CN109833891A - A kind of catalyst for hydro-processing heavy distillate and its application - Google Patents
A kind of catalyst for hydro-processing heavy distillate and its application Download PDFInfo
- Publication number
- CN109833891A CN109833891A CN201711220716.2A CN201711220716A CN109833891A CN 109833891 A CN109833891 A CN 109833891A CN 201711220716 A CN201711220716 A CN 201711220716A CN 109833891 A CN109833891 A CN 109833891A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydro
- oxide
- heavy distillate
- processing heavy
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
A kind of catalyst for hydro-processing heavy distillate and its application.Catalyst includes active component and catalyst carrier, and based on catalyst weight percent, active component includes 10%~40% group vib metal oxide, 1%~20% group VIII metal oxide and/or 0.1%~10% VA race oxide；Based on catalyst carrier weight percent, catalyst carrier includes mesoporous TiO2‑Al2O310~50wt%, 1~5wt% of 30~80wt% of aluminium oxide, 5~25wt% of adhesive and extrusion aid；Meso-porous alumina presoma is wherein obtained with template guiding legal system, titanium oxide, isopropyl titanate or butyl titanate are then introduced in the precursor solution, obtaining has the modified mesoporous alumina carrier of the titanium of large specific surface area and Kong Rong.Catalyst towards heavy matter petroleum distillate of the invention has preferable hydrodesulfurization and hydrodenitrogenationactivity activity.
Description
Technical field
The present invention relates to one kind with mesoporous TiO2-Al2O3, aluminium oxide adds at hydrogen as the heavier petroleum fraction of complex carrier
Manage catalyst.
Background technique
With the aggravation of crude oil heaviness, in poor quality trend in world wide, the ratio of inferior heavy oil constantly increases, effectively
Ground processing heavy distillate just seems even more important, and hydrotreating is then maximally efficient one of the processing technology of heavy distillate.
The key of hydrotreating techniques is catalyst, and the basis for promoting catalyst performance is the exploitation of new catalytic material.It is many
Well known, carrier material needs to have biggish specific surface area, Kong Rong and aperture, to improve the metal loading of catalyst and divide
Property is dissipated, the diffusion of molecule in reaction process is conducive to；Carrier material also needs suitable acid intensity and distribution, is added with meeting
The requirement of the reactions such as hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons saturation and cracking in hydrogen treatment process.
Currently, carrier of hydrogenating catalyst for heavy oil employed both at home and abroad is mainly the blending of titanium oxide and molecular sieve
Object, the aperture of this kind of carrier material is smaller, hole link is poor, lacks the mesopore orbit for adapting to heavy oil solid tumor；It calls in
Molecular sieve pore passage is smaller, acid relatively strong, acid type is more single, easily lead to overcracking and condensation green coke, be also unfavorable for
Take into account the requirement of different type hydrogenation reaction in hydroprocessing processes.Thus both at home and abroad in terms of the modification of carrier material and preparation
Carry out a few thing, such as:
CN1356380 provides the complex carrier preparation method of a kind of aluminium oxide and molecular sieve, the preparation process of the material
Aluminium oxide and molecular sieve are mixed using the method for mechanical mixture, extruded moulding obtains catalyst carrier.This complex method
The characteristics of be it is simple and easy, be common industrial production process；But that there is also mixing uniformity is poor, hole link is bad, is situated between
The deficiencies of hole ratio is small.
CN1448468 proposes a kind of method for preparing sial composite oxides using sol-gel process, prepares
Composite oxides have biggish specific surface and Kong Rong, but the mesoporous ratio of this based composite oxide is smaller, and it is big to be not suitable for heavy oil
Needs of molecule diffusion, and the acidity of composite oxides is weaker, sour amount is lower, to the partial hydrogenation of heavy oil macromolecular saturation and
Cracking capability is insufficient.
U.S4459367 discloses a kind of aluminium oxide and system with molecular sieve for preparing for the method for complex carrier, and this method is by aluminium oxide
With HCl treatment is used after molecular sieve mixed-forming again, to generate a certain number of macropores and mesoporous, but this sour corrosion reaming
There is also certain dealuminizations to molecular sieve for method, make acid decrease, the molecular sieve crystallinity decline of complex carrier, are unfavorable for
The preparation of high performance catalyst.
U.S.6171474B1 discloses a kind of using Y molecular sieve as the catalyst for cracking heavy oil of carrier, which has larger
Specific surface area, but the catalyst exists simultaneously aperture and hole and holds lesser disadvantage, is unfavorable for the macromolecular of heavy distillate
Diffusion, therefore influence the hydrofinishing performance of the catalyst.
