CN103769194A - Hydro-dearomatization catalyst and preparation method thereof - Google Patents
Hydro-dearomatization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydro-dearomatization catalyst and a preparation method thereof. In the catalyst, the main active component is Pt, the auxiliary component is Pd, and the carrier is a composite molecular sieve of amorphous silicon-aluminum and SBA-15/Y. The preparation method comprises the following steps: subjecting the SBA-15/Y composite molecular sieve and amorphous silicon-aluminum to processes of kneading, forming, drying, and burning so as to obtain a catalyst carrier, then loading Pd and Pt onto the catalyst carrier by adopting an impregnation method, drying, and burning so as to obtain the hydro-dearomatization catalyst. The catalyst has a higher hydro-dearomatization activity, and is especially suitable for hydro-dearomatization process and decoloring process of heavy aromatics-containing naphthenic high-viscosity white oil and solvent oil.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, relate in particular to catalytic hydro-dearomatization catalyst and preparation method thereof.This catalyst is suitable for the hydrogenation process of aromatic hydrocarbons, is particularly suitable for the hydrogenation aromatics-removing process containing the naphthene base crude oil of heavy aromatics.
Background technology
Under aerobic conditions, it is very sensitive to daylight, ultraviolet radiation that hydrotreatment generates oil (as top-grade lubricating oil, food-level white oil etc.), is exposed in daylight and air and causes that oil product appearance property is unstable, and oil product color can be deepened, and produces precipitation when serious.This type of oil requires viscosity low, and flash-point and boiling point are high, and volatility is little.Colorless and odorless, arene content is low, non-corrosiveness, good thermostability and oxidation stability, be difficult for causing gel; Biological property is good, meets environmental requirement.
Address the above problem, effective method carries out deep hydrogenation aromatic saturation to it exactly.Adopt conventional Hydrobon catalyst, because the fault of construction of catalyst and cycloalkyl viscous crude cut have, viscosity is large, molecular weight is high, the many features of condensed ring structure, cause polycyclic aromatic hydrocarbon in large molecule cut to be difficult to obtain sufficient hydrogenation saturated, therefore need to adopt the catalyst of special construction to improve the selective and activity stability of catalyst.
What CN1769379A, CN1140748A, CN1070215A all related to is common metal catalyst, and the defect of this catalyst is that activity is lower, can not effectively solve the deeply de-aromatizing problem of lubricating oil; CN98117511.2, CN90100187.2 all relate to platiniferous and the bimetallic noble metal hydrogenation catalyst of palladium, but due to the A1 in these two kinds of catalyst carriers
2o
3content is lower, is all no more than 30wt%, therefore the acidity of this catalyst a little less than, be only suitable for the hydrogenation process of light-end products, distillate, and be not suitable for the deeply hydrodearomatized process of heavy grease.
US5393408 relates to two kinds of catalyst of a kind of macropore amorphous aluminum silicide and a kind of mesopore amorphous aluminum silicide carrier-supported precious metal, need adopt two-stage hydrogenation to hydrogenation lube base oil, just can reach the object of Arene removal.
US4263127, US4325804 disclose the method for a kind of Hydrogenation for food-level white oil, and its catalyst relating to is noble metal catalyst, and the carrier of this catalyst is aluminium oxide, and aided metal is silicon, zinc or magnesium.CN101745383A discloses a kind of preparation method of deeply hydrodearomatized catalyst, and main active component is Pt, and auxiliary agent is Pd, and carrier is amorphous silicon alumina supporter, SiO
2content is 40%～60% of vehicle weight.The support acidity of catalyst prepared by above method is low, and metal dispersion is poor, and catalyst activity is lower, de-aromatic hydrocarbons weak effect.
