CN102463142B - Hydrogenation catalyst carrier and preparation method thereof - Google Patents
Hydrogenation catalyst carrier and preparation method thereof Download PDFInfo
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- CN102463142B CN102463142B CN 201010535599 CN201010535599A CN102463142B CN 102463142 B CN102463142 B CN 102463142B CN 201010535599 CN201010535599 CN 201010535599 CN 201010535599 A CN201010535599 A CN 201010535599A CN 102463142 B CN102463142 B CN 102463142B
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Abstract
The invention discloses a hydrogenation catalyst carrier which comprises, by weight, 0 to 40% of a molecular sieve, 20 to 75% of amorphous silica-alumina and 5 to 75% of alumina. The hydrogenation catalyst carrier has the following properties: a specific surface area is 200 m<2>/g to 500 m<2>/g; a pore volume is 0.40 cm<3>/g to 0.80 cm<3>/g. A preparation method for the hydrogenation catalyst carrier comprises the following steps: carrying out hydrothermal treatment on amorphous silica-alumina dry glue powder; weighing the above-mentioned components of the catalyst carrier in desired proportion; carrying out mixing and milling, molding, drying and activation on the components so as to obtain the catalyst carrier. Compared to conventional hydrogenation catalyst carriers, the catalyst carrier provided in the invention has the following advantages: the catalyst carrier has a greater pore volume, a greater specific surface area, a proper amount of acid and good nitrogen resistance; a catalyst prepared from the catalyst carrier is applicable to hydrotreatment of vacuum distillates which are heavier and poorer but can produce more middle distillates.
Description
Technical field
The present invention relates to a kind of catalyst carrier for hydrgenating and preparation method thereof, particularly have high anti-nitrogen ability and can handle carrier of hydrocracking catalyst of charging inferior and preparation method thereof.
Technical background
In recent years, the hydrocracking ability continues to increase in the world wide, and wherein the Asian-Pacific area increases the fastest.The sustainable growth of China's economy is also powerful to have spurred the constantly high of domestic Oil Product Market, and the existing hydrocracking unit working ability of China has surpassed 40.0Mt/a at present.But because crude quality variation year by year, the sour crude of import increases considerably, and the refinery is for increasing economic efficiency, crude oil decompression deep drawing technology is generally adopted in beginning, make doing by original 520 ℃ of vacuum distillate bring up to about 600 ℃, impurity contents such as its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulphur nitrogen are also more and more, increased the difficulty of hydrocracked, treated greatly, these are all had higher requirement to hydrocracking technology and hydrocracking catalyst.
Because the advantage on the Diesel engine performance and widely-used, so market is very vigorous always to the demand of diesel oil.The diesel oil of oil plant production at present mainly contains straight-run diesel oil and secondary processing diesel oil, and the main path of producing secondary processing diesel oil has catalytic cracking, hydrocracking and delayed coking etc.Because environmental regulation increasingly stringent, the standard of clean fuel also improve greatly, catalytic diesel oil and coker gas oil product can not satisfy index request, need further processing just can dispatch from the factory.Hydrocracking technology is as one of main means of heavy oil lighting, have that adaptability to raw material is strong, product solution flexibly, purpose product selectivity height, good product quality, added value advantages of higher, can satisfy market to the demand of clean fuel, become the main oil Refining Technologies of 21st century.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, namely contains acidic components and hydrogenation activity component simultaneously.Wherein acidity mainly is to be provided by various molecular sieves and/or the heat-resistant inorganic oxide that constitutes carrier, and the character of acidic components selectively has a very significant effects to the activity of hydrocracking catalyst and intermediate oil.Aggravation along with heaviness He the poor qualityization of raw material, the handled charging of hydrocracking technology becomes more and more heavier, aromatic hydrocarbons wherein, particularly the content of condensed-nuclei aromatics increases, unmanageable nitrogen-containing compound has very big influence to the even running of hydrocracking unit, this just has higher requirement to hydrocracking catalyst, requires catalyst to have the ability of good anti-impurity, guarantees the application of hydrocracking technology.
