CN103861644B - A kind of modified clay Catalysts and its preparation method for deolefination - Google Patents
A kind of modified clay Catalysts and its preparation method for deolefination Download PDFInfo
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- CN103861644B CN103861644B CN201410105277.0A CN201410105277A CN103861644B CN 103861644 B CN103861644 B CN 103861644B CN 201410105277 A CN201410105277 A CN 201410105277A CN 103861644 B CN103861644 B CN 103861644B
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- clay
- acid
- catalyst
- rare earth
- deolefination
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Abstract
For a modified clay catalyst for deolefination, composition and parts by weight are: clay 60 ~ 80 parts, heteropoly acid 1 ~ 10 part, 0.1 ~ 2 part, rare earth element and aluminum solutions are (with Al
2o
3content meter) 10 ~ 40 parts.Described rare earth element load is in clay duct, and described loaded by heteropoly acid is at surface of clay; Described Al
2o
3be coated on clay outer surface.With clay with low cost for raw material Kaolinite Preparation of Catalyst, it has good catalyst activity and stability, and can regenerate after catalysqt deactivation and repeatedly recycle.Experiment shows, still has the activity higher than fresh activity carclazyte, have obvious economic benefit after 4 uses that circulate.
Description
Technical field
The present invention relates to a kind of modified clay catalyst, in particular for removing the catalyst of the trace amounts of olefin in reformed oil.
Background technology
Reformed oil comprises various ingredients, and main component is aromatic hydrocarbons, wherein the most important thing is benzene,toluene,xylene." triphen " occupies extremely important status in petroleum products, and it is mainly produced 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; be easy to be polymerized and form the quality that colloid affects aromatic hydrocarbon product; harmful effect is produced to some follow-up chemical processes, affects the further processing and utilization of aromatic hydrocarbons.Such as in the xylene distillation tower reboiler that some temperature are very high, alkene easily causes coking or fouling and clogging pipeline, affects carrying out smoothly of course of reaction; At mixed xylenes by molecular sieve adsorption separation process, the duct that alkene occupies molecular sieve can reduce adsorbing separation effect significantly, these are to the highstrung chemical engineering process of alkene, even if olefin(e) centent considerably less (ppm level) also can produce very adverse influence to course of reaction; Alkene significantly can affect the effect of extracting in 120# rubber industry solvent naphtha production process; Also have benzene and sulfuric acid reaction to produce in benzene sulfonic acid technique, make product with color due to reaction can be carried out containing a small amount of alkene in benzene.In order to obtain qualified industrial chemicals and ensure 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.
Patent CN102728394A describes a kind of Concave-convex clay rod catalyst of sour modification, and its main method is at attapulgite clay loaded SO4
2-, uniform temperature is dry after sulfuric acid activated, then roasting at a certain temperature.Although catalyst preparing is simple, its life-span is on the low side, and hardness and wearability all do not reach industrial requirements, and does not mention whether can regenerating use.
Patent CN102091648B describes a kind of preparation method of full white-clay type olefinic hydrocarbon expelling catalyzer.Be characterized in taking carclazyte as raw material, obtain having through sulfuric acid treatment and turn brilliant active carclazyte, brilliant atlapulgite and solid caustic soda mixing will be turned, add dispersant, extrusion aid and peptizing agent and mediate mixing, extrusion molding or roll shaping on bowling machine on banded extruder, after formed body drying, roasting, carries out hydrothermal crystallizing reaction under sodium metasilicate, NaOH, deionized water, directed agents etc. exist, obtain NaY zeolite content and silica alumina ratio higher, the crystallization product that crystallite dimension is less.Again product is carried out exchanging 2 roastings for 3 times and obtain final products.This catalyst preparation process is complicated, and higher to carclazyte component requirements, need repeatedly exchange, roasting, and condition is harsh.
Patent CN101433856A disclose in modification Y or beta-molecular sieve, to add lanthanide rare, the compound of one or more elements of P, W, Nb, Mo prepares olefine lowering catalyst.This catalyst main component is molecular sieve, and molecular sieve price is 15 ~ 20 times of clay price, and rare earth element addition is very large, and be 3% ~ 25%, rare earth price is expensive especially.This catalyst is not suitable for large-scale industrial production and uses.
