalyst, the side reaction such as coking and carbon distribution of having avoided strong acidic site to bring, activity and the stability of catalyst are all significantly improved.
3, the active component of load can produce a large amount of L acid sites in surface and the inside of mesoporous material, the electronics that is subject to of L acid position is conducive to the effect of catalyst and aromatic hydrocarbons and alkene more, increase the touch opportunity of active sites on reactant and catalyst, improve the reactivity worth of catalyst.
4, used ultrasonic processing when rare earth modified and load active component, ultrasonicly can make rare earth element and active component distribute more uniformly and more easily enter material internal, for reaction provides lasting acidic catalyst, the life-span is greatly improved.
5, after the catalyst that prepared by the application is renewable, repeatedly recycling, can be used the 8-12 month first continuously, after regeneration, can also continue to use to exceed the 8-12 month, cycle-index 3 times, and long service life, use cost is low.
The specific embodiment
Further illustrate the present invention with following instance, but the present invention is not limited to this:
Embodiment 1
1, get Concave-convex clay rod 10g and sodium carbonate 10g mixes, by mixture roasting 2 hours at 850 ℃, the material after roasting is incorporated with in the container of stirring, add deionized water 80ml, it is fully mixed.Get butyl titanate 4ml and deionized water 4ml is mixed and made into butyl titanate solution.In container before butyl titanate solution being joined under the condition of rapid stirring.Continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 9, stirs and stops for 2 hours, filters, and washing, to neutral, is dried, and 500 ℃ of roastings obtain mesoporous material for 4 hours.
2, get 0.5g lanthanum nitrate and be mixed with 50ml lanthanum nitrate hexahydrate, get the mesoporous material 10g that step prepares and join in lanthanum nitrate hexahydrate, ultrasonic 1 hour, leave standstill 2h post-drying, obtain rare earth modified material at 600 ℃ of roasting 1h.
3, getting 2g aluminium chloride is dissolved in 30ml deionized water, get the rare earth modified material of 8g and put into above-mentioned solution, stir, ultrasonic 4 hours, flood 12 hours, after oven dry, add 0.2g sesbania powder, drip rare nitric acid (mass concentration is 2.0%～4.0%) and be adjusted to the degree that is applicable to extrusion, extruded moulding on screw rod extrusion device, then obtain catalyst through super-dry, last 300 ℃ of roastings.Be designated as catalyst A.
Embodiment 2
1, get Concave-convex clay rod 10g and sodium carbonate 12g mixes, by mixture roasting 3 hours at 900 ℃, the material after roasting is incorporated with in the container of stirring, add deionized water 75ml, it is fully mixed.Get butyl titanate 3.5ml and deionized water 4.2ml is fully mixed and made into butyl titanate solution.Under the condition of rapid stirring, will enter in the container of butyl titanate solution before joining.Continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 8, stirs and stops for 1 hour, filters, and washing, to neutral, is dried, and 600 ℃ of roastings obtain mesoporous material for 3 hours.
2, get 0.3g lanthanum nitrate and 0.2g neodymium nitrate is mixed with 60ml solution, get the mesoporous material 10g that step prepares and join in solution, ultrasonic 1.5 hours, leave standstill 4h post-drying, at 500 ℃ of rare earth modified materials of roasting 1.5h.
3, getting 1.5g aluminium chloride is dissolved in 25ml deionized water, get the rare earth modified material of 8.5g and put into above-mentioned solution, stir, ultrasonic 4.5 hours, flood 14 hours, after oven dry, add 0.15g sesbania powder, drip rare nitric acid (mass concentration is 2.0%～4.0%) and be adjusted to the degree that is applicable to extrusion, extruded moulding on screw rod extrusion device, then obtain catalyst through super-dry, last 200 ℃ of roastings.Be designated as catalyst B.
Embodiment 3
1, get Concave-convex clay rod 10g and sodium carbonate 13g mixes, by mixture roasting 1.5 hours at 700 ℃, the material after roasting is incorporated with in the container of stirring, add deionized water 82ml, it is fully mixed.Get butyl titanate 3ml and deionized water 3.9ml is mixed and made into butyl titanate solution.In container before butyl titanate solution being joined under the condition of rapid stirring.Continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 10, stirs and stops for 2 hours, filters, and washing, to neutral, is dried, and 600 ℃ of roastings obtain mesoporous material for 2 hours.
2, get 0.3g lanthanum nitrate and 0.3g ammonium ceric nitrate is mixed with 55ml solution, get the mesoporous material 10g that step prepares and join in solution, ultrasonic 2 hours, leave standstill 2h post-drying, obtain rare earth modified material at 400 ℃ of roasting 2h.
3, getting 3g aluminium chloride is dissolved in 20ml deionized water, get the rare earth modified material of 7g and put into above-mentioned solution, stir, ultrasonic 5 hours, flood 16 hours, after oven dry, add 0.25g sesbania powder, drip rare nitric acid (mass concentration is 2.0%～4.0%) and be adjusted to the degree that is applicable to extrusion, extruded moulding on screw rod extrusion device, then obtain catalyst through super-dry, last 200 ℃ of roastings.Be designated as catalyst C.