CN97122139.1 discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, earlier with after amorphous aluminum silicide and aluminium oxide kneading extrusion, drying and the roasting, under certain pressure and uniform temperature through hydrothermal treatment consists, then with the solution impregnating carrier that contains W, Ni, final drying and roasting obtain catalyst prod, amorphous aluminum silicide after the roasting carries out hydrothermal treatment consists again, and character modulation effect is limited.CN00110021.1, CN00110016.5 disclose a kind of Preparation of catalysts method, and catalyst is with unformed SiO
2-A1
2O
3And A1
2O
3Mixture be carrier, with WO
3With NiO be the hydrogenation activity component, this Preparation of catalysts method is, earlier carrier mediated extrusion, drying, then under certain pressure and uniform temperature through hydrothermal treatment consists, with the solution impregnating carrier that contains W, Ni, final drying and roasting obtain catalyst prod then.This method is that catalyst carrier is all carried out hydrothermal treatment consists, because amorphous aluminum silicide and aluminium oxide elder generation kneading and compacting, the amorphous silicon aluminum feedstock of roasting and alumina raw material do not have higher chemism, amorphous aluminum silicide and aluminium oxide have formed certain glue connection effect, under the hydrothermal treatment consists condition, both have formed collaborative crystalline form transformation, property adjustments to amorphous aluminum silicide plays adverse influence, part duct is destroyed, influence the performance performance of amorphous aluminum silicide, in addition carrier has all been carried out the saving that hydrothermal treatment consists also is unfavorable for the energy.
US4738767 discloses a kind of hydrocracking catalyst, main acidic components are amorphous aluminum silicides, the preparation method of the amorphous aluminum silicide that carrier is used be with aluminum precipitation in the silicon gel, this just causes the specific area of sial and pore volume all less, amorphous silicon aluminic acid amount is hanged down characteristics such as reaching sour skewness, prepared poor catalyst activity.US4517074 also adopts above-mentioned amorphous aluminum silicide, and has added an amount of molecular sieve, and the content of silica has reached more than 50% in the amorphous aluminum silicide, and the anti-nitrogen ability of prepared catalyst is descended, and is difficult to guarantee activity of such catalysts.
No matter be that catalyst carrier is carried out hydrothermal treatment consists by above analysis, still adopt the anti-nitrogen ability of catalyst of conventional method preparation all lower, catalyst activity is relatively poor, can not satisfy the requirement of the long-term operation of hydrocracking unit.
Summary of the invention
At the deficiencies in the prior art, and the problem of the anti-nitrogen scarce capacity of middle oil type catalyst, the present invention has prepared a kind of catalyst carrier for hydrgenating, wherein the amorphous aluminum silicide as acidic components carries out hydrothermal treatment consists earlier, catalyst carrier of the present invention has bigger pore volume and specific area, the acid amount is suitable, have good anti-nitrogen ability, be suitable for handling more heavy, vacuum distillate more inferior and hydrotreatment process or the hydrocracking process of voluminous intermediate oil by the prepared catalyst of carrier of the present invention.
Catalyst carrier for hydrgenating of the present invention by weight, comprises molecular sieve 0～40%, amorphous aluminum silicide 20%～75% and aluminium oxide 5%～75% in the catalyst carrier, catalyst carrier for hydrgenating has following character, and specific area is 200m
2/ g～500m
2/ g, pore volume are 0.40cm
3/ g～0.80cm
3/ g.
In the catalyst carrier for hydrgenating of the present invention, amorphous aluminum silicide for the amorphous aluminum silicide dry glue powder through the product after the hydrothermal treatment consists, make catalyst carrier with other carrier material then.
In the catalyst carrier for hydrgenating of the present invention, molecular sieve can be one or more compound uses of Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve, is preferably Y zeolite or beta-molecular sieve.Molecular sieve kind and content can be determined according to the requirement optimization of concrete catalyst.
In the catalyst carrier for hydrgenating of the present invention, amorphous aluminum silicide is main cracking component, is the place that disperses a large amount of hydrogenation active metals simultaneously, therefore requires to have bigger pore volume and specific area and proper acidic matter.Index request through amorphous aluminum silicide after the high-temperature water heat treatment: the amorphous aluminum silicide specific area is 400～700m
2/ g, pore volume are 0.5～1.5cm
3/ g, the silica weight content is 20%～80%, is preferably 30%～65%.Average pore diameter is in 10～20nm scope, and preferably at 10～15nm, meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.2～1.0mmol/g.