Patent CN101992117A discloses a kind of catalyst for removing olefins from reforming oil, and this catalyst contains 20% ~ 90% molecular sieve, 10% ~ 80%SiO
2, Al
2o
3or its mixture, simultaneously also containing Ni, Mo, Zr, Nb metal or its oxide, Cl, Br, S element or its oxide, F, P element or its oxide.Secondary catalyst preparing price is also very high, and use is restricted.
Patent CN103230788A discloses a kind of reformate and refines olefinic hydrocarbon expelling catalyzer, this catalyst contains the common carclazyte in mass fraction 60 ~ 90%, 5 ~ 40% silicone modified aluminum hydroxide solid elastomers and/or amorphous aluminum silicide, in element mass fraction, 0.01 ~ 2% minimum a kind of element selected in Cl, S, P, and the Alumina gel aqueous solution of alumina content 0 ~ 30%.This catalyst is mentioned regeneration and is reused, but shows in this patent, and this catalyst can only regenerate 1 ~ 2 time, effect and similar to carclazyte.
Summary of the invention
For solving the deficiency that in prior art, olefinic hydrocarbon expelling catalyzer is expensive, regenerability is poor, the invention provides a kind of modified clay Catalysts and its preparation method for deolefination, with the catalyst that clay with low cost is prepared for raw material, it has good catalyst activity and stability, and can regenerate, can repeatedly use, and regeneration process is simple.
The technical solution adopted in the present invention is: a kind of modified clay catalyst for deolefination, and composition and parts by weight are: clay 60 ~ 80 parts, heteropoly acid 1 ~ 10 part, 0.1 ~ 2 part, rare earth element and aluminum solutions are (with Al
2o
3content meter) 10 ~ 40 parts.
Further, described rare earth element load is in clay duct, and described loaded by heteropoly acid is at surface of clay; Described Al
2o
3be coated on clay outer surface.
The preparation method of the above-mentioned modified clay catalyst for deolefination, processing step comprises:
(1) pretreated clay is joined in rare earth compound solution, ultrasonic agitation 0.5 ~ 2h; Then in slurries, add the heteropoly acid after 100 DEG C ~ 200 DEG C activation, stir 1 ~ 2h, then flood at least 12h, dry, obtain modified clay;
(2) the precursor deionized water of aluminium is mixed with aluminum solutions, clay modified for step (1) is joined in aluminum solutions, stir under the condition of heating, be stirred to solution by evaporate to dryness;
(3) add auxiliary agent and binding agent in the material after above-mentioned evaporate to dryness, be in harmonious proportion and extrude evenly or to roll shaping, more shaping through super-dry, last roasting, bake out temperature is 100 DEG C ~ 110 DEG C, sintering temperature is 150 DEG C ~ 650 DEG C, preferably 250 ~ 550 DEG C, and roasting time is 1 ~ 4h.
Further, the clay described in step (1) is selected from one or more in kaolin, bentonite, sepiolite, galapectite, Concave-convex clay rod, diatomite or illitic soil;
Described rare earth compound is the one in the chloride of La, Ce, Pr or Nd or nitrate; Described rare earth compound solution rare earth elements mass fraction is 0.05 ~ 1%; Described clay and rare earth compound solution quality volume ratio are 0.3 ~ 3g/ml.
Described heteropoly acid is the one in phosphotungstic acid, silico-tungstic acid, silicomolybdic acid, phosphomolybdic acid or germanotungstic acid, preferred phosphotungstic acid or silico-tungstic acid;
The precursor of described aluminium be selected from boehmite, boehmite, monohydrate alumina, aluminium isopropoxide, Alumina gel, diaspore or gibbsite one or more.
As preferably, the clay described in step (1) is for have passed through dispersion, reaming and acidification in advance; Wherein dispersant is calgon, and mass concentration is 0.6%; Expanding agent is citric acid, and mass concentration is 0.5%; The acid of acidifying is selected from one in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid or nitric acid or 2 kinds, and acid concentration presses H
+meter, concentration is 0.1mol/L ~ 2mol/L.
