CN103769194B - A kind of catalytic hydro-dearomatization catalyst and preparation method thereof - Google Patents
A kind of catalytic hydro-dearomatization catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103769194B CN103769194B CN201210409477.6A CN201210409477A CN103769194B CN 103769194 B CN103769194 B CN 103769194B CN 201210409477 A CN201210409477 A CN 201210409477A CN 103769194 B CN103769194 B CN 103769194B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- hours
- sba
- composite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of catalytic hydro-dearomatization catalyst and preparation method thereof.In this catalyst, main active component is Pt, adjuvant component is Pd, carrier is amorphous aluminum silicide and SBA-15/Y composite molecular screen, and its preparation method is by SBA-15/Y composite molecular screen and amorphous aluminum silicide and adhesive through kneading, shaping, dry and roasting, obtain catalyst carrier, adopt infusion process on a catalyst support after load P d and Pt, drying and roasting, obtain catalytic hydro-dearomatization catalyst.It is active that this catalyst has higher hydrogenation aromatics-removing, is particularly suitable for containing the cycloalkyl high viscosity white oil of heavy aromatics and the hydrogenation aromatics-removing of solvent naphtha and decolorization.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, particularly relate 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 of the naphthene base crude oil containing 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.), and be exposed in daylight and air and cause oil product appearance property unstable, oil product color can be deepened, and produces precipitation time serious.This type of oil requires that viscosity is low, flash-point and boiling point high, volatility is little.Colorless and odorless, arene content is low, non-corrosiveness, and good thermostability and oxidation stability, not easily cause gel; Biological property is good, meets environmental requirement.
Solve the problem, most 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 cyclic structure, cause the polycyclic aromatic hydrocarbon in large molecular fraction to be difficult to obtain sufficient hydrotreated lube base oil, therefore need to adopt the catalyst of special construction to improve the selective of catalyst and activity stability.
What CN1769379A, CN1140748A, CN1070215A all related to is conventional metallic catalyst, and the defect of this catalyst is that activity is lower, effectively can not 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%, and therefore the acidity of this catalyst is more weak, is only suitable for the hydrogenation process of light-end products, distillate, and is 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 mesoporous amorphous silica-alumina supports carried noble metal, need adopt two-stage hydrogenation, just can reach the object of Arene removal to hydro-treated lubricating base oil.
US4263127, US4325804 disclose the method for a kind of Hydrogenation for food-level white oil, and its catalyst related 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, Porous deproteinized bone weak effect.
CN201010197869.1 discloses a kind of preparation method of lube hydrofmishing catalyst, and carrier is made up of silica-alumina, and active component is mainly Pd and Pt; The method Middle molecule sieve and amorphous aluminum silicide form mixed powder by physical mixed, be sprayed at by the precious metal colloid of preparation on Y zeolite and amorphous aluminum silicide mixed powder, then through kneading, extrusion, catalyst 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 distribution still need further improvement.Because noble metal is being sprayed on Y zeolite and amorphous aluminum silicide mixture in the method, again through kneading, extrusion, roasting just can make catalyst, noble metal loses larger in the process, improve the cost of catalyst greatly, catalyst preparing 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.It is active that this catalyst has higher hydrogenation aromatics-removing, is particularly suitable for containing the cycloalkyl high viscosity white oil of heavy aromatics and the hydrogenation aromatics-removing of solvent naphtha and decolorization.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, with the weight of catalyst for 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, and be 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, shaping, dry and roasting, obtains catalyst carrier; Adopt infusion process on a catalyst support 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 joins in acid solution by (), be stirred to till becoming clear solution;
B cationic surfactant is dissolved in the water and stirs by (), and control suitable pH value;
C () Y zeolite carries out hydrothermal treatment consists, described hydrothermal treatment consists temperature is 350 ~ 650 DEG C, pressure is 0.5 ~ 3.0MPa, 1 ~ 6 hour reaction time;
D the solution of step (a) gained is added in the mixed solution of the compositions comprising cationic surfactants of step (b) gained by (), stir, then the molecular sieve of step (c) gained is added, after mixing, hydrothermal treatment consists 24 ~ 72 hours at 70 ~ 150 DEG C, after filtration, wash, then drying, obtain 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 the aqueous solution of one or more 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, makes the pH value of system be 2 ~ 6, preferably react 2 ~ 20 hours at the temperature of 10 ~ 50 DEG C, obtain 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.