The hydrothermal treatment consists condition of amorphous aluminum silicide dry glue powder is in the catalyst carrier for hydrgenating of the present invention: atmosphere is water vapour, processing pressure 0.05～0.3MPa, and 450～750 ℃ for the treatment of temperatures, the processing time is 0.5～5h.
The molecular sieve that adopts in the catalyst carrier for hydrgenating of the present invention is beta-molecular sieve, and its character is: specific area 450～750m
2/ g, pore volume are 0.3～0.5cm
3/ g, silica alumina ratio are 30～100, and meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.1～0.5mmol/g.
The aluminium oxide character that adopts in the catalyst carrier for hydrgenating of the present invention is: specific area 200～500m
2/ g, pore volume are 0.8～1.5cm
3/ g.
The preparation method of catalyst carrier for hydrgenating of the present invention is as follows:
(1) the amorphous aluminum silicide dry glue powder is carried out hydrothermal treatment consists;
(2) according to the various materials of material's proportion weighing of catalyst carrier;
(3) material is carried out mixed grind, moulding, drying, activation and obtain catalyst carrier.
Amorphous aluminum silicide is the product after the hydrothermal treatment consists in the carrier of hydrocracking catalyst of the present invention, and concrete hydrothermal treatment consists condition is as follows: before the hydrothermal treatment consists, the weight butt of amorphous aluminum silicide dry glue powder is 50%～80%, and specific area is 300～600m
2/ g, pore volume are 0.4～1.2cm
3/ g, meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.4～1.5mmol/g.Under the effect of saturated vapor, carry out hydrothermal treatment consists.The hydrothermal treatment consists condition is: processing pressure 0.05～0.3MPa, and 450～750 ℃ for the treatment of temperatures, the processing time is 0.5～5h.The physico-chemical property of handling the back amorphous aluminum silicide is: specific area is 400～700m
2/ g, pore volume are 0.5～1.5cm
3/ g, the silica weight content is 20%～80%, is preferably 30%～65%.Average pore diameter is in 10～20nm scope, and preferably at 10～15nm, meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.2～1.0mmol/g.
Among the catalyst carrier for hydrgenating preparation method of the present invention, other preparation process and condition are technology contents well known to those skilled in the art.
Catalyst carrier for hydrgenating of the present invention can be optimized carrier component, cooperate the suitable hydrogenation metal component, the inferior distillate oil hydrotreating catalyst that obtains suiting, vacuum distillate hydrocracking catalyst, lubricant base oil fraction catalyst for hydro-upgrading etc. have purposes widely in field of hydrogenation.
Amorphous aluminum silicide in the catalyst carrier for hydrgenating of the present invention after the employing hydrothermal treatment consists is as main acidic components, compare the sial that does not carry out hydrothermal treatment consists, have bigger specific area and pore volume, part strong acid center in the sial obtains reduction, the intensity that makes the acid site in the sial is homogeneous comparatively, and be evenly distributed, be easy to carry reactive metal, when having avoided carrying out hydrothermal treatment consists simultaneously with aluminium oxide since common transformation to the influence of amorphous aluminum silicide character, be equipped with the good beta-molecular sieve of anti-nitrogen performance in addition, compare with the catalyst carrier for hydrgenating that adopts conventional kneading and compacting method preparation, catalyst carrier of the present invention has better anti-nitrogen ability, higher catalyst activity, even can not have to handle charging inferior under the prerequisite of catalyst for refining, and obtain desirable midbarrel oil product.
The catalyst carrier for hydrgenating of the present invention's preparation, wherein the amorphous aluminum silicide as acidic components carries out hydrothermal treatment consists earlier, catalyst carrier of the present invention has bigger pore volume and specific area, the acid amount is suitable, have good anti-nitrogen ability, be suitable for handling more heavy, vacuum distillate more inferior and the hydrotreatment process of voluminous intermediate oil by the prepared catalyst of carrier of the present invention.