As preferably, the heating-up temperature described in step (2) is 40 ~ 85 DEG C.
Further, the extrusion aid described in step (3) is sesbania powder or starch, and quality is 0.5% ~ 2% of the quality of material after evaporate to dryness.
As preferably, the binding agent described in step (3) is dust technology, and wherein the mass concentration of dilute nitric acid solution is 1.0% ~ 4.0%, and the addition of dust technology is advisable with applicable extrusion.
Beneficial effect of the present invention, advantage are:
1, catalyst preparing flow process is simple, plant investment and operating cost low, can be mass-produced application.
2, add a small amount of rare earth element as the first active component, make clay material be able to modification, make structure more stable on the one hand.On the other hand rare earth element can reduce the acid strength of catalyst, produces more sour position, forms more acid site, decreases the side reactions such as coking that strong acidic site brings and carbon distribution.Heteropoly acid is the second active component, is also main active component, for reaction provides a large amount of acidity.Two kinds of mutual coordinative roles of active component overcome the problem of catalyst easy in inactivation, more current industrial carclazyte, significantly improve life-span and the initial activity of catalyst.
3, rare earth modifiedly employ ultrasonic process, the ultrasonic rare earth element that can make enters inside, duct, and distributes uniformly.Again by infusion process by loaded by heteropoly acid to surface of clay, for reaction lasting acidic catalyst is provided, the life-span is greatly improved.
4, the clay after double activated component modification puts into aluminum solutions, by adding the method for thermal agitation, the predecessor of aluminium can be made to be coated on the outer surface of clay, then by high-temperature calcination, the predecessor of aluminium is finally converted into γ-Al
2o
3or α-Al
2o
3.With Al
2o
3the structure formed for composition is coated on clay outer surface, greatly improves the physical property of catalyst on the one hand, as rate of wear, compression strength, specific surface, pore volume, bulk density etc., meets industrial production demand.On the other hand, this Rotating fields can protect the loss of the double activated component of load on clay.Can regenerate after making catalysqt deactivation and repeatedly recycle.Experiment shows, still has the activity higher than fresh activity carclazyte, have obvious economic benefit after 4 uses that circulate.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of catalyst A prepared by embodiment 1.
Detailed description of the invention
Further illustrate the present invention with following instance, but the present invention is not limited to this:
Embodiment 1
Get pretreated Concave-convex clay rod 14.5g, add the lanthanum nitrate hexahydrate of 39ml containing elements La 0.5% (mass fraction), stir ultrasonic 1h; Then in slurries, add the phosphotungstic acid 1g through 180 DEG C of roastings, continue to stir 1h, then flood 14h, dry.Obtain the modified attapulgite clay of load 2 kinds of active components.
Get boehmite 6.4g, water 40ml puts into beaker, stirs and forms solution.Get the modified attapulgite clay prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 70 DEG C.
After oven dry, in powder after the drying, add 0.2g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 450 DEG C of roasting 2.5h.Be designated as catalyst A.
As can be seen from Figure 1, catalyst A structure is: rare earth element load in clay duct, loaded by heteropoly acid is at surface of clay, Al
2o
3be coated on clay outer surface.
Embodiment 2
Get pretreated Concave-convex clay rod 16g, add the neodymium nitrate solution of 40ml containing element neodymium 1% (mass fraction), stir ultrasonic 1.2h; Then in slurries, add the phosphotungstic acid 1.2g through 200 DEG C of roastings, continue to stir 1.5h, then flood 12h, dry.Obtain the modified attapulgite clay of load 2 kinds of active components.
Get Alumina gel 7.8g, water 24ml puts into beaker, stirs and forms solution.Get the modified attapulgite clay prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 60 DEG C.
After oven dry, in powder after the drying, add 0.1g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 350 DEG C of roasting 3h.Be designated as catalyst B.