With the gross weight of step (a) and (b) and (c) gained material for benchmark, the consumption of described cationic surfactant is 5wt% ~ 20wt%, and the concentration of the cationic surfactant working solution prepared 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 drying condition described in step (d) is as follows: temperature is 50 ~ 120 DEG C, and the time is 6 ~ 12 hours.
The present invention's amorphous aluminum silicide used can be prepared by coprecipitation or grafting copolymerization process, prepares by conventional method 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 introducing Pt and Pd adopts infusion process.The present invention is by amorphous aluminum silicide, SBA-15/Y composite molecular screen and adhesive kneading, shaping, and drying and roasting obtain carrier, and then adopt infusion process supporting Pt and Pd, drying and roasting, obtain catalytic hydro-dearomatization catalyst.Wherein, catalyst can carry out shaping according to actual needs, and shape can be cylindrical bars, clover etc.Described carrier strip through 100 ~ 130 DEG C of dryings 12 ~ 14 hours, 450 ~ 550 DEG C of roastings 5 ~ 10 hours.Described infusion process can adopt the method for saturated dipping or excessive dipping, and after dipping Pt and Pd, the condition that catalyst carries out drying and roasting was as follows: 100 ~ 130 DEG C of dryings 12 ~ 14 hours, roasting 5 ~ 10 hours at 500 ~ 600 DEG C.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, the hydrofinishing of hyperviscosity cycloalkyl distillate can be met again, 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, the saturated arene content of fused moiety 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 free out as the aluminium source of synthesising mesoporous molecular sieve from the duct of micro porous 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.The synthesis of this composite molecular screen takes full advantage of the non-framework aluminum that micro porous molecular sieve takes off, and eliminates aluminium source additional when routine prepares molecular sieve, is conducive to the silica alumina ratio improving composite molecular screen, also improves 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, be not only reactant and provide 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 contribute to the dispersiveness improving active metal, make 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, is easy to operation, is applicable to industrial production.Catalyst of the present invention is particularly suitable for the hydrogenation process of aromatic hydrocarbons, is particularly suitable for the hydrogenation aromatics-removing containing the cycloalkyl high viscosity white oil of heavy aromatics, solvent naphtha and hydrocracking tail oil and decolorization, can obtains good result of use.
Catalyst of the present invention process naphthene base crude oil time, 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 during liquid
-1, reaction temperature 180 ~ 250 DEG C.
Detailed description of the invention
The specific area of product of the present invention and pore volume adopt low temperature liquid nitrogen determination of adsorption method.Acid amount and Acidity employing infrared spectrometer record, use adsorbent for 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 being joined concentration is in the HCl solution of 0.28mol/L, and stir about 3 hours at 35 DEG C, to becoming clear solution;
(2) be dissolved in the water by 100g diethanol amine, maintaining pH value is stir 2 hours at 3,40 DEG C, obtains the mixed liquor of compositions comprising cationic surfactants;
(3) 1200g molecular sieve Y-1(specific area 794m is got
2/ g, pore volume 0.39mL/g, relative crystallinity 99, acid amount 0.632mmol/g) to join in hydro-thermal stove with 550 DEG C, reaction 2 hours under 2MPa pressure, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, stir 24 hours at 40 DEG C, then the molecular sieve Y-1 after step (3) hydrothermal treatment consists is added, hydrothermal treatment consists 48 hours at 100 DEG C, with a large amount of deionized water rinsing filter cakes to neutral, drying 6 hours at 120 DEG C, then roasting 7 hours at air atmosphere 550 DEG C, removing 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 678m
2/ g, pore volume is 0.60/g, and infrared acidity is 0.439mol/g, relative crystallinity 39%.