CN1488726 discloses a kind of preparation method for preparing molecular sieve and aluminium oxide composite carrier, and this method is adopted
With the mechanical mixture forming method of kneading, extrusion, by molecular sieve together with alumina composite, prepared carrier has larger
Specific surface area, but Kong Rong, aperture are relatively small, and acid strength is weaker, thus with catalyst towards heavy matter fraction made from this carrier
The Hydrogenation of oil is also not satisfactory.
CN1493656A discloses a kind of Y molecular sieve catalyst with substance modifications such as rare earth, clays, the water of the catalyst
Thermal stability is good, and heavy oil conversion performance is strong.But the lattice constant of the catalyst is small, also, uses binder by rare earth, glues
Soil is modified with molecular sieve, is easy a part of duct of blocking, is unfavorable for supporting for active metal.
CN 1136983C discloses a kind of composite molecular sieve catalyst, which is by small pore molecular sieve and inorganic acid
It is mutually compound with the large pore molecular sieve after rare earth modified, so that a kind of compound duct molecular sieve is made, so that different size in heavy oil
Molecule, which enters in different types of duct, to be reacted.But with inorganic acid modified molecular screen, it is readily incorporated impurity, the patent
And not yet explicitly removal methods of foreign atom.
CN 103212432A discloses a kind of heavy distillate hydrodenitrogenation catalyst, method include to Y and aluminium oxide into
Row surface acid etching, processed molecular sieve is as complex carrier.Catalyst hydrodenitrogenationactivity activity with higher, the disadvantage is that
Liquid is received low.
Therefore, the increase based on current crude oil heaviness and in poor quality trend, the hydrotreating difficulty of inferior heavy oil are more next
Bigger, finding one kind has that gradient pore size distribution, average pore size be larger, large specific surface area, and urging with suitable acid distribution
Agent carrier material is very necessary for promoting the raising of heavy Oil Hydrotreating Processes level.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst for hydro-processing heavy distillate.
The object of the invention is also to provide a kind of applications of catalyst for hydro-processing heavy distillate.
To achieve the above object, the present invention provides a kind of catalyst for hydro-processing heavy distillate, including active component and
Catalyst carrier, based on catalyst weight percent, the active component includes 10%~40% group vib metal oxide,
1%~20% group VIII metal oxide and/or 0.1%~10% VA race oxide；By catalyst carrier weight percent
Than meter, the catalyst carrier includes mesoporous TiO2-Al2O310~50wt% of presoma, 30~80wt% of aluminium oxide, adhesive 5
1~5wt% of~25wt% and extrusion aid；
Wherein, the mesoporous TiO2-Al2O3The preparation step of presoma is as follows:
(1) boehmite powder is add to deionized water mashing uniformly, inorganic acid solution, which is added dropwise, makes its peptization, adjusts
It is 2.0~5.0 to pH value of solution；
(2) it is 8~9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, and template is then added,
0.5~1h is reacted in 40~50 DEG C of stirred in water bath；
(3) ethyl alcohol is added to mixture obtained by step (2), reacts 0.5~1h, be then added titanium oxide, isopropyl titanate or
Then butyl titanate, the reaction was continued 0.5~1h are transferred to 10~20h of crystallizing kettle aging；
(4) mixture obtained by step (3) is filtered, then by filtration cakes torrefaction, obtains mesoporous TiO2-Al2O3Presoma.
Catalyst for hydro-processing heavy distillate of the present invention, the template are cetyl trimethylammonium bromide
Or hexadecyltrimethylammonium chloride.
Catalyst for hydro-processing heavy distillate of the present invention, vib metals oxide are the oxygen of molybdenum and/or tungsten
Compound, group VIII metal oxide are the oxide of cobalt and/or nickel, and V A race's oxide is the oxide of phosphorus.
Catalyst for hydro-processing heavy distillate of the present invention, inorganic acid described in step (1) be hydrochloric acid, sulfuric acid and
One or both of nitric acid.
Catalyst for hydro-processing heavy distillate of the present invention, template in step (2): A13+Molar ratio be
0.005~0.010.
Catalyst for hydro-processing heavy distillate of the present invention, filtration cakes torrefaction is at 60~200 DEG C in step (4)
At a temperature of dry 3~for 24 hours.
Catalyst for hydro-processing heavy distillate of the present invention, the specific surface area of the catalyst is 150~
350m2/ g, Kong Rongwei 0.3~0.6ml/g, Ti4+With Al3+Molar ratio is 0.01~0.3.