Embodiment 3
Get pretreated Concave-convex clay rod 12g, add the ceric ammonium nitrate solution of 34ml containing elemental cerium 0.3% (mass fraction), stir ultrasonic 1.5h; Then in slurries, add the silicomolybdic acid 2g through 150 DEG C of roastings, continue to stir 2h, then flood 14h, dry.Obtain the modified attapulgite clay of load 2 kinds of active components.
Get diaspore 8.1g, water 45ml puts into beaker, stirs and forms solution.Get the modified attapulgite clay prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 50 DEG C.
After oven dry, in powder after the drying, add 0.2g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 250 DEG C of roasting 4h.Be designated as catalyst C.
Embodiment 4
Get pretreated Concave-convex clay rod 13g, add the neodymium nitrate solution of 45ml containing element neodymium 0.15% (mass fraction), stir ultrasonic 0.5h; Then in slurries, add the silico-tungstic acid 1.6g through 100 DEG C of roastings, continue to stir 2h, then flood 16h, dry.Obtain the modified attapulgite clay of load 2 kinds of active components.
Get boehmite 7.3g, water 38ml puts into beaker, stirs and forms solution.Get the modified attapulgite clay prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 40 DEG C.
After oven dry, in powder after the drying, add 0.12g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 500 DEG C of roasting 1.5h.Be designated as catalyst D.
Embodiment 5
Get pretreated bentonite 14g, add the lanthanum nitrate hexahydrate of 38ml containing elements La 0.4% (mass fraction), stir ultrasonic 2h; Then in slurries, add the phosphotungstic acid 0.4g through 150 DEG C of roastings, continue to stir 1.5h, then flood 12h, dry.Obtain the bentonite of the modification of load 2 kinds of active components.
Get boehmite 7.8g, water 50ml puts into beaker, stirs and forms solution.Get the modified alta-mud prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 85 DEG C.
After oven dry, in powder after the drying, add 0.2g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 550 DEG C of roasting 1h.Be designated as catalyst E.
Embodiment 6
Get pretreated kaolin 16g, add the ceric ammonium nitrate solution of 40ml containing elemental cerium 0.05% (mass fraction), stir ultrasonic 1.1h; Then in slurries, add the phosphotungstic acid 1.5g through 180 DEG C of roastings, continue to stir 1.5h, then flood 14h, dry.Obtain the modified kaolin of load 2 kinds of active components.
Get Alumina gel 8.2g, water 15ml puts into beaker, stirs and forms solution.Get the modified kaolin prepared above all to join in beaker.Stir under the condition of heating, be stirred to solution by evaporate to dryness, heating-up temperature is 80 DEG C.
After oven dry, in powder after the drying, add 0.15g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 400 DEG C of roasting 3h.Be designated as catalyst F.
Comparative example 1
Remove adding aluminum solutions step in embodiment 1, other conditions are constant, are specially:
Get pretreated Concave-convex clay rod 14.5g, add the lanthanum nitrate hexahydrate of 39ml containing elements La 0.5% (mass fraction), stir ultrasonic 1h; Then in slurries, add the phosphotungstic acid 1g through 180 DEG C of roastings, continue to stir 1h, then flood 14h, dry.Obtain the modified attapulgite clay of load 2 kinds of active components.
After oven dry, in powder after the drying, add 0.2g sesbania powder, drip the degree that dust technology is adjusted to applicable extrusion, extruded moulding on screw rod extrusion device, then through super-dry, last 450 DEG C of roastings.Be designated as catalyst G.
Comparative example 2
Get NC-01 granular carclazyte and be designated as catalyst H.
The modified clay olefinic hydrocarbon expelling catalyzer of above-mentioned preparation, its reaction carries out on fixed bed reactors, and the amount of filling out of catalyst is 10ml(20 ~ 40 order), feedstock oil (reformed oil) bromine valency is 3200mgBr/100g.Reaction condition is: reaction temperature 160 ~ 180 DEG C, operating pressure 1.0 ~ 2.0MPa, and Feed space velocities is 2 ~ 10hr
-1.