CN201010197869.1 discloses a kind of preparation method of lube hydrotreating catalyst, and carrier is made up of silica-alumina, and active component is mainly Pd and Pt; In the method, molecular sieve and amorphous aluminum silicide are to form mixed powder by physical mixed, the precious metal colloid of preparation is sprayed on Y zeolite and amorphous aluminum silicide mixed powder, then passes through kneading, and extrusion, catalyst is made in roasting.Specific area and the pore volume of the catalyst of the method gained are less, and acid centre part is capped, and total acid content and acidity distribute still needs further improvement.In the method because noble metal is to be sprayed on Y zeolite and amorphous aluminum silicide mixture, pass through again kneading, extrusion, roasting just can be made catalyst, noble metal loses larger in this process, improved greatly the cost of catalyst, catalyst syntheti c route poor operability, is not suitable for large-scale production.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of preparation method of noble metal catalyst of hydrogenation aromatics-removing.This catalyst has higher hydrogenation aromatics-removing activity, is particularly suitable for containing the cycloalkyl high viscosity white oil of heavy aromatics and hydrogenation aromatics-removing and the decolorization of solvent naphtha.Catalytic hydro-dearomatization catalyst of the present invention, main active component is Pt, adjuvant component is Pd, and carrier is amorphous aluminum silicide and SBA-15/Y composite molecular screen, take the weight of catalyst as benchmark, the content of Pt is 0.1wt%～0.5wt%, the content of Pd is 0.3wt%～0.8wt%, and the content of amorphous aluminum silicide is 50wt%～90wt%, is preferably 70wt%～85wt%, the content of SBA-15/Y composite molecular screen is 5wt%～20wt%, and the content of adhesive is 9wt%～30wt%; In SBA-15/Y composite molecular screen, Y zeolite weight content is 50wt%～90wt%, is preferably 60wt%～80wt%; The character of SBA-15/Y composite molecular screen used is as follows: SiO
2/ A1
2o
3mol ratio is 40 ~ 85, and specific area is 400m
2/ g～1000m
2/ g, pore volume is 0.5cm
3/ g～2.0cm
3/ g, infrared acidity is 0.3～0.6mmol/g.
Dioxide-containing silica 15wt%～45wt% in described amorphous aluminum silicide.Be preferably 20wt%～35wt%.
The character of the catalytic hydro-dearomatization catalyst of gained of the present invention is as follows: specific area is 350～550m
2/ g, is preferably 380～500m
2/ g, pore volume is 0.5～1.2ml/g, is preferably 0.6～0.9ml/g, meleic acid amount is 0.3～1.0mmol/g, is preferably 0.4～0.8mmol/g.
The preparation method of catalytic hydro-dearomatization catalyst of the present invention, comprising: by SBA-15/Y composite molecular screen and amorphous aluminum silicide and adhesive, through kneading, moulding, dry and roasting, obtains catalyst carrier; Adopt infusion process in catalyst carrier after load P d and Pt, drying and roasting, obtain catalytic hydro-dearomatization catalyst.
In the inventive method, the preferred preparation method of SBA-15/Y composite molecular screen, comprising:
(a) silicon source is joined in acid solution, till being stirred to and becoming clear solution;
(b) cationic surfactant is dissolved in the water and is stirred, and control suitable pH value;
(c) Y zeolite carries out hydrothermal treatment consists, and described hydrothermal treatment consists temperature is that 350 ~ 650 ℃, pressure are 0.5 ~ 3.0MPa, reaction time 1 ~ 6 hour;
(d) solution of step (a) gained is added in the mixed solution of compositions comprising cationic surfactants of step (b) gained, stir, then add the molecular sieve of step (c) gained, after mixing, hydrothermal treatment consists 24 ~ 72 hours at 70 ~ 150 ℃, after filtration, washing, then drying, obtains SBA-15/Y composite molecular screen.
In the inventive method, adhesive can adopt the adhesive that Kaolinite Preparation of Catalyst is conventional, is preferably aluminium oxide.In shaping of catalyst process, also can add the shaping assistants such as peptization acid, extrusion aid.
In the inventive method, in step (a), described acid solution can be one or more the aqueous solution in phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the concentration of acid solution is 0.01 ~ 0.10mol/L.Described silicon source can be organic silicone grease alkane or inorganic silicon source, organic silicone grease alkane can be one or more in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, and described inorganic silicon source can be one or more in sodium metasilicate, white carbon.Silicon source is joined in acid solution, and making the pH value of system is 2 ~ 6, is preferably at the temperature of 10 ~ 50 ℃ and reacts 2 ~ 20 hours, obtains clear solution.
In the present invention, described cationic surfactant can be one or more in polyethylene polyamines class, ethanolamines and quaternary ammonium salts.Described polyethylene polyamines class is one or more in ethylenimine, Diethylenetriamine etc.; Ethanolamines is one or more in diethanol amine, triethanolamine etc.; Quaternary ammonium salts is one or more in single head quaternary ammonium salt, bi-quaternary ammonium salt, three quaternary ammonium salts.