The specific embodiment
The preparation method of catalyst carrier of the present invention is as follows:
(1) hydrothermal treatment consists of amorphous aluminum silicide dry glue powder
Physico-chemical property before the used amorphous aluminum silicide dry glue powder of the catalyst carrier of the present invention hydrothermal treatment consists is: butt weight is 50%～80%, and surface area is 300～600m
2/ g, pore volume are 0.4～1.2cm
3/ g.Meleic acid amount (the infrared absorption spectrographic determination of pyridine) between 0.4～1.5mmol/g, can adopt commercial goods amorphous aluminum silicide dry glue powder, also can prepare by this area conventional method.
Adopt saturated vapor to carry out hydrothermal treatment consists, processing pressure 0.05～0.3MPa, 450～750 ℃ for the treatment of temperatures, the processing time is 0.5～5h.
The character of amorphous aluminum silicide is after the hydrothermal treatment consists: specific area is 400～700m
2/ g, pore volume are 0.5～1.5cm
3/ g, the silica weight content is 20%～80%, is preferably 30%～65%.Average pore diameter is in 10～20nm scope, and preferably at 10～15nm, meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.2～1.0mmol/g.
(2) (its character is amorphous aluminum silicide, the beta-molecular sieve after the mensuration hydrothermal treatment consists: specific area 450～750m
2/ g, pore volume are 0.3～0.5cm
3/ g, silica alumina ratio are 30～100, and meleic acid amount (the infrared absorption spectrographic determination of pyridine) is between 0.1～0.5mmol/g.) and aluminium oxide (specific area 200～5000m
2/ g, pore volume are 0.8～1.5cm
3/ g.) waiting the actual butt of material, weighing is accurately stand-by.
(3) put into the amorphous aluminum silicide after the hydrothermal treatment consists, beta-molecular sieve and aluminium oxide in the kneading machine successively, mix and pinched 5～30 minutes, then compound is put in the roller, rolled 20～60 minutes, adding a certain amount of dilute nitric acid solution (wherein the concentration of rare nitric acid is 1～10g nitric acid/100mL solution) continues to roll formation and can squeeze the paste shape, extruded moulding then, the catalyst carrier shape can be column, clover, bunge bedstraw herb and other different in nature bar etc., length control 3～8mm.
(4) strip drying, the activation that step (3) is obtained, at first under 100～150 ℃ of conditions dry 2～10 hours, carry out roasting then, 400～600 ℃ of sintering temperatures, the time is 3～10 hours, prepares catalyst carrier.
The beta-molecular sieve of used interpolation is modified beta molecular sieve among the present invention, has passed through treatment process such as stripper plate agent, acidifying, hydrothermal treatment consists and pulverizing and prepares beta-molecular sieve.The beta-molecular sieve modification processing method is method well known to those skilled in the art.
Among the present invention, specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, and the pyridine adsorption infra-red sepectrometry is adopted in meleic acid amount, B acid and L acid, and wherein the summation of B acid and L acid is the meleic acid amount, and trace element adopts plasma emission spectrometry.
The following examples are used for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiment, and the percentage composition that relates to is weight percentage.
Embodiment 1
(commercial goods, butt are 70.13%, and specific area is 458m to get amorphous aluminum silicide dry glue powder 1000g
2/ g, pore volume are 0.75cm
3/ g, silica weight content are 45%, meleic acid amount 1.0mmol/g), the hydrothermal treatment consists temperature is 500 ℃, processing pressure is 0.2MPa, processing time 2h.Obtain being numbered GL-1, product property sees Table 1.
Embodiment 2
Get amorphous aluminum silicide dry glue powder 1000g (with embodiment 1), the hydrothermal treatment consists temperature is 600 ℃, and processing pressure is 0.2MPa, processing time 2h.Obtain being numbered GL-2, product property sees Table 1.
Embodiment 3
Get amorphous aluminum silicide dry glue powder 1000g (with embodiment 1), the hydrothermal treatment consists temperature is 700 ℃, and processing pressure is 0.2MPa, processing time 2h.Obtain being numbered GL-3, product property sees Table 1.