Embodiment 4
1, get Concave-convex clay rod 10g and sodium carbonate 20g mixes, by mixture roasting 1 hour at 750 ℃, the material after roasting is incorporated with in the container of stirring, add deionized water 78ml, it is fully mixed.Get butyl titanate 2ml and deionized water 2.8ml is mixed and made into butyl titanate solution.In container before butyl titanate solution being joined under the condition of rapid stirring.Continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 8, stirs and stops for 1 hour, filters, and washing, to neutral, is dried, and 500 ℃ of roastings obtain mesoporous material for 2.5 hours.
2, get 0.2g neodymium nitrate and 0.3g ammonium ceric nitrate is mixed with 65ml solution, get the mesoporous material 10g that step prepares and join in solution, ultrasonic 2.5h hour, leaves standstill 2.5h post-drying, obtains rare earth modified material at 450 ℃ of roasting 2.5h.
3, getting 0.5g aluminium chloride is dissolved in 25ml deionized water, get the rare earth modified material of 9.5g and put into above-mentioned solution, stir, ultrasonic 4.5 hours, flood 14 hours, after oven dry, add 0.3g sesbania powder, drip rare nitric acid (mass concentration is 2.0%～4.0%) and be adjusted to the degree that is applicable to extrusion, extruded moulding on screw rod extrusion device, then obtain catalyst through super-dry, last 300 ℃ of roastings.Be designated as catalyst D.
Embodiment 5
1, get Concave-convex clay rod 10g and sodium carbonate 16g mixes, by mixture roasting 2.5 hours at 800 ℃, the material after roasting is incorporated with in the container of stirring, add deionized water 85ml, it is fully mixed.Get butyl titanate 3.6ml and deionized water 5.4ml is mixed and made into butyl titanate solution.In container before butyl titanate solution being joined under the condition of rapid stirring.Continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 9, stirs and stops for 2 hours, filters, and washing, to neutral, is dried, and 550 ℃ of roastings obtain mesoporous material for 3.5 hours.
2, get 0.2g lanthanum nitrate, 0.2g neodymium nitrate and 0.2g ammonium ceric nitrate and be mixed with 60ml solution, get the mesoporous material 10g that step prepares and join in solution, ultrasonic 3 hours, leave standstill 2.5h post-drying, obtain rare earth modified material at 550 ℃ of roasting 3h.
3, getting 1g aluminium chloride is dissolved in 30ml deionized water, get the rare earth modified material of 9g and put into above-mentioned solution, stir, ultrasonic 4.5 hours, flood 12 hours, after oven dry, add 0.1g sesbania powder, drip rare nitric acid (mass concentration is 2.0%～4.0%) and be adjusted to the degree that is applicable to extrusion, extruded moulding on screw rod extrusion device, then obtain catalyst through super-dry, last 250 ℃ of roastings.Be designated as catalyst E.
Embodiment 6
In embodiment 6, make the Concave-convex clay rod in embodiment 5 steps 1 into bentonite, other operations are all identical with embodiment 5.Be designated as catalyst F.
Embodiment 7
In embodiment 7, make the aluminium chloride in embodiment 5 steps 1 into aluminum sulfate, other operations are all identical with embodiment 5.Be designated as catalyst G.
Comparative example 1
In comparative example 1, the 0.2g lanthanum nitrate in embodiment 5 steps 2,0.2g neodymium nitrate and 0.2g ammonium ceric nitrate are changed into the sodium nitrate wiring solution-forming of 0.6g, other operations are all identical with embodiment 5.Be designated as catalyst H.
Comparative example 2
Get current industrial NC-01 granular carclazyte and be designated as catalyst I.
Comparative example 3
Prepare comparative example 3 by the disclosed method of patent CN102728394A:
Take certain Concave-convex clay rod, adding finite concentration is 13% aqueous sulfuric acid, under the reaction temperature of 80 ℃, activate 10 hours, Concave-convex clay rod sulfuric acid after activation is suspended at 120 ℃ and is dried 0.5 hour, 450 ℃ of roastings of dried powder 8 hours, make the Concave-convex clay rod catalyst of sour modification.Be designated as catalyst J.
Following table be the catalyst deolefination made of different process Performance Ratio, initial activity is to sample for the first time the olefin removal rate recording, and using olefin removal rate 60% as the standard that judges catalysqt deactivation; After inactivation, 450 ℃ of air oxidations are regenerated 24 hours, remove the polymer, the poisonous substance etc. that on catalyst, hide active component, then reuse mensuration, can be recycled more than three times.
Contrast test condition: reaction is to carry out on micro fixed-bed reactor, the amount of filling out of catalyst is 2ml(20～40 order), feedstock oil (reformed oil) bromine valency is 3256mgBr/100g.160～180 ℃ of reaction temperatures, operating pressure 1.0～2.0MPa, charging air speed is 10～30hr
-1.