Catalyst for hydro-processing heavy distillate of the present invention, the mesoporous TiO2-Al2O3Specific surface area be 200
~500m2/ g, Kong Rongwei 0.5~1.2ml/g, Ti4+With Al3+Molar ratio is 0.08~1.5.
Catalyst for hydro-processing heavy distillate of the present invention, the alumina ratio surface area are 150~450m2/
0.25~0.6ml/g of g, Kong Rongwei.
To achieve the above object, the present invention also provides a kind of catalyst for hydro-processing heavy distillate in hydrocracking heavy oil
In application, hydrotreating reaction condition are as follows: 300 DEG C~450 DEG C of reaction temperature, hydrogen partial pressure 8MPa~20MPa, hydrogen to oil volume ratio
500:1~2000:1, volume space velocity 0.5h when liquid-1~3.0h-1。
Beneficial effects of the present invention:
Mesoporous TiO provided by the invention2-Al2O3Preparation method, rich in mesoporous, and meanwhile it is modified by Ti, it can be effectively improved
The interaction of carrier and active metal can effectively improve desulfurization, the denitrification ability of catalyst, reduce carbon deposit and generate.And have
There are biggish specific surface area, Kong Rong and suitable acid distribution, can satisfy heavier petroleum fraction catalytic hydrogenation reaction and diffusion
To the Property requirements of carrier material.
Specific embodiment
The present invention provide it is a kind of be suitable for process Heavy Petroleum Fractions with mesoporous TiO2-Al2O3, aluminium oxide be carrier material
The hydrotreating catalyst of material, and the mesoporous TiO is provided2-Al2O3Preparation method.
It is characteristic of the invention that being oriented to synthesising mesoporous aluminium oxide by template, while titanium oxide is introduced into mesoporous oxidation
In alumina supporter.With mesoporous TiO2-Al2O3Presoma, aluminium oxide be as complex carrier, by adjusting the content of each carrier component,
The carrier of hydrogenating catalyst for heavy oil of different titaniums are modified, different surfaces product and appropriate acid distribution can be prepared.
Catalysis provided by the invention includes active component and catalyst carrier, based on catalyst weight percent, the work
Property component includes 10%~40% group vib metal oxide, and 1%~20% group VIII metal oxide and/or 0.1%~
10% VA race oxide；Based on catalyst carrier weight percent, the catalyst carrier includes mesoporous TiO2-Al2O3Forerunner
10~50wt% of body, 1~5wt% of 30~80wt% of aluminium oxide, 5~25wt% of adhesive and extrusion aid.
Catalyst provided by the invention uses extruded moulding, and by adding phosphate in forming process, then roasting comes real
Existing P Modification.The preferred monoammonium phosphate of used phosphate, ammonium dihydrogen phosphate.
Catalyst preparation provided by the invention supports active metal using well known isometric solution dipping method on carrier
Component Ni, W, Mo.The preferred metatungstic acid ammonia of the maceration extract of catalyst activity component, nickel nitrate and ammonium molybdate；It is preferred that dipping temperature is
Room temperature, dip time 4~6 hours；It is preferred that drying temperature is 110~120 DEG C, drying time 4~8 hours；It is preferred that maturing temperature
It is 450~650 DEG C, calcining time 3~4 hours；Through overmolding, be ground up, sieved after preferably 3~3.6mm particle be it is of the invention
Preformed catalyst.
The preferred tenor of catalyst provided by the invention is respectively as follows: NiO 1~3%, WO in terms of oxide content3
10~25%.These metal components must in the form of sulfide competence exertion catalytic activity, thus catalyst is needed before use
Carry out presulfurization.
It is respectively 150~350m that the specific surface area of catalyst provided by the invention and hole, which hold,2/ g, 0.3~0.6ml/g, have
Good hydrofinishing performance.
Carrier and method for preparing catalyst provided by the present invention are as follows:
(1) the synthesising mesoporous TiO of template direction2-Al2O3Presoma.
(2) a certain amount of monoammonium phosphate is taken to be made into a certain concentration aqueous solution.Take the made mesoporous TiO of a certain amount of step (1)2-
Al2O3Presoma, and finished product aluminium oxide is taken to be sufficiently stirred, a certain amount of sesbania powder is added, is uniformly mixed, it is molten with ammonium hydrogen phosphate
Liquid mixing, extrusion forming, then 2~6 hours dry, small in 450~550 DEG C of roastings 3~5 at 100~120 DEG C according to a conventional method
When, obtain P Modification complex carrier.It is 0.25~0.60ml/g that alumina pore used in the present invention, which holds,；Specific surface area be 150~
450m2/g。
(3) P Modification complex carrier obtained by step (2) is made into maceration extract with the metallic salt containing active metal component,
Incipient impregnation or saturation infusion process can be used in impregnation method, after dipping in baking oven 100 DEG C~130 DEG C dry 2~6 hours,
Then it is roasted 3~5 hours at 400~800 DEG C in Muffle furnace, catalyst is just made.