Embodiment 2
(1) with embodiment 1;
(2) with embodiment 1;
(3) 900 sieve Y-2(specific area 759m are got
2/ g, pore volume 0.37mL/g, relative crystallinity 96%, acid amount 0.593mmol/g) to join in hydro-thermal stove with 550 DEG C, reaction 2 hours under 2MPa pressure, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, stir 24 hours at 40 DEG C, then the molecular sieve Y-2 after step (3) hydrothermal treatment consists is added, hydrothermal treatment consists 48 hours at 100 DEG C, with a large amount of deionized water rinsing filter cakes to neutral, drying 6 hours at 120 DEG C, then roasting 7 hours at air atmosphere 550 DEG C, removing 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, and infrared acidity is 0.446mmol/g, relative crystallinity 43.
Embodiment 3
(1) join in the salpeter solution of 0.30mol/L by 200g ethyl orthosilicate, stir about 3 hours at 35 DEG C, to becoming clear solution;
(2) be dissolved in the water by 100g ethylenimine, maintaining pH value is stir 2 hours at 3,40 DEG C, obtains the mixed liquor of compositions comprising cationic surfactants;
(3) 700g molecular sieve Y-1(specific area 794m is got
2/ g, pore volume 0.39mL/g, relative crystallinity 99, acid amount 0.632mmol/g) to join in hydro-thermal stove with 550 DEG C, reaction 2 hours under 2MPa pressure, then take out;
(4) solution of step (1) gained is added in the mixed liquor of step (2) gained, stir 24 hours at 40 DEG C, then the hydrothermal treatment consists 48 hours at 100 DEG C of the molecular sieve Y-1 after step (3) hydrothermal treatment consists is added, with a large amount of deionized water rinsing filter cakes to neutral, at 120 DEG C dry 6 hours, and then roasting 7 hours at air atmosphere 550 DEG C, removing 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, and 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), 9.5gF-1 composite molecular screen and 15gSB aluminium oxide, 100g dust technology kneading, roll, making can the paste of extrusion, extruded moulding.110 DEG C of dryings 6 hours, 550 DEG C of roastings 4 hours, obtained 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 (Pt0.15wt%; Pd0.5wt%) step impregnation is in type carrier, leaves standstill 12h, 110 DEG C of dryings 6 hours, 480 DEG C of roastings 4 hours, obtained catalyst catA.
Embodiment 5
Preparation condition is with example 4.F-1 is replaced, obtained carrier B and catalyst catB by F-2.
Embodiment 6
Preparation condition is with embodiment 4.F-1 is replaced, obtained support C and catalyst catC by F-3.
Embodiment 7
(1) join in the HCl solution of 0.28M by 400g ethyl orthosilicate and 2g aluminium isopropoxide, stir about 3 hours at 35 DEG C, to becoming clear solution;
(2) be dissolved in the water by 200g diethanol amine, maintaining specific pH value is stir 2 hours at 3,40 DEG C, 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, stir 24 hours at 40 DEG C, then the molecular sieve Y-1 of 1200g without hydrothermal treatment consists is added, hydrothermal treatment consists 48 hours at 100 DEG C, with a large amount of deionized water rinsing filter cakes to neutral, at 120 DEG C dry 6 hours, and then roasting 7 hours at air atmosphere 550 DEG C, removing surfactant molecule, obtains 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, and infrared acidity is 0.415mol/g, relative crystallinity 36%.
Embodiment 8
Preparation condition is with embodiment 4.F-1 is replaced, obtained carrier D and catalyst catD by F-4.
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 mixing.
(2) with containing the chlorine being equivalent to 5gPd, acid and the chloroplatinic acid being equivalent to 1.5gPt are mixed with aqueous solution 100ml, the PVP solution 6ml of 5g/L is added in above-mentioned solution, stirs 2h, add the HCHO solution 15ml that concentration is 2%, stir reduction 5h, after reduction, obtain precious metal colloid.