Utilize the olefin removal rate of the aromatic hydrocarbon product of formula calculating below:
Olefin removal rate=(raw material bromine valency-product bromine valency)/raw material bromine valency × 100%.
Claims (10)
1. a method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material, is characterized in that comprising
Following steps:
(1) be that 1:0.5～2 clay and sodium carbonate mix by mass ratio, mixture roasting 1～3 hour at 700 ℃～900 ℃, packs the material after roasting with in the container stirring into, adds deionized water, and it is fully mixed; Butyl titanate and deionized water are fully mixed and made into butyl titanate solution with the volume ratio of 1:1～2, and described butyl titanate and above-mentioned clay mass ratio are 1:2～5; Under the condition of rapid stirring, butyl titanate solution is joined in said vesse, continuing to drip ammoniacal liquor under the condition stirring, regulating pH is 8～10, stir and stop after 1～2 hour, filter, washing is to neutral, dry, under 300 ℃～700 ℃ conditions, roasting obtains mesoporous material for 1～4 hour;
(2) get the mesoporous material that step (1) prepares, joined in the earth solution preparing, ultrasonic 1～4 hour, leave standstill post-drying, obtain rare earth modified mesoporous material 400 ℃～600 ℃ roastings; Described earth solution is one or more in oxide, chloride, nitrate, sulfate or the carbonate solution of rare earth, and the rare earth element quality in earth solution accounts for 0.1～5% of described mesoporous material quality;
(3) get by mass 5～30 parts of active components and deionized water and be made into the aqueous solution, the mass ratio of active component and deionized water is 1:5～20, active component is the one in chloride, sulfate or heteropoly acid, getting by mass the rare earth modified mesoporous material of 70～95 parts of steps (2) puts into the aqueous solution and stirs, ultrasonic 4～6 hours, flood 8～16 hours, after oven dry, add extrusion aid and binding agent, extrusion molding or the moulding of rolling on bowling machine on banded extruder, then through super-dry, finally obtain catalyst 150 ℃～450 ℃ roasting moulding.
2. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: the described clay of step (1) is the one in Concave-convex clay rod, bentonite, kaolin, illite, sepiolite, galapectite, rectorite or diatomite.
3. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: the mass ratio of step (1) medium clay soil and sodium carbonate is 1:1～1.2.
4. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: the temperature that step (1) is dried rear roasting is 500 ℃～600 ℃.
5. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: the rare earth element described in step (2) be in La, Ce or Nd one or several.
6. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: described in step (3), active component is one or more in aluminium chloride, zinc chloride, gallium chloride, aluminum sulfate or phosphotungstic acid.
7. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 6, is characterized in that: active component described in step (3) be in aluminium chloride, gallium chloride or aluminum sulfate one or several.
8. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: 200～300 ℃ of sintering temperatures after drying in step (3).
9. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 1, is characterized in that: described in step (3), extrusion aid is sesbania powder, addition is gross mass 1～5%, and described binding agent is inorganic acid.
10. a kind of method of preparing olefinic hydrocarbon expelling catalyzer take clay as raw material according to claim 9, is characterized in that: described inorganic acid is nitric acid, the mass concentration of salpeter solution is 2.0%～4.0%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| CN106268792A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay basic weight is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN106268797A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay base precious metal reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN109876861A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of highly acid ball-type atlapulgite and its preparation method and application |
| CN112403520A (en) * | 2019-08-22 | 2021-02-26 | 昌吉学院 | Preparation and application of vermiculite supported phosphotungstic acid green catalyst |
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| JPS5653746A (en) * | 1979-10-08 | 1981-05-13 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| CN102580718A (en) * | 2012-02-02 | 2012-07-18 | 福州大学 | Cerium-zirconium composite material, preparation method thereof and application thereof |
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| JPS5653746A (en) * | 1979-10-08 | 1981-05-13 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| CN104588089B (en) * | 2015-01-07 | 2016-10-19 | 盱眙恒信粘土科技有限公司 | A kind of method of the de-olefin of reforming oil catalyst of ammonium fluoride modification preparation |
| CN106268792A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay basic weight is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN106268797A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay base precious metal reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN106268797B (en) * | 2016-07-15 | 2018-10-19 | 常州大学 | A kind of recessed soil matrix noble metal reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN106268792B (en) * | 2016-07-15 | 2018-10-19 | 常州大学 | A kind of recessed soil matrix reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
| CN109876861A (en) * | 2017-12-06 | 2019-06-14 | 中国石化扬子石油化工有限公司 | A kind of highly acid ball-type atlapulgite and its preparation method and application |
| CN112403520A (en) * | 2019-08-22 | 2021-02-26 | 昌吉学院 | Preparation and application of vermiculite supported phosphotungstic acid green catalyst |
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| CN103769076B (en) | 2015-07-08 |
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