Wherein, mesoporous TiO2-Al2O3Presoma the preparation method is as follows:
(1) boehmite powder is add to deionized water mashing uniformly, inorganic acid solution, which is added dropwise, makes its peptization；, adjust
Section to pH value of solution is 2.0~5.0, and inorganic acid is the one or two of hydrochloric acid, sulfuric acid, nitric acid；
(2) it is 8~9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, and template ten is then added
Six alkyl trimethyl ammonium bromides (CTABr) or hexadecyltrimethylammonium chloride (CTACl), in 40~50 DEG C of stirred in water bath
React 0.5~1h, template: A13+Molar ratio be 0.005~0.010；
(3) a certain amount of ethyl alcohol is added to mixture obtained by step (2), reacts 0.5~1h, a certain amount of oxidation is then added
Then titanium, isopropyl titanate or butyl titanate, the reaction was continued 0.5~1h are transferred to 10~20h of crystallizing kettle aging.
(4) mixture obtained by step (3) is filtered, then by filtration cakes torrefaction to get arriving mesoporous TiO2-Al2O3Presoma；Filter
Biscuit it is dry for 60~200 DEG C at a temperature of it is dry 3~for 24 hours.
1 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-1
(1) 230 grams of boehmites are added to stirring to pulp in 200ml water, the nitre of the lmol/L of 300ml is added dropwise
Acid solution, the boehmite suspension being acidified, the pH for adjusting sol solution is 4；
(2) it is 9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, and template 16 is then added
Alkyl trimethyl ammonium bromide (CTABr) 7g reacts 0.5h, template: A1 in 45 DEG C of stirred in water bath3+Molar ratio be
0.006；
(3) 20g ethyl alcohol is added to mixture obtained by step (2), reacts 0.5h, 200g butyl titanate, reaction is then added
Then 0.5h is transferred to crystallizing kettle aging 15h.
(4) mixture obtained by step (3) is filtered, then 4h dry at a temperature of 120 DEG C of filter cake is mesoporous to get arriving
TiO2-Al2O3Presoma.
2 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-2
(1) 300 grams of boehmites are added to stirring to pulp in 200ml water, are added dropwise the l mol/L's of 300ml
Nitric acid solution, the boehmite suspension being acidified, the pH for adjusting sol solution is 4；
(2) it is 9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, and template 16 is then added
Alkyl trimethyl ammonium chloride (CTACl) 10g reacts 0.5h, template: A1 in 40-50 DEG C of stirred in water bath3+Molar ratio be
0.0067；
(3) 20g ethyl alcohol is added to mixture obtained by step (2), reacts 0.5h, 200g butyl titanate, reaction is then added
Then 0.5h is transferred to crystallizing kettle aging 15h.
(4) mixture obtained by step (3) is filtered, then 4h dry at a temperature of 120 DEG C of filter cake is mesoporous to get arriving
TiO2-Al2O3Presoma.
3 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-3
(1) 300 grams of boehmites are added to stirring to pulp in 200ml water, are added dropwise the l mol/L's of 300ml
Nitric acid solution, the boehmite suspension being acidified, the pH for adjusting sol solution is 4；
(2) it is 9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, and template 16 is then added
Alkyl trimethyl ammonium bromide (CTABr) 10g reacts 0.5h, template: A1 in 40-50 DEG C of stirred in water bath3+Molar ratio be
0.0067；
(3) 20g ethyl alcohol is added to mixture obtained by step (2), reacts 0.5h, 200g butyl titanate, reaction is then added
Then 0.5h is transferred to crystallizing kettle aging 15h.
(4) mixture obtained by step (3) is filtered, then 4h dry at a temperature of 120 DEG C of filter cake is mesoporous to get arriving
TiO2-Al2O3Presoma.
4 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-4
The embodiment is difference from example 1 is that the amount that butyl titanate is added is 555g, gained complex carrier note
For TA-4.
5 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-5
The embodiment is difference from example 1 is that the amount that butyl titanate is added is 1110g, gained complex carrier note
For TA-5.