Embodiment 4
Get amorphous aluminum silicide dry glue powder 1000g (with embodiment 1), the hydrothermal treatment consists temperature is 600 ℃, and processing pressure is 0.1MPa, processing time 4h.Obtain being numbered GL-4, product property sees Table 1.
Embodiment 5
Get amorphous aluminum silicide dry glue powder 1000g (with embodiment 1), the hydrothermal treatment consists temperature is 700 ℃, and processing pressure is 0.3MPa, processing time 4h.Obtain being numbered GL-5, product property sees Table 1.
Embodiment 6
Get amorphous aluminum silicide among the embodiment 2 (GL-2) 200g (butt 97.5%), (butt 97.0%, specific area are 550m to beta-molecular sieve
2/ g, pore volume are 0.36cm
3/ g) 22.31g and aluminium oxide (butt 71.36%, specific area are 350m
2/ g, pore volume are 1.1cm
3/ g) 303g puts into kneading machine together, mix and pinched 10 minutes, then the material that mixes is put into roll 25 minutes in the roller after, add a certain amount of rare nitric acid (5g nitric acid/100mL solution), continue to roll formation and can squeeze the paste shape, extruded moulding then, catalyst carrier is shaped as column, at 110 ℃ of dry 6h, obtain the dry catalyst carrier then.Dried carrier program ascending order is warmed up to 550 ℃, and constant temperature was handled 5 hours.Obtain catalyst carrier ZT-1, character sees Table 2.
Embodiment 7
Get amorphous aluminum silicide among the embodiment 2 (GL-2) 100g (butt 97.5%), (butt 97.0%, specific area are 550m to beta-molecular sieve
2/ g, pore volume are 0.36cm
3/ g) 23.45g and aluminium oxide (butt 71.36%, specific area are 350m
2/ g, pore volume are 1.1cm
3/ g) 287g puts into kneading machine together, mix and pinched 10 minutes, then the material that mixes is put into roll 25 minutes in the roller after, add a certain amount of rare nitric acid (5g nitric acid/100mL solution), continue to roll formation and can squeeze the paste shape, extruded moulding then, catalyst carrier is shaped as column, at 110 ℃ of dry 6h, obtain the dry catalyst carrier then.Dried carrier program ascending order is warmed up to 550 ℃, and constant temperature was handled 5 hours.Obtain catalyst carrier ZT-2, character sees Table 2.
Embodiment 8
Get amorphous aluminum silicide among the embodiment 5 (GL-5) 200g (butt 97.5%), (butt 97.0%, specific area are 550m to beta-molecular sieve
2/ g, pore volume are 0.36cm
3/ g) 22.31g and aluminium oxide (butt 71.36%, specific area are 350m
2/ g, pore volume are 1.1cm
3/ g) 303g puts into kneading machine together, mix and pinched 10 minutes, then the material that mixes is put into roll 25 minutes in the roller after, add a certain amount of rare nitric acid (5g nitric acid/100mL solution), continue to roll formation and can squeeze the paste shape, extruded moulding then, catalyst carrier is shaped as column, at 110 ℃ of dry 6h, obtain the dry catalyst carrier then.Dried carrier program ascending order is warmed up to 550 ℃, and constant temperature was handled 5 hours.Obtain catalyst carrier ZT-3, character sees Table 2.
Embodiment 9
Get amorphous aluminum silicide among the embodiment 5 (GL-5) 150g (butt 97.5%), (butt 97.0%, specific area are 550m to beta-molecular sieve
2/ g, pore volume are 0.36cm
3/ g) 18.84g and aluminium oxide (butt 71.36%, specific area are 350m
2/ g, pore volume are 1.1cm
3/ g) 282g puts into kneading machine together, mix and pinched 10 minutes, then the material that mixes is put into roll 25 minutes in the roller after, add a certain amount of rare nitric acid (5g nitric acid/100mL solution), continue to roll formation and can squeeze the paste shape, extruded moulding then, catalyst carrier is shaped as column, at 110 ℃ of dry 6h, obtain the dry catalyst carrier then.Dried carrier program ascending order is warmed up to 550 ℃, and constant temperature was handled 5 hours.Obtain catalyst carrier ZT-4, character sees Table 2.