(3) precious metal colloid that step (2) obtains is sprayed at mixed carrier that step (1) obtains on the surface, need during sprinkling to stir support powder, 60h is dried under normal temperature, normal pressure, keep relative air humidity 60%, then every 3min heats up 1 DEG C, temperature is risen to 55 DEG C, dry 20h, every 3min heats up 1 DEG C again, by temperature to 100 DEG C, dries 48h; Need during oven dry first will vacuumize, then pass into nitrogen, remain on nitrogen atmosphere.(4) product that obtains of step (3) and 12gSB aluminium oxide, 80g dust technology kneading, roll, and making can the paste of extrusion, extruded moulding, is slowly warming up to 110 DEG C, dries 16h under nitrogen atmosphere, then temperature programming 550 DEG C of roasting 3h in an oxygen-free atmosphere, obtain catalyst catE.
Table 1 lists the physico-chemical property that embodiment of the present invention 1-8 and comparative example 1 obtain catalyst.
The physico-chemical property of table 1 catalyst
| Catalyst is numbered | catA | catB | catC | catD | catE |
| Catalyst forms | |||||
| 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 is carried out reactivity worth evaluation test.Test is carried out on 200ml small hydrogenation device, and with the lube stock of low-voltage hydrogenation isomate >320 DEG C for 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, reaction temperature 220 DEG C, volume space velocity 0.6h in hydrogen dividing potential drop
-1process conditions under, carried out hydrogenation and produced the engineer testing of white oil, reactivity worth evaluation test the results are shown in Table 3.
Table 2 low-voltage hydrogenation isomery >320 DEG C of lube stock character
| Analysis project | |
| Density (20 DEG C)/kgm -3 | 857.1 |
| Sulphur/μ gg -1 | 3.0 |
| Nitrogen/μ gg -1 | 1.0 |
| Pour point/DEG C | -30 |
| Viscosity (100 DEG C)/mm 2·s -1 | 5.097 |
| Viscosity (40 DEG C)/mm 2·s -1 | 27.41 |
| Carbon residue, wt% | 0.01 |
| Aromatic hydrocarbons, wt% | 10.7 |
Table 3 catalyst activity evaluation result
| Catalyst is numbered | catA | catB | catC | catD | catE |
| Reaction temperature, DEG C | 224 | 225 | 223 | 228 | 235 |
| Liquid is received, wt% | 99.7 | 99.5 | 99.6 | 99.3 | 98.8 |
| Viscosity (40 DEG C)/mm 2·s -1 | 33.38 | 33.04 | 32.78 | 32.86 | 31.09 |
| Viscosity (100 DEG C)/mm 2·s -1 | 6.978 | 6.921 | 6.9616 | 6.841 | 6.109 |
| Pour point/DEG C | -14 | -13 | -14 | -12 | -10 |
| Saybolt color/number | +33 | +32 | +33 | +31 | +30 |
| Readily carbonizable substance (100 DEG C) | 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 (20)
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 with the weight of catalyst for 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 the content of 50wt% ~ 90wt%, 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 according to claim 1, it is characterized in that the SiO in described SBA-15/Y composite molecular screen
2/ A1
2o
3mol ratio is 55 ~ 85.
3. according to catalyst according to claim 1, it is characterized in that in described catalytic hydro-dearomatization catalyst, the content of amorphous aluminum silicide is 70wt% ~ 85wt%.
4., according to catalyst according to claim 1, it is characterized in that in described SBA-15/Y composite molecular screen, Y zeolite weight content is 60wt% ~ 80wt%.
5., according to catalyst according to claim 1, it is characterized in that dioxide-containing silica 15wt% ~ 45wt% in described amorphous aluminum silicide.
6. according to catalyst according to 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, and meleic acid amount is 0.3 ~ 1.0mmol/g.