Take step (a) and (b) with (c), the gross weight of gained material is as benchmark, and the consumption of described cationic surfactant is 5wt% ~ 20wt%, and the concentration of the cationic surfactant working solution of preparing is 5wt%～20wt%.Described silicon source is with SiO
2meter is 0.2 ~ 15.0 with the mass ratio of cationic surfactant.
In the present invention, the character of described Y zeolite is as follows: SiO
2/ A1
2o
3mol ratio is 35 ~ 70, and lattice constant is 2.426 ~ 2.433nm, and relative crystallinity is 95% ~ 110%.
In the inventive method, the described drying condition of step (d) is as follows: temperature is 50 ~ 120 ℃, and the time is 6 ~ 12 hours.
The present invention's amorphous aluminum silicide used can be prepared by coprecipitation or grafting copolymerization process, by conventional method preparation in document.SiO in the amorphous aluminum silicide of gained
2weight content be 15% ~ 45%, be preferably 20% ~ 35%.
In method for preparing catalyst of the present invention, the method for introducing Pt and Pd adopts infusion process.The present invention is by amorphous aluminum silicide, SBA-15/Y composite molecular screen and adhesive kneading, moulding, and drying and roasting obtain carrier, then adopts infusion process supporting Pt and Pd, and drying and roasting, obtain catalytic hydro-dearomatization catalyst.Wherein, catalyst can carry out moulding according to actual needs, and shape can be cylindrical bars, clover etc.Described carrier strip through 100 ~ 130 ℃ dry 12 ~ 14 hours, 450 ~ 550 ℃ of roastings 5 ~ 10 hours.Described infusion process can adopt the method for saturated dipping or excessive dipping, and after dipping Pt and Pd, catalyst is dried with the condition of roasting as follows: be dried 12 ~ 14 hours, roasting 5 ~ 10 hours at 500 ~ 600 ℃ at 100 ~ 130 ℃.Above-mentioned catalyst preparation process and condition are all well known to those skilled in the art.
Catalyst of the present invention adopts noble metal as active component, carrier adopts amorphous aluminum silicide and SBA-15/Y composite molecular screen, wherein SBA-15/Y composite molecular screen has different bore diameter gradients and suitable acidity, match with amorphous aluminum silicide simultaneously, make catalyst both can meet more micromolecular hydrofinishing, can meet again the hydrofinishing of hyperviscosity cycloalkyl distillate, more be conducive to the selective opening of aromatic hydrocarbons, be suitable for especially in the hydrogenation aromatics-removing process of the cycloalkyl raw material that viscosity is high, condensed ring fractional saturation arene content is high.
In the inventive method, SBA-15/Y composite molecular screen adopts preferred preparation method, wherein Y zeolite adopts suitable condition to carry out hydrothermal treatment consists, and part aluminium removes formation non-framework aluminum from skeleton, and these non-framework aluminum major parts are present in the duct of molecular sieve.Y zeolite after hydrothermal treatment consists is added in the mixed system of silicon source and acid solution and surfactant, these non-framework aluminums are in above-mentioned system, can be from the duct of micro porous molecular sieve free out as the aluminium source of synthesising mesoporous molecular sieve, also make micro porous molecular sieve expose more aluminium active sites, be conducive to the compound of micro porous molecular sieve and mesopore molecular sieve.This composite molecular screen synthetic takes full advantage of the non-framework aluminum that micro porous molecular sieve takes off, and removed conventional aluminium source additional while preparing molecular sieve from, is conducive to improve the silica alumina ratio of composite molecular screen, also improved hydro-thermal and the heat endurance of composite molecular screen.The SBA-15/Y composite molecular screen that catalyst of the present invention adopts method for optimizing to prepare, because it has larger specific surface and pore volume and acid centre, not only for reactant provides enough passages, be conducive to the turnover of reactant and product, the active ingredient of carrier is improved greatly, improve the uniformity that acid centre distributes in duct, and contributed to improve the dispersiveness of active metal, made catalyst of the present invention more be conducive to the selective opening of aromatic hydrocarbons.
Catalyst preparation process of the present invention is simple, convenient, and easy operating is applicable to industrial production.Catalyst of the present invention is particularly suitable for the hydrogenation process of aromatic hydrocarbons, is particularly suitable for hydrogenation aromatics-removing and decolorization containing cycloalkyl high viscosity white oil, solvent naphtha and the hydrocracking tail oil of heavy aromatics, can obtain good result of use.