Comparative Examples 1
The disclosed catalyst carrier preparation method of CN00110021.1, with 106.7 grams do not carry out the amorphous aluminum silicide dry glue powder (with embodiment 1), 11.1g aluminium oxide of hydrothermal treatment consists, by rare nitric acid and aperture Al
2O
3Adhesive 133.4 gram of preparation is put into roller, rolls 30 minutes, adds suitable quantity of water, grinds to can squeezing paste, and extrusion is extruded bar 110 ℃ of dryings 4 hours.Above-mentioned dried strip is put into 600 ℃ in hydrothermal treatment consists stove, and hydrothermal treatment consists is 1 hour under the 0.1MPa, makes catalyst carrier DZT-1, and character sees Table 2.
Comparative Examples 2
Press the catalyst carrier preparation method that CN00110021.1 announces, adopt the material (wherein the amorphous aluminum silicide dry glue powder directly uses without hydrothermal treatment consists) and the ratio that relate in the embodiment of the invention 6 to prepare catalyst carrier DZT-2, character sees Table 2.
Embodiment 10
Adopt the method for saturated dipping to support hydrogenation metal in the carrier among embodiment 6 and the embodiment 8, hydrogenation metal adopts tungsten-nickel system, and the preparation catalyst is respectively CAT-1 and CAT-2, and catalyst property sees Table 3.
Comparative Examples 3
Adopt the method for saturated dipping to support hydrogenation metal in the carrier in the Comparative Examples 2, hydrogenation metal adopts tungsten-nickel system, and the preparation catalyst is respectively DCAT-1, and catalyst property sees Table 3.
Embodiment 11
Present embodiment has been introduced the catalyst activity evaluation result that is prepared by carrier of the present invention.Estimate at the fixed bed hydrogenation experimental rig, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.0h
-1, adopt single hop once by technological process, use vacuum distillate inferior as feedstock oil, the control conversion per pass is 70%, feedstock oil character is listed in table 4.Catalyst CAT-1 is estimated under identical process conditions with DCAT-1, and the evaluation result that obtains is listed in table 5.
By evaluation result as can be seen, catalyst carrier of the present invention and the catalyst for preparing are under identical process conditions and feedstock oil nitrogen content conditions of higher, and intermediate oil is selective, yield and product quality all are better than reference catalyst, and the hydrogen consumption is lower.
The character of amorphous aluminum silicide after the hydrothermal treatment consists among table 1 embodiment
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Sample number into spectrum | GL-1 | GL-2 | GL-3 | GL-4 | GL-5 |
| The hydrothermal treatment consists temperature, ℃ | 500 | 600 | 700 | 600 | 700 |
| Hydrothermal treatment consists pressure, MPa | 0.2 | 0.2 | 0.2 | 0.1 | 0.3 |
| The hydrothermal treatment consists time, h | 2 | 2 | 2 | 4 | 4 |
| Pore volume, ml/g | 0.83 | 0.94 | 1.08 | 0.85 | 1.14 |
| The BET specific surface, m 2/g | 663 | 647 | 619 | 654 | 608 |
| Si 2O content, % | 45 | 45 | 45 | 45 | 45 |
| The meleic acid amount, mmol/g | 0.53 | 0.44 | 0.36 | 0.48 | 0.41 |
The physical property of table 2 catalyst carrier
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative Examples 1 | Comparative Examples 2 | |
| Sample number into spectrum | ZT-1 | ZT-2 | ZT-3 | ZT-4 | DZT-1 | DZT-2 |
| Amorphous aluminum silicide | 45 | 30 | 45 | 40 | 40 | 45 |
| Molecular sieve | 5 | 7 | 5 | 5 | 5 | |
| Aluminium oxide | 50 | 63 | 50 | 55 | 60 | 50 |
| Hydrothermal temperature, ℃ | 500 | 600 | ||||
| Hydro-thermal pressure, MPa | 0.10 | 0.20 | ||||
| The hydro-thermal time, h | 1.0 | 2.0 | ||||
| Pore volume, ml/g | 0.65 | 0.68 | 0.74 | 0.77 | 0.66 | 0.55 |
| Specific surface, m 2/g | 392 | 346 | 335 | 329 | 380 | 369 |
The physical property of table 3 catalyst
| Embodiment 10 | Embodiment 10 | Comparative Examples 3 | |
| Sample number into spectrum | CAT-1 | CAT-2 | DCAT-1 |