6 template of embodiment is oriented to synthesising mesoporous TiO2-Al2O3TA-6
For the embodiment difference from example 1 is that isopropyl titanate 167g is added, gained complex carrier is denoted as TA-6.
Embodiment 7 prepares catalyst CTA-1
(1) take 15g monoammonium phosphate that monoammonium phosphate solution 1000ml is made；
(2) the mesoporous TiO of 350g is weighed2-Al2O3(alumina ratio surface area is 220m to presoma TA-1,700g aluminium oxide2/
G, Kong Rongwei 0.28ml/g), 30g sesbania powder, be sufficiently stirred, be uniformly mixed, obtain mixed powder；
(3) mixed powder obtained by step (2) is mixed with ammonium hydrogen phosphate solution, according to a conventional method extrusion forming, 120 DEG C dry
After dry 4h, the lower 450 DEG C of roastings 4h of air atmosphere, P Modification complex carrier TAB-1 is obtained, support is shown in Table 1.
(4) the P Modification complex carrier for weighing 800g, with ammonia spirit (the wherein MoO of a certain amount of ammonium molybdate and nickel nitrate3
Concentration is 44.5g/100ml；NiO concentration is 8.8g/100ml) supersaturation dipping 1h, filter redundant solution, 120 DEG C of dry 4h,
Then 450 DEG C of roasting 4h in air atmosphere, obtain catalyst.Support is shown in Table 1, and evaluation feedstock property is shown in Table 4, is reacting
Pressure 10.0MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 800:1, under 370 DEG C of reaction temperature of operating condition, evaluation result
It is shown in Table 5.
Embodiment 8 prepares catalyst CTA-2
(1) take 15g monoammonium phosphate that monoammonium phosphate solution 1000ml is made；
(2) the mesoporous TiO of 330g is weighed2-Al2O3(alumina ratio surface area is 220m to presoma TA-2,650g aluminium oxide2/
G, Kong Rongwei 0.28ml/g), 30g sesbania powder, be sufficiently stirred, be uniformly mixed, obtain mixed powder；
(3) mixed powder obtained by step (2) is mixed with ammonium hydrogen phosphate solution, according to a conventional method extrusion forming, 120 DEG C dry
After dry 4h, the lower 450 DEG C of roastings 4h of air atmosphere, P Modification complex carrier TAB-2 is obtained, support is shown in Table 1.
(4) the P Modification complex carrier for weighing 800g, with ammonia spirit (the wherein MoO of a certain amount of ammonium molybdate and nickel nitrate3
Concentration is 44.5g/100ml；NiO concentration is 8.8g/100ml) supersaturation dipping 1h, filter redundant solution, 120 DEG C of dry 4h,
Then 450 DEG C of roasting 4h in air atmosphere, obtain catalyst.Support is shown in Table 1, and evaluation feedstock property is shown in Table 4, is reacting
Pressure 10.0MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 800:1, under 370 DEG C of reaction temperature of operating condition, evaluation result
It is shown in Table 5.
Embodiment 9 prepares catalyst CTA-3
(1) take 15g monoammonium phosphate that monoammonium phosphate solution 1000ml is made；
(2) the mesoporous TiO of 380g is weighed2-Al2O3(alumina ratio surface area is 220m to presoma TA-3,750g aluminium oxide2/
G, Kong Rongwei 0.28ml/g), 30g sesbania powder, be sufficiently stirred, be uniformly mixed, obtain mixed powder；
(3) mixed powder obtained by step (2) is mixed with ammonium hydrogen phosphate solution, according to a conventional method extrusion forming, 120 DEG C dry
After dry 4h, the lower 450 DEG C of roastings 4h of air atmosphere, P Modification complex carrier TAB-3 is obtained, support is shown in Table 1.
(4) the P Modification complex carrier for weighing 800g, with ammonia spirit (the wherein MoO of a certain amount of ammonium molybdate and nickel nitrate3
Concentration is 44.5g/100ml；NiO concentration is 8.8g/100ml) supersaturation dipping 1h, filter redundant solution, 120 DEG C of dry 4h,
Then 450 DEG C of roasting 4h in air atmosphere, obtain catalyst.Evaluation feedstock property is shown in Table 3, in reaction pressure 10.0MPa, body
Product air speed 1.0h-1, hydrogen to oil volume ratio 800:1, under 370 DEG C of reaction temperature of operating condition, evaluation result is shown in Table 5.
Embodiment 10 prepares catalyst CTA-4
The embodiment is with embodiment 7 the difference is that the mesoporous TiO of addition2-Al2O3Presoma is TA-4, and gained is multiple
It closes carrier and is denoted as TAB-4, gained catalyst is denoted as CTA-4.