7. according to catalyst according to 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, and meleic acid amount is 0.4 ~ 0.8mmol/g.
8. the preparation method of the arbitrary described catalyst of claim 1 ~ 7, comprising: by SBA-15/Y composite molecular screen and amorphous aluminum silicide and adhesive through kneading, shaping, drying and roasting, obtain catalyst carrier; Adopt infusion process on a catalyst support after load P d and Pt, drying and roasting, obtain catalytic hydro-dearomatization catalyst.
9. in accordance with the method for claim 8, it is characterized in that: the condition of shaping rear carrier drying and roasting is as follows: through 100 ~ 130 DEG C of dryings 12 ~ 14 hours, 450 ~ 550 DEG C of roastings 5 ~ 10 hours.
10. in accordance with the method for claim 8, 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 that is dry and roasting was as follows: 100 ~ 130 DEG C of dryings 12 ~ 14 hours, roasting 5 ~ 10 hours at 500 ~ 600 DEG C.
11. in accordance with the method for claim 8, it is characterized in that the preparation method of described SBA-15/Y composite molecular screen, comprising:
A silicon source joins in acid solution by (), be stirred to till becoming clear solution;
B cationic surfactant is dissolved in the water and stirs by ();
C () Y zeolite carries out hydrothermal treatment consists, described hydrothermal treatment consists temperature is 350 ~ 650 DEG C, pressure is 0.5 ~ 3.0MPa, 1 ~ 6 hour reaction time;
D the solution of step (a) gained is added in the aqueous solution of the compositions comprising cationic surfactants of step (b) gained by (), stir, then the molecular sieve of step (c) gained is added, after mixing, hydrothermal treatment consists 24 ~ 72 hours at 70 ~ 150 DEG C, after filtration, wash, then drying, obtain mesoporous-microporocomposite composite molecular sieve.
12. in accordance with the method for claim 11, it is characterized in that in step (a), described acid solution is the aqueous solution of one or more in phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the concentration of described acid solution is 0.01 ~ 0.10mol/L.
13. in accordance with the method for claim 11, it is characterized in that in step (a), described silicon source is organo-silicon ester alkane or inorganic silicon source, organo-silicon ester 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.
14. in accordance with the method for claim 11, it is characterized in that, in step (a), joining in acid solution by silicon source, makes the pH value of system be 2 ~ 6, reacts 2 ~ 20 hours, obtain clear solution at the temperature of 10 ~ 50 DEG C.
15. in accordance with the method for claim 11, 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 prepared is 5wt% ~ 20wt%.
16. in accordance with the method for claim 15, 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.
17. in accordance with the method for claim 11, it is characterized in that the consumption of described cationic surfactant is 5wt% ~ 20wt% with the gross weight of step (a) and (b) and (c) gained material for benchmark.
18. in accordance with the method for claim 11, it is characterized in that described silicon source is with SiO
2meter is 0.2 ~ 15.0 with the mass ratio of cationic surfactant.
19. in accordance with the method for claim 11, it is characterized in that the drying condition described in step (d) is as follows: temperature is 50 ~ 120 DEG C, and the time is 6 ~ 12 hours.