Catalyst of the present invention is processing when naphthene base crude oil, reaction condition generally under hydrogen existence condition, the best 10 ~ 20MPa of reaction pressure, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 7.0h when liquid
-1, 180 ~ 250 ℃ of reaction temperatures.
The specific embodiment
The specific area of product of the present invention and pore volume are to adopt low temperature liquid nitrogen determination of adsorption method.Acid amount and Acidity adopt infrared spectrometer to record, and the adsorbent that uses is pyridine.Relative crystallinity adopts XRD to record, and the degree of crystallinity of standard sample NaY is 100.In the present invention, wt% is mass fraction.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
(1) 200g ethyl orthosilicate is joined in the HCl solution that concentration is 0.28mol/L, stir about 3 hours at 35 ℃, till becoming clear solution;
(2) 100g diethanol amine is dissolved in the water, maintaining pH value is at 3,40 ℃, to stir 2 hours, obtains the mixed liquor of compositions comprising cationic surfactants;
(3) get 1200g molecular sieve Y-1(specific area 794 m
2/ g, pore volume 0.39 mL/g, relative crystallinity 99, acid amount 0.632 mmol/g) join in hydro-thermal stove with under 550 ℃, 2MPa pressure and react 2 hours, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, at 40 ℃, stir 24 hours, then add the molecular sieve Y-1 after step (3) hydrothermal treatment consists, hydrothermal treatment consists 48 hours at 100 ℃ to neutral, is dried 6 hours with a large amount of deionized water rinsing filter cakes at 120 ℃, then roasting 7 hours at 550 ℃ of air atmospheres, remove surfactant molecule, obtain microporous-mesoporous composite molecular sieve F-1, wherein the content of Y zeolite is 80%.The SiO of this composite molecular screen
2/ A1
2o
3mol ratio 55, specific area is 678 m
2/ g, pore volume is 0.60/g, infrared acidity is 0.439mol/g, relative crystallinity 39%.
Embodiment 2
(1) with embodiment 1;
(2) with embodiment 1;
(3) get 900 sieve Y-2(specific area 759 m
2/ g, pore volume 0.37 mL/g, relative crystallinity 96%, acid amount 0.593 mmol/g) join in hydro-thermal stove with under 550 ℃, 2MPa pressure and react 2 hours, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, at 40 ℃, stir 24 hours, then add the molecular sieve Y-2 after step (3) hydrothermal treatment consists, hydrothermal treatment consists 48 hours at 100 ℃ to neutral, is dried 6 hours with a large amount of deionized water rinsing filter cakes at 120 ℃, then roasting 7 hours at 550 ℃ of air atmospheres, remove surfactant molecule, obtain microporous-mesoporous composite molecular sieve F-2, wherein the content of Y zeolite is 75%.The SiO of this composite molecular screen
2/ A1
2o
3mol ratio 60, specific surface is 657m
2/ g, pore volume is 0.58ml/g, infrared acidity is 0.446mmol/g, relative crystallinity 43.
Embodiment 3
(1) 200g ethyl orthosilicate is joined in the salpeter solution of 0.30 mol/L, stir about 3 hours at 35 ℃, till becoming clear solution;
(2) 100g ethylenimine is dissolved in the water, maintaining pH value is at 3,40 ℃, to stir 2 hours, obtains the mixed liquor of compositions comprising cationic surfactants;
(3) get 700g molecular sieve Y-1(specific area 794 m
2/ g, pore volume 0.39 mL/g, relative crystallinity 99, acid amount 0.632 mmol/g) join in hydro-thermal stove with under 550 ℃, 2MPa pressure and react 2 hours, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, at 40 ℃, stir 24 hours, then add molecular sieve Y-1 after step (3) hydrothermal treatment consists hydrothermal treatment consists 48 hours at 100 ℃, extremely neutral with a large amount of deionized water rinsing filter cakes, at 120 ℃ dry 6 hours, and then roasting 7 hours at 550 ℃ of air atmospheres, remove surfactant molecule, obtain microporous-mesoporous composite molecular sieve F-3, wherein the content of Y zeolite is 70wt%.The SiO of this composite molecular screen
2/ A1
2o
3mol ratio 66, specific surface is 699m
2/ g, pore volume is 0.59ml/g, infrared acidity is 0.502mmol/g, relative crystallinity 45.