Embodiment 11 prepares catalyst CTA-5
The embodiment is with embodiment 7 the difference is that the mesoporous TiO of addition2-Al2O3Presoma is TA-5, and gained is multiple
It closes carrier and is denoted as TAB-5, gained catalyst is denoted as CTA-5.
Embodiment 12 prepares catalyst CTA-6
The embodiment is with embodiment 7 the difference is that the mesoporous TiO of addition2-Al2O3Presoma is TA-6, and gained is multiple
It closes carrier and is denoted as TAB-6, gained catalyst is denoted as CTA-6.
Comparative example CTA-7
(1) the mesoporous TiO of 350g is weighed2-Al2O3(alumina ratio surface area is 220m to presoma TA-1,700g aluminium oxide2/
G, Kong Rongwei 0.28ml/g), 30g sesbania powder, be sufficiently stirred, be uniformly mixed, extrusion forming according to a conventional method, 120 DEG C of dry 4h,
After the lower 450 DEG C of roastings 4h of air atmosphere, complex carrier TAB-7 is obtained, support is shown in Table 1.
(2) the complex carrier TAB-7 for weighing 800g, with ammonia spirit (the wherein MoO of a certain amount of ammonium molybdate and nickel nitrate3
Concentration is 44.5g/100ml；NiO concentration is 8.8g/100ml) supersaturation dipping 1h, filter redundant solution, 120 DEG C of dry 4h,
Then 450 DEG C of roasting 4h in air atmosphere, obtain catalyst.Support is shown in Table 1, and evaluation feedstock property is shown in Table 3, is reacting
Pressure 10.0MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 800:1, under 370 DEG C of reaction temperature of operating condition, evaluation result
It is shown in Table 5.
Comparative example CTA-8
A kind of hydrotreating catalyst CTA-8 of industrial application (deriving from Fushun Effect of Catalysis In Petrochemistry agent factory), molecular sieve
For a kind of Al of modification2O3Molecular sieve, main physico-chemical property: WO3Content is 24.3wt%, and NiO content is 5.9wt%, compares table
Area 230m2/ g, Kong Rong 0.32ml/g.
The hydrofinishing performance of embodiment 10Ni-W catalyst
Catalyst hydrogenation, which refines performance evaluation, to be carried out on 200ml hydrogenation plant, and loaded catalyst 100ml is urged
Agent carries out presulfurization, conditions of vulcanization first are as follows: 5%CS2/ hydrotreated kerosene be vulcanization liquid, 320 DEG C of temperature, pressure 10.0MPa,
Air speed 1.5h-1, hydrogen-oil ratio 500 (V/V), vulcanization time 30h.The raw material that catalyst hydrogenation refines performance evaluation is high nitrogen-containing
Wax tailings inferior, reaction condition are as follows: 370 DEG C of temperature, pressure 10.0MPa, air speed 1.0h-1, hydrogen-oil ratio 800 (V/V).It is above-mentioned
The hydrofinishing performance desulfurization degree (HDS) and denitrification percent (HDN) for the Ni-W catalyst that different carriers obtain indicate, as a result such as table
Shown in 5.
1 support of table
L acid acid measures high meeting so that the lytic activity of catalyst enhances, and the carbon distribution of catalyst, which is inclined to, to be improved, and B acid is to raising
Hydrogenation activity is advantageous.Table 2 is the acidity of TA-1 carrier, it can be seen that TA-1 carrier has L acid and B acid simultaneously, this is conducive to aromatic hydrocarbons
Saturation.