| WO 3，％ | 23.9 | 24.6 | 25.4 |
| NiO，％ | 5.6 | 5.7 | 5.5 |
Table 4 feedstock oil character
| Feedstock oil | Vacuum distillate |
| Density (20 ℃), kg/m 3 | 920.6 |
| Boiling range, ℃ | |
| IBP/10％ | 328/413 |
| 30％/50％ | 450/471 |
| 70％/90％ | 493/522 |
| 95％/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
| Sulphur, % | 1.98 |
Table 5 evaluating catalyst result
Claims (8)
1. a catalyst carrier for hydrgenating by weight, comprises molecular sieve 0～40%, amorphous aluminum silicide 20%～75% and aluminium oxide 5%～75% in the catalyst carrier, and catalyst carrier for hydrgenating has following character, and specific area is 200m
2/ g～500m
2/ g, pore volume are 0.40cm
3/ g～0.80cm
3/ g; It is characterized in that: amorphous aluminum silicide for the amorphous aluminum silicide dry glue powder through the product after the hydrothermal treatment consists, make catalyst carrier with other carrier material then; The hydrothermal treatment consists condition of amorphous aluminum silicide dry glue powder is: atmosphere is water vapour, processing pressure 0.05～0.3MPa, and 450～750 ℃ for the treatment of temperatures, the processing time is 0.5～5h; Character through amorphous aluminum silicide after the hydrothermal treatment consists is: specific area is 400～700m
2/ g, pore volume are 0.5～1.5cm
3/ g, silica weight content are 20%～80%, and average pore diameter is in 10～20nm scope, and the meleic acid amount is between 0.2～1.0mmol/g; Wherein molecular sieve is one or more compound uses of Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve.
2. according to the described carrier of claim 1, it is characterized in that: the average pore diameter of amorphous aluminum silicide is in 10～15nm scope after the process hydrothermal treatment consists.
3. according to the described carrier of claim 1, it is characterized in that: the character of beta-molecular sieve is: specific area is 450～750m
2/ g, pore volume are 0.3～0.5cm
3/ g, silica alumina ratio are 30～100, and the meleic acid amount is between 0.1～0.5mmol/g.
4. according to the described carrier of claim 1, it is characterized in that: the specific area of aluminium oxide is 200～500m
2/ g, pore volume are 0.8～1.5cm
3/ g.
5. according to the described carrier of claim 1, it is characterized in that: the silica weight content through amorphous aluminum silicide after the hydrothermal treatment consists is 30%～65%.
6. the preparation method of the described carrier of the arbitrary claim of claim 1 to 5 is characterized in that: comprise following process:
(1) the amorphous aluminum silicide dry glue powder is carried out hydrothermal treatment consists;
(2) according to the various materials of material's proportion weighing of catalyst carrier;
(3) material is carried out mixed grind, moulding, drying, activation and obtain catalyst carrier.
7. in accordance with the method for claim 6, it is characterized in that: the character of amorphous aluminum silicide dry glue powder is: the weight butt is 50%～80%, and specific area is 300～600m
2/ g, pore volume are 0.4～1.2cm
3/ g, the meleic acid amount is between 0.4～1.5mmol/g.
8. in accordance with the method for claim 6, it is characterized in that: the described drying of step (3), activation process are: at first under 100～150 ℃ of conditions dry 2～10 hours, carry out roasting then, and 400～600 ℃ of sintering temperatures, the time is 3～10 hours.
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| CN104587993B (en) * | 2013-11-03 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| RU2722157C1 (en) | 2015-07-22 | 2020-05-27 | Басф Корпорейшн | Catalysts with high geometrical surface area for producing vinyl acetate monomer |
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| CN101172259A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Method for preparing carrier material |
| CN101239328A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Amorphous silica-alumina and its preparing method |
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