Embodiment 4
Carrier A involved in the present invention and catalyst catA.(specific surface is 349m to get 100g amorphous aluminum silicide
2/ g, pore volume is 0.79ml/g), 9.5g F-1 composite molecular screen and 15gSB aluminium oxide, the rare nitric acid kneading of 100g, roll, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, 550 ℃ of roastings 4 hours, make carrier A.Adopt the method for conventional incipient impregnation, by PdC1
2(analyzing pure) and Pt (NH
4)
4c1
2the solution of (analyzing pure) is by final catalyst metals amount (Pt 0.15wt %; Pd0.5wt %) step impregnation in type carrier, leave standstill 12h, 110 ℃ dry 6 hours, 480 ℃ of roastings 4 hours, make catalyst catA.
Embodiment 5
Preparation condition is with example 4.Replace F-1 by F-2, make carrier B and catalyst catB.
Embodiment 6
Preparation condition is with embodiment 4.Replace F-1 by F-3, make support C and catalyst catC.
Embodiment 7
(1) 400g ethyl orthosilicate and 2g aluminium isopropoxide are joined in the HCl solution of 0.28M, stir about 3 hours at 35 ℃, till becoming clear solution;
(2) 200g diethanol amine is dissolved in the water, maintaining specific pH value is at 3,40 ℃, to stir 2 hours, obtains the mixed liquor of compositions comprising cationic surfactants;
(3) molecular sieve Y-1 is not treated;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, at 40 ℃, stir 24 hours, then add the molecular sieve Y-1 of 1200g without hydrothermal treatment consists, hydrothermal treatment consists 48 hours at 100 ℃, with a large amount of deionized water rinsing filter cakes to neutral, at 120 ℃ dry 6 hours, and then roasting 7 hours at 550 ℃ of air atmospheres, remove surfactant molecule, obtain microporous-mesoporous composite molecular sieve F-4.Wherein the content of Y zeolite is 80%.The SiO of this composite molecular screen
2/ A1
2o
3mol ratio 56, specific area is 615m
2/ g, pore volume is 0.55mL/g, infrared acidity is 0.415mol/g, relative crystallinity 36%.
Embodiment 8
Preparation condition is with embodiment 4.Replace F-1 by F-4, make carrier D and catalyst catD.
Comparative example 1
(1) by 12g modification Y-1 molecular sieve (with embodiment 1) and 75g amorphous aluminum silicide, (specific surface is 349m
2/ g, pore volume is 0.79ml/g) machinery mixes.
(2) be mixed with aqueous solution 100ml with containing the chloroplatinic acid that is equivalent to the chlorine handle acid of 5gPd and is equivalent to 1.5gPt, the PVP solution 6ml of 5g/L is added in above-mentioned solution, stir 2h, adding concentration is 2% HCHO solution 15ml, stir reduction 5h, after reduction, obtain precious metal colloid.
(3) precious metal colloid step (2) being obtained is sprayed on the mixed carrier surface that step (1) obtains, when sprinkling, need to stir support powder, under normal temperature, normal pressure, dry 60h, keep relative air humidity 60 %, then every 3min heats up 1 ℃, and temperature is risen to 55 ℃, dry 20h, every 3min heats up 1 ℃ again, and temperature is warming up to 100 ℃, dries 48h; When oven dry, need to first will vacuumize, then pass into nitrogen, remain on nitrogen atmosphere.(4) product that step (3) obtains and 12gSB aluminium oxide, the rare nitric acid kneading of 80g, roll, make can extrusion paste, extruded moulding, is slowly warming up to 110 ℃, under nitrogen atmosphere, dries 16h, then at 550 ℃ of roasting 3h of oxygen-free atmosphere Program intensification, obtain catalyst catE.
The physico-chemical property of catalyst listed embodiment of the present invention 1-8 and comparative example 1 and made by table 1.