2 modified support of table is acid
3 catalyst property of table
4 raw material oil nature of table
| Feedstock oil | CGO |
| Specific gravity, g/cm3 | 0.9608 |
| Total nitrogen content, μ g/g | 8500 |
| Total sulfur content, μ g/g | 3700 |
| Carbon residue, % | 0.73 |
| Race's composition, w% | |
| Saturated hydrocarbons | 41.03 |
| Aromatic hydrocarbons | 55.84 |
| Polar compound | 3.13 |
| Boiling range, DEG C | |
| HK | 216 |
| 10% | 379 |
| 50% | 427 |
| 90% | 468 |
| KK | 497 |
5 evaluating catalyst result of table
| Catalyst | CTA-1 | CTA-2 | CTA-3 | CTA-4 | CTA-5 | CTA-6 | CTA-7 | CTA-8 |
| HDS, % | 97.3 | 97.1 | 97.6 | 97.2 | 96.4 | 97.3 | 95.9 | 94.8 |
| HDN, % | 77.5 | 77.2 | 77.8 | 77.3 | 76.3 | 77.3 | 76.1 | 73.8 |
| Carbon residue, % | 0.04 | 0.04 | 0.03 | 0.04 | 0.06 | 0.04 | 0.07 | 0.09 |
From above-described embodiment, it can be seen that, carrier and catalyst provided by the invention have biggish specific surface area, Kong Rong
And aperture, when in for wax tailings hydroprocessing processes inferior, shows good hydrodesulfurization activity and add hydrogen de-
Nitrogen activity.Therefore, catalyst provided by the present invention is suitable for the hydroprocessing processes of petroleum distillate, is particularly suitable for application to weight
Matter distillate hydrogenation treatment process.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (10)
1. a kind of catalyst for hydro-processing heavy distillate, including active component and catalyst carrier, which is characterized in that by catalysis
Agent weight percent meter, the active component include 10%~40% group vib metal oxide, 1%~20% VIII group
Metal oxide and/or 0.1%~10% VA race oxide；Based on catalyst carrier weight percent, the catalyst is carried
Body includes mesoporous TiO2-Al2O310~50wt% of presoma, 30~80wt% of aluminium oxide, 5~25wt% of adhesive and extrusion aid 1
~5wt%；
Wherein, the mesoporous TiO2-Al2O3The preparation step of presoma is as follows:
(1) boehmite powder is add to deionized water mashing uniformly, inorganic acid solution, which is added dropwise, makes its peptization, is adjusted to molten
Liquid pH is 2.0~5.0；
(2) it is 8~9 that ammonium hydroxide is added into the mixture of step (1) and adjusts the pH of reaction system, template is then added, 40
~50 DEG C of stirred in water bath reacts 0.5~1h；
(3) ethyl alcohol is added to mixture obtained by step (2), reacts 0.5~1h, titanium oxide, isopropyl titanate or metatitanic acid is then added
Then butyl ester, the reaction was continued 0.5~1h are transferred to 10~20h of crystallizing kettle aging；
(4) mixture obtained by step (3) is filtered, then by filtration cakes torrefaction, obtains mesoporous TiO2-Al2O3Presoma.
2. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that the template is 16
Alkyl trimethyl ammonium bromide or hexadecyltrimethylammonium chloride.
3. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that vib metals oxidation
Object is the oxide of molybdenum and/or tungsten, and group VIII metal oxide is the oxide of cobalt and/or nickel, and V A race's oxide is phosphorus
Oxide.
4. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that nothing described in step (1)
Machine acid is one or both of hydrochloric acid, sulfuric acid and nitric acid.
5. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that template in step (2):
A13+Molar ratio be 0.005~0.010.
6. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that filter cake is dry in step (4)
It is dry for 60~200 DEG C at a temperature of it is dry 3~for 24 hours.
7. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that the ratio table of the catalyst
Area is 150~350m2/ g, Kong Rongwei 0.3~0.6ml/g, Ti4+With Al3+Molar ratio is 0.01~0.3.
8. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that the mesoporous TiO2-
Al2O3The specific surface area of presoma is 200~500m2/ g, Kong Rongwei 0.5~1.2ml/g, Ti4+With Al3+Molar ratio be 0.08~
1.5。
9. catalyst for hydro-processing heavy distillate according to claim 1, which is characterized in that the alumina ratio surface
Product is 150~450m20.25~0.6ml/g of/g, Kong Rongwei.