The Performance comparision of the catalyst deolefination that following table 1 is prepared for different process, initial activity is sample the olefin removal rate recorded for the first time, and using 60% of olefin removal rate as the standard judging catalysqt deactivation.Regenerate 4 hours 400 DEG C of air oxidations after inactivation, terminate rear nitrogen and purge, remove the polymer, poisonous substance etc. that catalyst hide active component, then reuse, measure.
Utilize the olefin removal rate of formulae discovery aromatic hydrocarbon product below:
Olefin removal rate=(raw material bromine valency-institute's sample thief bromine valency)/raw material bromine valency × 100%.
The physicochemical property of the catalyst that following table 2 is prepared for different process
Claims (6)
1., for a preparation method for the modified clay catalyst of deolefination, it is characterized in that,
Composition and the parts by weight of the raw materials of the described modified clay catalyst for deolefination are: clay 60 ~ 80 parts, heteropoly acid 1 ~ 10 part, 0.1 ~ 2 part, rare earth element and aluminum solutions 10 ~ 40 parts, wherein the parts by weight of aluminum solutions are with Al
2o
3content meter;
Described rare earth compound is the one in the chloride of La, Ce, Pr or Nd or nitrate;
Described heteropoly acid is the one in phosphotungstic acid, silico-tungstic acid, silicomolybdic acid, phosphomolybdic acid or germanotungstic acid;
Described rare earth element load is in clay duct, and described loaded by heteropoly acid is at surface of clay; Described aluminum solutions is with Al
2o
3form is coated on clay outer surface;
The processing step of described preparation method comprises,
(1) pretreated clay is joined in rare earth compound solution, ultrasonic agitation 0.5 ~ 2h; Then in slurries, add the heteropoly acid after 100 DEG C ~ 200 DEG C activation, stir 1 ~ 2h, then flood at least 12h, dry, obtain modified clay;
(2) the precursor deionized water of aluminium is mixed with aluminum solutions, clay modified for step (1) is joined in aluminum solutions, stir under the condition of heating, be stirred to solution by evaporate to dryness;
(3) add auxiliary agent and binding agent in the material after above-mentioned evaporate to dryness, be in harmonious proportion and extrude evenly or to roll shaping, then through drying, last roasting is shaping, bake out temperature is 100 DEG C ~ 110 DEG C, and sintering temperature is 250 ~ 550 DEG C, and roasting time is 1 ~ 4h.
2. the preparation method of the modified clay catalyst for deolefination according to claim 1, is characterized in that: the clay described in step (1) is selected from one or more in kaolin, bentonite, sepiolite, galapectite, Concave-convex clay rod, diatomite or illitic soil;
Described rare earth compound solution rare earth elements mass fraction is 0.05 ~ 1%; Described clay and rare earth compound solution quality volume ratio 0.3 ~ 3g/ml;
The precursor of described aluminium be selected from boehmite, aluminium isopropoxide, Alumina gel, diaspore or gibbsite one or more.
3. the preparation method of the modified clay catalyst for deolefination according to claim 1, is characterized in that: the clay described in step (1) is for have passed through dispersion, reaming and acidification in advance; Wherein dispersant is calgon, and mass concentration is 0.6%; Expanding agent is citric acid, and mass concentration is 0.5%; The acid of acidifying is selected from one in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid or nitric acid or two kinds, and acid concentration presses H
+meter, concentration is 0.1mol/L ~ 2mol/L.
4. the preparation method of the modified clay catalyst for deolefination according to claim 1, is characterized in that: the heating-up temperature described in step (2) is 40 ~ 85 DEG C.
5. the preparation method of the modified clay catalyst for deolefination according to claim 1, it is characterized in that: the auxiliary agent described in step (3) is sesbania powder or starch, quality is 0.5% ~ 2% of the quality of material after evaporate to dryness.
6. the preparation method of the modified clay catalyst for deolefination according to claim 1, it is characterized in that: the binding agent described in step (3) is dust technology, wherein the mass concentration of dilute nitric acid solution is 1.0% ~ 4.0%.
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| CN105536760B (en) * | 2015-12-03 | 2018-04-24 | 淮阴工学院 | A kind of preparation method of high long-acting compound clay olefinic hydrocarbon expelling catalyzer |
| 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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