The physico-chemical property of table 1 catalyst
| Catalyst numbering | catA | catB | catC | catD | catE |
| Catalyst composition | |||||
| Pt，wt% | 0.15 | 0.18 | 0.20 | 0. 19 | 0.16 |
| Pd，wt% | 0.52 | 0.57 | 0.60 | 0.54 | 0.49 |
| Catalyst property | |||||
| Specific area, m 2/g | 402 | 405 | 408 | 395 | 350 |
| Pore volume, ml/g | 0.71 | 0.70 | 0.72 | 0.68 | 0.58 |
| Infrared total acid content, mmol/g | 0.446 | 0.419 | 0.457 | 0.398 | 0.376 |
The invention described above catalyst catA, catB, catC, catD and comparative example catalyst atE are carried out to reactivity worth evaluation test.Test is carried out on 200ml small hydrogenation device, and take the lube stock of >320 ℃ of low-voltage hydrogenation isomate as raw material, its character is in table 2.Adopting high-pressure hydrogenation post-refining process process, is 15.0MPa, hydrogen to oil volume ratio 1000,220 ℃ of reaction temperatures, volume space velocity 0.6h in hydrogen dividing potential drop
-1process conditions under, the engineer testing of having carried out hydrogenation and producing white oil, reactivity worth evaluation test the results are shown in Table 3.
>320 ℃ of lube stock character of table 2 low-voltage hydrogenation isomery
| Analysis project | |
| Density (20 ℃)/kgm -3 | 857.1 |
| Sulphur/μ gg -1 | 3.0 |
| Nitrogen/μ gg -1 | 1.0 |
| Pour point/℃ | -30 |
| Viscosity (100 ℃)/mm 2·s -1 | 5.097 |
| Viscosity (40 ℃)/mm 2·s -1 | 27.41 |
| Carbon residue, wt% | 0.01 |
| Aromatic hydrocarbons, wt% | 10.7 |
Table 3 catalyst activity evaluation result
| Catalyst numbering | catA | catB | catC | catD | catE |
| Reaction temperature, ℃ | 224 | 225 | 223 | 228 | 235 |
| Liquid is received, wt% | 99.7 | 99.5 | 99.6 | 99.3 | 98.8 |
| Viscosity (40 ℃)/mm 2·s -1 | 33.38 | 33.04 | 32.78 | 32.86 | 31.09 |
| Viscosity (100 ℃)/mm 2·s -1 | 6.978 | 6.921 | 6.9616 | 6.841 | 6.109 |
| Pour point/℃ | -14 | -13 | -14 | -12 | -10 |
| Saybolt color/number | +33 | +32 | +33 | +31 | +30 |
| Readily carbonizable substance (100 ℃) | Pass through | Pass through | Pass through | Pass through | Pass through |
| Condensed-nuclei aromatics (260～420nm)/cm | <0.1 | <0.1 | <0.1 | <0.1 | <0.1 |
Claims (19)
1. a catalytic hydro-dearomatization catalyst, main active component is Pt, adjuvant component is Pd, carrier is amorphous aluminum silicide and SBA-15/Y composite molecular screen, and take the weight of catalyst as benchmark, the content of Pt is 0.1wt%～0.5wt%, the content of Pd is 0.3wt%～0.8wt%, the content of amorphous aluminum silicide is 50wt%～90wt%, and the content of SBA-15/Y composite molecular screen is 5wt%～20wt%, and the content of adhesive is 9wt%～30wt%; In SBA-15/Y composite molecular screen, Y zeolite weight content is 50wt%～90wt%; The character of SBA-15/Y composite molecular screen used is as follows: SiO
2/ A1
2o
3mol ratio is 40 ~ 85, and specific area is 400m
2/ g～1000m
2/ g, pore volume is 0.5cm
3/ g～2.0cm
3/ g, infrared acidity is 0.3～0.6mmol/g.
2. according to catalyst claimed in claim 1, it is characterized in that in described catalytic hydro-dearomatization catalyst, the content of amorphous aluminum silicide is 70wt%～85wt%.
3. according to catalyst claimed in claim 1, it is characterized in that in described SBA-15/Y composite molecular screen, Y zeolite weight content is 60wt%～80wt%.
4. according to catalyst claimed in claim 1, it is characterized in that dioxide-containing silica 15wt%～45wt% in described amorphous aluminum silicide.
5. according to catalyst claimed in claim 1, it is characterized in that the character of described catalytic hydro-dearomatization catalyst is as follows: specific area is 350～550m
2/ g, pore volume is 0.5～1.2ml/g, meleic acid amount is 0.3～1.0mmol/g.
6. according to catalyst claimed in claim 1, it is characterized in that the character of described catalytic hydro-dearomatization catalyst is as follows: specific area is 380～500m
2/ g, pore volume is 0.6～0.9ml/g, meleic acid amount is 0.4～0.8mmol/g.