20. in accordance with the method for claim 11, it is characterized in that the character of the Y zeolite described in 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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769194A CN103769194A (en) | 2014-05-07 |
| CN103769194B true CN103769194B (en) | 2016-03-30 |
Family
ID=50562228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409477.6A Active CN103769194B (en) | 2012-10-24 | 2012-10-24 | A kind of catalytic hydro-dearomatization catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769194B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728023B (en) * | 2014-12-08 | 2018-11-16 | 中国石油天然气股份有限公司 | Molecular sieve catalyst and preparation method for the reaction of fischer-tropsch wax hydroisomerizing |
| CN106669782B (en) * | 2015-11-09 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method and application |
| CN108067290B (en) * | 2016-11-17 | 2021-05-04 | 中国石油化工股份有限公司 | Carrier and catalyst containing bimolecular sieve, and preparation method and application thereof |
| CN109851468B (en) * | 2017-11-30 | 2021-12-31 | 中国石油化工股份有限公司 | Preparation method of medical intermediate hexadecahydropyrene |
| CN108579735A (en) * | 2018-05-28 | 2018-09-28 | 中国中化股份有限公司 | A kind of preparation method of platinum-palladium bimetallic catalytic hydro-dearomatization catalyst |
| CN114433210B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrodearene catalyst and preparation method and application thereof |
| CN114453013B (en) * | 2020-10-21 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of hydrodearomatization catalyst, hydrodearomatization catalyst and application |
| CN114453014B (en) * | 2020-10-21 | 2023-07-28 | 中国石油化工股份有限公司 | Hydrodearene catalyst and preparation method and application thereof |
| CN116060086A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in preparation of microcrystalline wax |
| CN116060112A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodearene catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393408A (en) * | 1992-04-30 | 1995-02-28 | Chevron Research And Technology Company | Process for the stabilization of lubricating oil base stocks |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101269343A (en) * | 2007-03-23 | 2008-09-24 | 中国石油天然气股份有限公司 | Composite mesoporous molecular sieve hydrocracking catalyst and uses thereof |
| CN101862670A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Carrier dry powder impregnation preparation method and application of lubricating oil hydrogenation catalyst |
-
2012
- 2012-10-24 CN CN201210409477.6A patent/CN103769194B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393408A (en) * | 1992-04-30 | 1995-02-28 | Chevron Research And Technology Company | Process for the stabilization of lubricating oil base stocks |
| CN101269343A (en) * | 2007-03-23 | 2008-09-24 | 中国石油天然气股份有限公司 | Composite mesoporous molecular sieve hydrocracking catalyst and uses thereof |
| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101862670A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Carrier dry powder impregnation preparation method and application of lubricating oil hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769194A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769194B (en) | A kind of catalytic hydro-dearomatization catalyst and preparation method thereof | |
| CN104588073B (en) | Hydrogenation dearomatization catalyst and preparation method thereof | |
| CN107922858A (en) | The manufacture method of lube base oil | |
| CN101254471B (en) | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same | |
| CN103100412B (en) | Preparation method of hydrocracking catalyst | |
| CN102909082A (en) | Preparation method for middle oil type hydrocracking catalyst carrier | |
| CN102553638B (en) | Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst | |
| CN104588074B (en) | A kind of preparation method of catalytic hydro-dearomatization catalyst | |
| CN108067290A (en) | Carrier and catalyst of a kind of sieve containing bimolecular and its preparation method and application | |
| CN104826647B (en) | The preparation method of catalytic hydro-dearomatization catalyst | |
| CN102553650B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN106669863B (en) | The method of modifying of catalyst for hydro-upgrading carrier | |
| CN101745383B (en) | Deeply hydrodearomatized catalyst and preparation method | |
| CN103769195B (en) | A kind of preparation method of catalytic hydro-dearomatization catalyst | |
| CN100515560C (en) | preparationof carrier superfine alloy hydrogenation catalyst for dearomatization | |
| CN100457869C (en) | Dewaxing catalyst for lubricant oil distillate and its uses | |
| CN105214717B (en) | A kind of preparation method of lube base oil isomerization dewaxing catalyst | |
| CN104826650B (en) | A kind of method preparing catalytic hydro-dearomatization catalyst | |
| CN102085488B (en) | Catalyst for decreasing cloud point of lube base oil and preparation method thereof | |
| CN107345161A (en) | A kind of method for hydrogen cracking of coal tar | |
| CN106669849B (en) | The method of modified catalyst for hydro-upgrading carrier | |
| CN106669796A (en) | Preparation method of hydro-upgrading catalyst | |
| CN107344117B (en) | Hydrocracking catalyst and its preparation method | |
| CN107344120B (en) | Carrier of hydrocracking catalyst and its preparation method | |
| CN106669848B (en) | A kind of method of modified catalyst for hydro-upgrading carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |