CN103861644A - Modified clay catalyst for removing olefin and preparation method thereof - Google Patents
Modified clay catalyst for removing olefin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified clay catalyst for removing olefin. The modified clay catalyst comprises the following components in parts by weight: 60-80 parts of clay, 1-10 parts of heteropoly acid, 0.1-2 parts of rare-earth elements and 10-40 parts of aluminium solution (according to the content of Al2O3). The rare-earth elements are loaded in pore channels of clay, and the heteropoly acid is loaded on the surface of the clay; the Al2O3 coats the clay. The modified clay catalyst is prepared by adopting the clay with low cost as the material, has good activity and stability and can be regenerated and circularly used for multiple times after being inactivated. Shown by experiment, the modified clay has higher activity than that of fresh active activated clay after being circularly used for 4 times, so that the modified clay catalyst has obvious economic benefit.
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 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.For example in the very high xylene distillation tower reboiler of some temperature, alkene easily causes coking or fouling blocking pipe, affects carrying out smoothly of course of reaction; Pass through in molecular sieve adsorption separation process at mixed xylenes, 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 can significantly 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, can react and make product with color owing to containing a small amount of alkene in benzene.In order to obtain qualified industrial chemicals and to 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 has introduced 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 persulfuric acid activation, then roasting at a certain temperature.Although catalyst preparation is simple, its life-span is on the low side, and hardness and wearability all do not reach industrial requirements, and do not mention the use of whether can regenerating.
Patent CN102091648B has introduced a kind of preparation method of full white-clay type olefinic hydrocarbon expelling catalyzer.Be characterized in taking carclazyte as raw material, obtain having the carclazyte that turns brilliant activity through sulfuric acid treatment, to turn brilliant atlapulgite and solid caustic soda mixes, adding dispersant, extrusion aid and peptizing agent to mediate mixes, on banded extruder, extrusion molding or the moulding of rolling on bowling machine after formed body drying, roasting, are carried out hydrothermal crystallizing reaction under the existence such as sodium metasilicate, NaOH, deionized water, directed agents, obtain NaY zeolite content and silica alumina ratio higher, the crystallization product that crystallite dimension is less.Again product is carried out to 2 roastings of 3 exchanges and obtain final products.This catalyst preparation process complexity, and carclazyte composition is had relatively high expectations, need repeatedly exchange, roasting, condition harshness.
Patent CN101433856A discloses and in modification Y or beta-molecular sieve, has added the compound of one or more elements of lanthanide rare, P, W, Nb, Mo to prepare 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, is 3%～25%, and 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 is containing 20%～90% molecular sieve, 10%～80%SiO
2, Al
2o
3or its mixture, also contain Ni, Mo, Zr, Nb metal or its oxide, Cl, Br, S element or its oxide, F, P element or its oxide simultaneously.It is also very high that inferior catalyst is prepared price, and use is restricted.
Patent CN103230788A discloses the refining olefinic hydrocarbon expelling catalyzer of a kind of reformate, 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 of selecting in Cl, S, P, and the aluminium colloidal sol 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 be regenerated 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, the catalyst of preparing taking clay with low cost as raw material, it has good catalyst activity and stability, and can regenerate, can be repeatedly used, and regeneration is processed simple.
The technical solution adopted in the present invention is: a kind of modified clay catalyst for deolefination, composition and parts by weight are: 60～80 parts of clays, 1～10 part of heteropoly acid, 0.1～2 part, rare earth element and aluminum solutions are (with Al
2o
3content meter) 10～40 parts.
Further, described rare earth element loads 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 to 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) precursor of aluminium is mixed with to aluminum solutions by deionized water, the clay after step (1) modification is joined in aluminum solutions, under the condition of heating, stir, be stirred to solution by evaporate to dryness;
(3) in the material after above-mentioned evaporate to dryness, add auxiliary agent and binding agent, the moulding of extruding or roll after mediation evenly, then through super-dry, last roasting moulding, bake out temperature is 100 DEG C～110 DEG C, sintering temperature is 150 DEG C～650 DEG C, and preferably 250～550 DEG C, roasting time is 1～4h.
Further, the described clay of 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 chloride or the nitrate of La, Ce, Pr or Nd; 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, preferably phosphotungstic acid or silico-tungstic acid;
The precursor of described aluminium is selected from one or more in boehmite, boehmite, monohydrate alumina, aluminium isopropoxide, aluminium colloidal sol, diaspore or gibbsite.
As preferably, the clay described in step (1) is for having passed through in advance dispersion, reaming and acidification; Wherein dispersant is calgon, and mass concentration is 0.6%; Expanding agent is citric acid, and mass concentration is 0.5%; The acid that acidifying is used is selected from a kind of in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid or nitric acid or 2 kinds, and acid concentration is pressed 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 quality of material after evaporate to dryness.
As preferably, the binding agent described in step (3) is rare nitric acid, and wherein the mass concentration of dilute nitric acid solution is 1.0%～4.0%, and the addition of rare nitric acid is advisable to be applicable to extrusion.
Beneficial effect of the present invention, advantage are:
1, catalyst preparation flow is simple, and plant investment and operating cost are low, and application can be mass-produced.
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.Rare earth element can reduce the acid strength of catalyst on the other hand, produces more acid position, forms more acid site, has reduced the side reaction such as coking and carbon distribution that strong acidic site brings.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 have overcome the problem of the easy inactivation of catalyst, compared with current industrial carclazyte, have obviously improved life-span and the initial activity of catalyst.
3, rare earth modifiedly used ultrasonic processing, the ultrasonic rare earth element that can make enters inside, duct, and distributes uniformly.By infusion process, loaded by heteropoly acid is arrived to surface of clay again, for reaction provides lasting acidic catalyst, the life-span is greatly improved.
4, the clay after double activated component modification is put into aluminum solutions, by adding the method for thermal agitation, can make the predecessor of aluminium 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 forming for composition is coated on clay outer surface, greatly improves on the one hand the physical property of catalyst, as rate of wear, compression strength, specific surface, pore volume, bulk density etc., meets industrial production demand.On the other hand, this layer of structure can be protected the loss of the double activated component of load on clay.Make can regenerate and repeatedly recycle after catalysqt deactivation.Experiment shows still there is the activity higher than fresh atlapulgite after 4 uses that circulate, and has obvious economic benefit.
Brief description of the drawings
Fig. 1 is the Electronic Speculum figure of the catalyst A prepared of 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 39ml to contain the lanthanum nitrate hexahydrate of 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 2 kinds of active components of load.
Get boehmite 6.4g, water 40ml puts into beaker, stirs and forms solution.Getting the modified attapulgite clay of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 70 DEG C.
After oven dry, in the powder after oven dry, add 0.2g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 loads 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 40ml to contain the neodymium nitrate solution of 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 2 kinds of active components of load.
Get aluminium colloidal sol 7.8g, water 24ml puts into beaker, stirs and forms solution.Getting the modified attapulgite clay of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 60 DEG C.
After oven dry, in the powder after oven dry, add 0.1g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 34ml to contain the ceric ammonium nitrate solution of 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 2 kinds of active components of load.
Get diaspore 8.1g, water 45ml puts into beaker, stirs and forms solution.Getting the modified attapulgite clay of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 50 DEG C.
After oven dry, in the powder after oven dry, add 0.2g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 45ml to contain the neodymium nitrate solution of 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 2 kinds of active components of load.
Get boehmite 7.3g, water 38ml puts into beaker, stirs and forms solution.Getting the modified attapulgite clay of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 40 DEG C.
After oven dry, in the powder after oven dry, add 0.12g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 38ml to contain the lanthanum nitrate hexahydrate of 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 2 kinds of active components of load.
Get boehmite 7.8g, water 50ml puts into beaker, stirs and forms solution.Getting the modified alta-mud of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 85 DEG C.
After oven dry, in the powder after oven dry, add 0.2g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 40ml to contain the ceric ammonium nitrate solution of 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 2 kinds of active components of load.
Get aluminium colloidal sol 8.2g, water 15ml puts into beaker, stirs and forms solution.Getting the modified kaolin of preparing above all joins in beaker.Under the condition of heating, stir, be stirred to solution by evaporate to dryness, heating-up temperature is 80 DEG C.
After oven dry, in the powder after oven dry, add 0.15g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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
To in embodiment 1, add aluminum solutions step to remove, other conditions be constant, are specially:
Get pretreated Concave-convex clay rod 14.5g, add 39ml to contain the lanthanum nitrate hexahydrate of 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 2 kinds of active components of load.
After oven dry, in the powder after oven dry, add 0.2g sesbania powder, drip rare nitric acid and be adjusted to the degree that is applicable to 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 is to carry out on fixed bed reactors, the amount of filling out of catalyst is 10ml(20～40 order), feedstock oil (reformed oil) bromine valency is 3200mgBr/100g.Reaction condition is: 160～180 DEG C of reaction temperatures, and operating pressure 1.0～2.0MPa, charging air speed is 2～10hr
-1.
, initial activity is to sample for the first time the olefin removal rate recording to the Performance Ratio of the catalyst deolefination that following table 1 is prepared for different process, and using olefin removal rate 60% as the standard that judges catalysqt deactivation.After inactivation, 400 DEG C of air oxidations regeneration 4 hours, finish afterwards with nitrogen blowing, remove the polymer, the poisonous substance etc. that on catalyst, hide active component, then reuse mensuration.
Utilize the olefin removal rate of the aromatic hydrocarbon product of formula calculating below:
Olefin removal rate=(raw material bromine valency-institute 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 (8)
1. for a modified clay catalyst for deolefination, it is characterized in that, composition and parts by weight are: 60～80 parts of clays, 1～10 part of heteropoly acid, 0.1～2 part, rare earth element and aluminum solutions are (with Al
2o
3content meter) 10～40 parts.
2. the modified clay catalyst for deolefination according to claim 1, is characterized in that: described rare earth element loads in clay duct, and described loaded by heteropoly acid is at surface of clay; Described Al
2o
3be coated on clay outer surface.
3. the preparation method of the modified clay catalyst for deolefination according to claim 1 and 2, is characterized in that, processing step comprises:
(1) pretreated clay is joined in rare earth compound solution to 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) precursor of aluminium is mixed with to aluminum solutions by deionized water, the clay after step (1) modification is joined in aluminum solutions, under the condition of heating, stir, be stirred to solution by evaporate to dryness;
(3) in the material after above-mentioned evaporate to dryness, add auxiliary agent and binding agent, the moulding of extruding or roll after mediation evenly, then through super-dry, last roasting moulding, bake out temperature is 100 DEG C～110 DEG C, and sintering temperature is 250～550 DEG C, roasting time is 1～4h.
4. the preparation method of the modified clay catalyst for deolefination according to claim 3, is characterized in that: the described clay of 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 chloride or the nitrate of La, Ce, Pr or Nd; 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;
Described heteropoly acid is the one in phosphotungstic acid, silico-tungstic acid, silicomolybdic acid, phosphomolybdic acid or germanotungstic acid;
The precursor of described aluminium is selected from one or more in boehmite, boehmite, monohydrate alumina, aluminium isopropoxide, aluminium colloidal sol, diaspore or gibbsite.
5. the preparation method of the modified clay catalyst for deolefination according to claim 3, is characterized in that: the clay described in step (1) is for having passed through in advance dispersion, reaming and acidification; Wherein dispersant is calgon, and mass concentration is 0.6%; Expanding agent is citric acid, and mass concentration is 0.5%; The acid that acidifying is used is selected from a kind of in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid or nitric acid or 2 kinds, and acid concentration is pressed H
+meter, concentration is 0.1mol/L～2mol/L.
6. the preparation method of the modified clay catalyst for deolefination according to claim 3, is characterized in that: the heating-up temperature described in step (2) is 40～85 DEG C.
7. the preparation method of the modified clay catalyst for deolefination according to claim 3, is characterized in that: the extrusion aid described in step (3) is sesbania powder or starch, and quality is 0.5%～2% of quality of material after evaporate to dryness.
8. the preparation method of the modified clay catalyst for deolefination according to claim 3, is characterized in that: the binding agent described in step (3) is rare nitric acid, wherein the mass concentration of dilute nitric acid solution is 1.0%～4.0%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536760A (en) * | 2015-12-03 | 2016-05-04 | 淮阴工学院 | Preparation method of composite clay alkene removal catalyst with high and lasting effect |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-03-20 CN CN201410105277.0A patent/CN103861644B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536760A (en) * | 2015-12-03 | 2016-05-04 | 淮阴工学院 | Preparation method of composite clay alkene removal catalyst with high and lasting effect |
| 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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