7. the preparation method of the arbitrary described catalyst of claim 1 ~ 6, comprising: SBA-15/Y composite molecular screen and amorphous aluminum silicide and adhesive, through kneading, moulding, are dried and roasting, obtain catalyst carrier; Adopt infusion process in catalyst carrier after load P d and Pt, drying and roasting, obtain catalytic hydro-dearomatization catalyst.
8. in accordance with the method for claim 7, it is characterized in that: after moulding, the condition of carrier drying and roasting is as follows: through 100 ~ 130 ℃ dry 12 ~ 14 hours, 450 ~ 550 ℃ of roastings 5 ~ 10 hours.
9. in accordance with the method for claim 7, it is characterized in that described infusion process adopts the method for saturated dipping or excessive dipping, after infusion process supporting Pt and Pd, condition dry and roasting is as follows: be dried 12 ~ 14 hours, roasting 5 ~ 10 hours at 500 ~ 600 ℃ at 100 ~ 130 ℃.
10. according to catalyst claimed in claim 7, it is characterized in that the preparation method of described SBA-15/Y composite molecular screen, comprising:
(a) silicon source is joined in acid solution, till being stirred to and becoming clear solution;
(b) cationic surfactant is dissolved in the water and is stirred;
(c) Y zeolite carries out hydrothermal treatment consists, and described hydrothermal treatment consists temperature is that 350 ~ 650 ℃, pressure are 0.5 ~ 3.0MPa, reaction time 1 ~ 6 hour;
(d) solution of step (a) gained is added in the mixed solution of compositions comprising cationic surfactants of step (b) gained, stir, then add the molecular sieve of step (c) gained, after mixing, hydrothermal treatment consists 24 ~ 72 hours at 70 ~ 150 ℃, after filtration, washing, then drying, obtains mesoporous-mesoporous-microporous composite molecular sieve.
11. in accordance with the method for claim 10, it is characterized in that in step (a), and described acid solution is one or more the aqueous solution in phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the concentration of described acid solution is 0.01 ~ 0.10mol/L.
12. in accordance with the method for claim 10, it is characterized in that in step (a), described silicon source is organic silicone grease alkane or inorganic silicon source, organic silicone grease alkane is one or more in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, and described inorganic silicon source is one or more in sodium metasilicate, white carbon.
13. in accordance with the method for claim 10, it is characterized in that, in step (a), silicon source being joined in acid solution, and the pH value that makes system is 2 ~ 6, reacts 2 ~ 20 hours at the temperature of 10 ~ 50 ℃, obtains clear solution.
14. in accordance with the method for claim 10, it is characterized in that described cationic surfactant is one or more in polyethylene polyamines class, ethanolamines and quaternary ammonium salts, the concentration of the cationic surfactant working solution of preparing is 5wt%～20wt%.
15. in accordance with the method for claim 14, it is characterized in that described polyethylene polyamines class is one or more in ethylenimine, Diethylenetriamine; Ethanolamines is one or more in diethanol amine, triethanolamine; Quaternary ammonium salts is one or more in single head quaternary ammonium salt, bi-quaternary ammonium salt, three quaternary ammonium salts.
16. in accordance with the method for claim 10, it is characterized in that the gross weight of gained material is as benchmark take step (a) and (b) with (c), and the consumption of described cationic surfactant is 5wt% ~ 20wt%.
17. in accordance with the method for claim 10, it is characterized in that described silicon source is with SiO
2meter is 0.2 ~ 15.0 with the mass ratio of cationic surfactant.
18. in accordance with the method for claim 10, it is characterized in that the described drying condition of step (d) is as follows: temperature is 50 ~ 120 ℃, and the time is 6 ~ 12 hours.
19. in accordance with the method for claim 10, it is characterized in that the character of the described Y zeolite of step (c) is as follows: SiO
2/ A1
2o
3mol ratio is 35 ~ 70, and lattice constant is 2.426 ~ 2.433nm, and relative crystallinity is 95% ~ 110%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409477.6A CN103769194B (en) | 2012-10-24 | 2012-10-24 | A kind of catalytic hydro-dearomatization catalyst and preparation method thereof |
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| CN114453014A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrogenation dearomatization catalyst, preparation method and application thereof |
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