10. catalyst for hydro-processing heavy distillate according to any one of claims 1 to 9 answering in hydrocracking heavy oil
With, which is characterized in that hydrotreating reaction condition are as follows: 300 DEG C~450 DEG C of reaction temperature, hydrogen partial pressure 8MPa~20MPa, hydrogen oil
Volume ratio 500:1~2000:1, volume space velocity 0.5h when liquid-1~3.0h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711220716.2A CN109833891B (en) | 2017-11-29 | 2017-11-29 | Heavy distillate oil hydrotreating catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711220716.2A CN109833891B (en) | 2017-11-29 | 2017-11-29 | Heavy distillate oil hydrotreating catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109833891A true CN109833891A (en) | 2019-06-04 |
| CN109833891B CN109833891B (en) | 2022-01-04 |
Family
ID=66881527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711220716.2A Active CN109833891B (en) | 2017-11-29 | 2017-11-29 | Heavy distillate oil hydrotreating catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833891B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115805079A (en) * | 2022-12-08 | 2023-03-17 | 上海化工研究院有限公司 | CO methanation purifying agent based on titanium oxide modified mesoporous alumina and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199935A (en) * | 2006-12-14 | 2008-06-18 | 中国石油天然气集团公司 | Titania-alumina mixed oxide hydrodesulfurization catalyst and preparing process thereof |
| CN101869839A (en) * | 2009-04-27 | 2010-10-27 | 北京海顺德钛催化剂有限公司 | Selective hydrogenation catalyst for catalytic cracking gasoline and preparation method thereof |
| US20130190527A1 (en) * | 2012-01-23 | 2013-07-25 | Celanese International Corporation | Bismuth Catalyst Composition and Process For Manufacturing Ethanol Mixture |
| CN104043479A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation and application thereof |
| CN104475168A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Preparation method of titanium-aluminum composite oxide with large specific surface and small aperture |
-
2017
- 2017-11-29 CN CN201711220716.2A patent/CN109833891B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101199935A (en) * | 2006-12-14 | 2008-06-18 | 中国石油天然气集团公司 | Titania-alumina mixed oxide hydrodesulfurization catalyst and preparing process thereof |
| CN101869839A (en) * | 2009-04-27 | 2010-10-27 | 北京海顺德钛催化剂有限公司 | Selective hydrogenation catalyst for catalytic cracking gasoline and preparation method thereof |
| US20130190527A1 (en) * | 2012-01-23 | 2013-07-25 | Celanese International Corporation | Bismuth Catalyst Composition and Process For Manufacturing Ethanol Mixture |
| CN104043479A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation and application thereof |
| CN104475168A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Preparation method of titanium-aluminum composite oxide with large specific surface and small aperture |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGBO LI等: "Superior Performance of Mesoporous TiO2–Al2O3 Supported NSR Catalysts with the Support Synthesized Using Nonionic and Cationic Surfactants as Co-Templates", 《CATALYSIS LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115805079A (en) * | 2022-12-08 | 2023-03-17 | 上海化工研究院有限公司 | CO methanation purifying agent based on titanium oxide modified mesoporous alumina and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109833891B (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11642664B2 (en) | Silica containing alumina supports, catalysts made therefrom and processes using the same | |
| JP4156859B2 (en) | Gas oil hydrotreating catalyst, method for producing the same, and gas oil hydrotreating method | |
| CN101376110B (en) | Preparation of hydrogenation catalyst | |
| CN101905175B (en) | Method for preparing heavy distillate hydrotreating catalyst | |
| CN102485847B (en) | Method for hydrorefining petroleum wax | |
| CN102451722B (en) | Preparation method of eggshell-type hydrogenation catalyst | |
| CN106669803B (en) | Produce the catalyst and preparation method thereof of high viscosity index (HVI) hydrocracking tail oil | |
| CN101590424A (en) | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof | |
| CN107029779B (en) | A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve | |
| CN101204659B (en) | Hydrogenation catalyst using Al, Ti and Si compound oxide as carrier and preparation method thereof | |
| CN108393096A (en) | Hydrobon catalyst, the grading composition method of Hydrobon catalyst and application | |
| CN105749922A (en) | Preparation method of heavy oil hydrotreating catalyst and heavy oil hydrotreating catalyst prepared by preparation method and use of heavy oil hydrotreating catalyst | |
| CN103861647B (en) | A kind of hydrocracking catalyst containing heteropoly acid and application thereof | |
| CN106391103B (en) | A kind of multi-stage porous hydrocracking catalyst of silicon-aluminum containing and its application | |
| CN109833891A (en) | A kind of catalyst for hydro-processing heavy distillate and its application | |
| CN104271238B (en) | Containing selenium hydrotreating catalyst, its purposes, and preparation method | |
| CN106925287B (en) | A kind of heavier petroleum fraction hydrotreating catalyst and preparation method thereof | |
| CN103962165B (en) | A kind of transition metal phosphide hydrogenation catalyst and its preparation method | |
| CN107961771B (en) | Alumina carrier and preparation method thereof, and hydrofining catalyst and preparation method thereof | |
| CN109772400B (en) | Hydrotreating catalyst and preparation method and application thereof | |
| CN104226322B (en) | Heavy-oil hydrotreatment catalyst and preparation and application thereof | |
| CN104449832B (en) | A kind of catalytically cracked stock weighted BMO spaces method | |
| JP4519379B2 (en) | Heavy hydrocarbon oil hydrotreating catalyst | |
| CN106031880B (en) | A kind of multi-stage porous hydrocracking catalyst and its application | |
| CN106140183A (en) | A kind of preparation method containing zirconium Hydrodemetalation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |