CN108404897A - A kind of catalyst carrier for hydrgenating heavy oil, preparation method, using its catalyst and catalyst preparation method - Google Patents
A kind of catalyst carrier for hydrgenating heavy oil, preparation method, using its catalyst and catalyst preparation method Download PDFInfo
- Publication number
- CN108404897A CN108404897A CN201710073142.4A CN201710073142A CN108404897A CN 108404897 A CN108404897 A CN 108404897A CN 201710073142 A CN201710073142 A CN 201710073142A CN 108404897 A CN108404897 A CN 108404897A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- catalyst carrier
- hydrgenating
- kneading
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of catalyst carrier for hydrgenating heavy oil, preparation method, using its catalyst and catalyst preparation method, support preparation method includes the following steps：Step 1, book clay and water are mixed with beating uniformly；Step 2, siliceous boehmite dry glue powder and peptization agent solution are added in kneading equipment, then the book clay slurries of step 1 are added in kneading 10 20 minutes, after Aluminum sol, then abundant kneading is added after 10 15min of kneading, extruded moulding；Step 3, aging 15 hours at 50 90 DEG C, it is 2 10 hours dry at 100 150 DEG C, catalyst carrier is then roasted 3~6 hours to obtain at 500~1100 DEG C；Wherein, on the basis of catalyst carrier, the mass content of book clay is 5 30%.Catalyst carrier of the present invention can be used for preparing hydrogenation catalyst, have good desulfurization, denitrogenation and de- carbon residue activity.
Description
Technical field
The present invention relates to a kind of catalyst carrier for hydrgenating heavy oil, the preparation method of carrier, the catalyst using it, catalyst
Preparation method.Particularly suitable for weight, the preparation of residuum hydrodesulfurization and hydrodenitrogeneration.
Background technology
The in short supply and in poor quality of global petroleum resources leads on Crude Oil Market the ratio of heavy crude and sour crude not
It is disconnected to improve；Increasingly strict with China's rapid development of economy and environmental regulation simultaneously, market also exists to clear gusoline demand
Rapidly increase.Therefore, light materialization of heavy oil and high quality are the current vital tasks for being badly in need of solving.Hydrotreating techniques are to solve
A kind of effective means of the above problem.In existing hydrogen addition technology, bed technology is the most ripe, most widely used.Usually
In the reaction of fixed bed residual hydrogenation, when oil product is after protective agent bed, metal remover bed, desulfurizing agent bed, major part is golden
Belong to and sulphur effectively removes, but remaining impurity high stability, is in particular in the fixed bed heavy-oil hydrogenation of current commercial Application
The reactor denitrogenation of device end and de- carbon residue are not ideal enough, this proposes higher to the activity and activity stability of catalyst and wants
It asks.
For many years, hydrogenation catalyst is generally using Ni (Co)-Mo (W) as active component, and aluminium oxide is as carrier, using leaching
It is prepared by stain method.The property of alumina support depends greatly on boehmite.Boehmite often has
Different pore structures and acidity, acidity are affected for catalyst performance with pore structure.For improve catalyst plus hydrogen
De- impurity activity, it will usually introduce the auxiliary agents such as P, B, F, Ti, Si, Zr, the acidity and pore structure of regulating catalyst carrier.But it aoxidizes
The acidity of aluminium itself is weaker, improves limitation to alumina acidic after additive modification, causes catalyst desulfurizing, denitrification ability difficult
To further increase, although and the problem of molecular sieve acidity is met the requirements, and it is small that there are ducts, heavy oil diffusion energy force difference.
CN103480390A provides a kind of catalyst and its preparation method and application with hydrogenation catalyst effect, this is urged
Agent contains carrier and loads at least one group VIII metallic element on the carrier and at least one group VIB
Metallic element, the carrier are hydrated alumina forming matter, by containing at least one hydrated alumina, at least one containing rare earth member
The compound of element and the raw material of at least one cellulose ether are made.Catalyst according to the invention is in hydrocarbon ils (especially heavy hydrocarbon
Oil) hydrodemetallization reaction in show higher catalytic activity, better catalytic stability and longer service life.But
Catalyst desulfurizing denitrification activity is general, it is hard to meet the requirements.
CN1352227A discloses a kind of hydrotreating catalyst and preparation method thereof, especially heavy oil hydrodesulfurization and is catalyzed
Agent and preparation method thereof.The invention is using a kind of cheap and environmental-friendly Ti-contained aluminium hydroxide carrier.Pass through titaniferous hydrogen-oxygen
Change the materials such as aluminium and metallic salt kneading process, promote metal dispersion, all materials after kneading is at plastic, extrusion at
Catalyst is made through high-temperature activation in type.The shaping of catalyst of preparation is easy, and Acidity is suitable, while having excellent plus hydrogen de-
Sulphur and preferable hydrodenitrogeneration and removal of ccr by hydrotreating activity.But it uses full kneading mode to prepare catalyst, active metal point
Divergence, specific surface area of catalyst and pore volume room for promotion are all little, and then the activity for influencing catalyst improves.
Invention content
The main purpose of the present invention is to provide a kind of catalyst carrier for hydrgenating heavy oil, preparation method, urging using it
The preparation method of agent and catalyst, with overcome in the prior art heavy-oil hydrogenation catalyst activity it is low, specific surface area of catalyst and
The smaller defect of pore volume.
In order to achieve the above object, the present invention provides a kind of preparation method of catalyst carrier for hydrgenating heavy oil, the preparations
Method includes the following steps：
Step 1, book clay and water are mixed with beating uniformly；
Step 2, it is added siliceous boehmite dry glue powder and peptization agent solution in kneading equipment, kneading 10-20 minutes,
Then the book clay slurries of step 1 are added, after Aluminum sol, then abundant kneading is added after kneading 10-15min, extruded moulding；
Step 3,2-10 hours dry at 100-150 DEG C aging 1-5 hours at 50-90 DEG C, then 500~1100
DEG C roasting 3~6 hours catalyst carrier；
Wherein, on the basis of catalyst carrier, the mass content of book clay is 5-30%.
The preparation method of catalyst carrier for hydrgenating heavy oil of the present invention, wherein it is preferred that the step 2 addition contains
Extrusion aid is added while silicon boehmite dry glue powder, the extrusion aid is preferably sesbania powder, starch, polyvinyl alcohol and methyl
One or more of formed group of cellulose.
The preparation method of catalyst carrier for hydrgenating heavy oil of the present invention, wherein the peptization agent solution is preferably nitre
Acid, acetic acid, formic acid or hydrochloric acid solution.
The preparation method of catalyst carrier for hydrgenating heavy oil of the present invention, wherein layered clay is preferably natural
Or the artificial synthesized regular interstratified mineral natural or artificial synthesized with the smectite class clay of expansile single-storeyed mineral structure
Mineral structure clay.
The preparation method of catalyst carrier for hydrgenating heavy oil of the present invention, wherein layered clay is further preferred
For montmorillonite, Hectorite, beidellite, rectorite, mica-smectite, glauconite-smectite and chlorite-smectite institute group
At one or more of group.
In order to achieve the above object, it is prepared the present invention also provides the preparation method of above-mentioned catalyst carrier for hydrgenating heavy oil
Catalyst carrier.
Catalyst carrier prepared by the preparation method of catalyst carrier for hydrgenating heavy oil of the present invention, wherein described to urge
It is preferably 0.40~0.90mL/g that the hole of agent carrier, which holds, and specific surface area is preferably 150~450m2/g。
In order to achieve the above object, the present invention also provides a kind of preparation method of heavy-oil hydrogenation catalyst, the preparation sides
Method is：
VIB and/or group VIII metal salting liquid are prepared, the method sprayed using saturation, by metal salt solution to be atomized shape
State sprays in the catalyst carrier of preparation method preparation of the catalyst carrier for hydrgenating heavy oil described in claim 6, then exists
It is 1~8 hour dry at 80~150 DEG C, then at 300~650 DEG C, roasts 2~6 hours, be prepared into heavy-oil hydrogenation catalyst；
Wherein, on the basis of catalyst quality, the load capacity of metal is in terms of oxide in catalyst, vib metal oxide
For 3.0~20.0% and/or group VIII metal oxide 2.0~8.0%.
The preparation method of heavy-oil hydrogenation catalyst of the present invention, wherein the VIB and/or group VIII metal salt are molten
Liquid is preferably the salting liquid of one or more of metal molybdenum, tungsten, nickel and the formed group of cobalt.
In order to achieve the above object, the present invention also provides catalysis prepared by the preparation method of above-mentioned heavy-oil hydrogenation catalyst
Agent.
Beneficial effects of the present invention：
The present invention selects book clay and siliceous boehmite as support material, and such be advantageous in that overcomes oxygen
Change the acidity of alumina supporter problem on the weak side, improves desulfurization, denitrogenation and de- the carbon residue activity of catalyst.It is prepared using the method that sprays
Catalyst, active component are uniformly dispersed, and catalyst has good desulfurization, denitrogenation and de- carbon residue activity, is led in mink cell focus plus hydrogen
Domain has wide practical use.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Book clay is a kind of solid acid, is the layer structure of some columns support, has two-dimensional channel, interlamellar spacing reachable
5nm or so is much larger than currently used Y molecular sieve aperture, advantageous to heavy oil solid tumor and reaction.
Book clay and siliceous boehmite are prepared into complex carrier by the present invention, and specific preparation process is：
Step 1, book clay and water are mixed with beating uniformly；
Step 2, it is added siliceous boehmite dry glue powder and peptization agent solution in kneading equipment, kneading 10-20 minutes,
Then the book clay slurries of step 1 are added, after Aluminum sol, then abundant kneading is added after kneading 10-15min, extruded moulding；
Step 3,2-10 hours dry at 100-150 DEG C aging 1-5 hours at 50-90 DEG C, then 500~1100
DEG C roasting 3~6 hours catalyst carrier；Wherein, on the basis of catalyst carrier, the mass content of book clay is 5-
30%.
Then again with the method that sprays by gained composite carrier load active component, gained catalyst total acid content 0.50-
0.80mmol.g-1, B acid amounts are 0.30-0.50mmol.g-1, it is 0.30~0.80mL/g, specific surface that catalyst pores of the present invention, which are held,
Product is 100~350m2/ g, and catalyst of the present invention can keep comparable intensity.
The shape of complex carrier of the present invention can be changed according to different requirements.
Technical solution of the present invention is described in detail with reference to specific embodiment.
Concentration, content unexplained reference are all mass concentration, mass content in following embodiment.
Embodiment 1
Weigh siliceous boehmite dry glue powder (SiO2Content is 35%) (Shandong star all petrochemical industry science and technology joint-stock companies
Production) 500g (butt), sesbania powder 15g is added and is uniformly mixed.Preceding is added in the acetum 300g of a concentration of 5.0wt%
In material, 40% concentration rectorite (SiO is added in kneading 15 minutes2Mass content is 40%, Hubei distinguished personages' rectorite science and technology share
Co., Ltd produces) slurries 100g, the Aluminum sol solution 120g of the pH=5-6 of 30% concentration is added in kneading 12 minutes, and kneading is complete
Cheng Hou, after the cylinder of a diameter of 2.0mm is extruded on single-screw extruder.In 70 DEG C of agings 2 hours, then dry 3 at 110 DEG C
Hour, then be placed in roaster, 780 DEG C are risen to 100~200 DEG C/h of speed, is roasted 3 hours.Obtain carrier A, property
It is shown in Table 1.
150g is weighed, water absorption rate is the above-mentioned carrier of 1.10mL/g, and spraying 165mL by saturated absorption amount of solution contains 38.6g
Ammonium molybdate (contains MoO382m%) and the ammonia spirit of 34.10g nickel nitrates (25.2m% containing NiO).5 are homogenized in spraying equipment
It is 2 hours dry at 60 DEG C after minute, it is 3 hours dry at 120 DEG C after taking-up, then roasted 3 hours in 500 DEG C of air, it is made
Catalyst.Number is C-1.
Embodiment 2
Weigh siliceous boehmite dry glue powder (SiO2Content is 10%) (Shandong star all petrochemical industry science and technology joint-stock companies
Production) 500g (butt), sesbania powder 15g is added and is uniformly mixed.Afore-mentioned materials are added in the acetum 200g of a concentration of 8wt%
In, 40% concentration bentonite (SiO is added in kneading 15 minutes2Mass content is 61%, Ke Laien Red Hill bentonites Co., Ltd
Production) slurries 200g, the Aluminum sol solution 120g of the pH=5-6 of 50% concentration is added in kneading 12 minutes, after the completion of kneading, so
The bunge bedstraw herb type of a diameter of 2.0mm is extruded on single-screw extruder afterwards.It is 3 hours dry at 120 DEG C, then be placed in roaster,
880 DEG C are risen to 100~200 DEG C/h of speed, is roasted 3 hours.Carrier B is obtained, property is shown in Table 1.
150g is weighed, water absorption rate is the above-mentioned carriers of 1.10mL/g, sprays 50mL ammonium molybdates containing 38.6g and (contains MoO382m%)
With the ammonia spirit of 34.1g cobalt nitrates (25.2m% containing CoO, Beijing chemical reagents corporation), at the uniform velocity dripped in spray-stain process moderate
Enter the ammonia spirit of 115mL a concentration of 15% in soaking in solution and stirring evenly, sprays, sprayed when instilling within 15 minutes.
It sprays and is homogenized in equipment after ten minutes, it is 5 hours dry at 120 DEG C, then roasted 4 hours in 500 DEG C of air, catalysis is made
Agent.Number is C-2.Its property is as shown in table 4.
Embodiment 3
Weigh boehmite dry glue powder (SiO2Content is that 10%) (star all petrochemical industry science and technology joint-stock companies in Shandong give birth to
Production) 500g (butt), sesbania powder 15g is added and is uniformly mixed.Afore-mentioned materials are added in the acetum 200g of a concentration of 8wt%
In, 30% concentration bentonite and rectorite slurries 300g (SiO is added in kneading 15 minutes2Content is 50%, bentonite and tired support
Stone by weight 1：1 ratio is added), the Aluminum sol solution 120g of the pH=5-6 of 50% concentration is added in kneading 12 minutes, and kneading is complete
Then Cheng Hou is extruded into the bunge bedstraw herb type of a diameter of 2.0mm on single-screw extruder.It is 3 hours dry at 120 DEG C, then it is placed in roasting
It burns in stove, rises to 880 DEG C with 100~200 DEG C/h of speed, roast 3 hours.Support C is obtained, property is shown in Table 1.
150g is weighed, water absorption rate is the above-mentioned carriers of 1.10mL/g, sprays 82.5mL ammonium molybdates containing 28.66g and (contains MoO3
82m%) with the ammonia spirit of 27.80g nickel nitrates (25.2m% containing NiO), spray within 10 minutes.10 are homogenized in spraying equipment
It is 2 hours dry at 60 DEG C after minute, it is 3 hours dry at 120 DEG C after taking-up, then roasted 3 hours in 500 DEG C of air, it is made
Catalyst.Number is C-3.
Comparative example 1
Weigh siliceous boehmite dry glue powder (SiO2Content is that 35%) 500g (butt), addition sesbania powder 15g are mixed
Uniformly, the acetum 500g of a concentration of 3.0wt% is added in afore-mentioned materials, kneading 35 minutes, after in single-screw extruder
On be extruded into the cylinder of a diameter of 2.0mm.It is 3 hours dry in 70 DEG C of agings 2 hours, then at 110 DEG C, then be placed in roaster,
780 DEG C are risen to 100~200 DEG C/h of speed, is roasted 3 hours.Carrier E is obtained, property is shown in Table 1.
150g is weighed, water absorption rate is the above-mentioned carrier of 1.10mL/g, and spraying 165mL by saturated absorption amount of solution contains 38.6g
Ammonium molybdate (contains MoO382m%) and the ammonia spirit of 34.10g nickel nitrates (25.2m% containing NiO).5 are homogenized in spraying equipment
It is 2 hours dry at 60 DEG C after minute, it is 3 hours dry at 120 DEG C after taking-up, then roasted 3 hours in 500 DEG C of air, it is made
Catalyst.Number is C-4.
Comparative example 2
It is (dry to weigh not siliceous boehmite dry glue powder (star all petrochemical industry science and technology joint-stock companies in Shandong produce) 500g
Base), sesbania powder 15g is added and is uniformly mixed.The acetum 280g of a concentration of 5.0wt% is added in afore-mentioned materials, kneading 15
Minute, 40% concentration rectorite (Hubei Mingliu Leituoshi Stone Science ＆ Technology Co. Ltd.'s production) slurries 100g is added, kneading 12 is divided
The Aluminum sol solution 120g of the pH=5-6 of 30% concentration is added in clock, after the completion of kneading, after be extruded on single-screw extruder it is straight
Diameter is the cylinder of 2.0mm.It is 3 hours dry in 70 DEG C of agings 2 hours, then at 110 DEG C, then be placed in roaster, with 100~
200 DEG C/h of speed rises to 780 DEG C, roasts 3 hours.Carrier F is obtained, property is shown in Table 1.
150g is weighed, water absorption rate is the above-mentioned carrier of 1.10mL/g, and spraying 165mL by saturated absorption amount of solution contains 38.6g
The ammonia spirit of ammonium molybdate (82m% containing MoO3) and 34.10g nickel nitrates (25.2m% containing NiO).5 are homogenized in spraying equipment
It is 2 hours dry at 60 DEG C after minute, it is 3 hours dry at 120 DEG C after taking-up, then roasted 3 hours in 500 DEG C of air, it is made
Catalyst.Number is C-5.
1 support of table
As shown in Table 1, compared with comparative example carrier E, carrier A, B, C of the embodiment of the present invention, acid amount is more, especially B acid
It measures more；And compared with comparative example carrier F, carrier A, B, C total acid content of the embodiment of the present invention and B acid amounts increased, but amplitude
It is smaller.
2 catalyst physical property of table
Embodiment 4
The present embodiment is catalyst C-1 stability tests, and is compared with C-4, C-5 stability.It is anti-small in 100mL tri-
It is evaluated on type fixed bed hydrogenation device.Compare for convenience, one anti-two it is counter load identical preposition dose, C-1, C-4, C-5 dress
It is anti-to fill in three.Evaluation feedstock oil is that the Middle East subtracts slag, and property is as shown in table 3.
3 test raw material oil main character of table
Evaluation condition is as shown in table 4.
4 process conditions of table
Opposite denitrification percent, desulfurization degree and de- carbon yield be with 500 hours denitrification percents of C-1 catalyst runs, desulfurization degree and
De- carbon yield, which compares for 1.00 as benchmark, to be obtained.Catalyst activity and stability contrast result are listed in table 5.As can be seen from Table 5,
With the extension of operating, the opposite carbon residue removal efficiency and denitrification percent of catalyst C-1 is obviously higher than C-4, C-5；Opposite carbon residue is de-
Sulphur rate is slightly above C-4, C-5.So showing active and steady by catalyst desulfurizing made from the method for the present invention, denitrogenation and de- carbon residue
Qualitative catalyst C-4, C-5 obtained better than comparative example method, especially de- carbon residue and denitrification activity are with the obvious advantage.
5 catalyst activity of table and stability contrast experiment
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method of catalyst carrier for hydrgenating heavy oil, which is characterized in that the preparation method includes the following steps：
Step 1, book clay and water are mixed with beating uniformly；
Step 2, it is added siliceous boehmite dry glue powder and peptization agent solution in kneading equipment, kneading 10-20 minutes, then
The book clay slurries of step 1 are added, after Aluminum sol, then abundant kneading is added after kneading 10-15min, extruded moulding；And
Step 3,2-10 hours dry at 100-150 DEG C aging 1-5 hours at 50-90 DEG C, then roasted at 500~1100 DEG C
Burn 3~6 hours to obtain catalyst carrier；
Wherein, on the basis of catalyst carrier, the mass content of book clay is 5-30%.
2. the preparation method of catalyst carrier for hydrgenating heavy oil according to claim 1, which is characterized in that the step 2 adds
Extrusion aid is added while entering siliceous boehmite dry glue powder, the extrusion aid is sesbania powder, starch, polyvinyl alcohol and methyl
One or more of formed group of cellulose.
3. the preparation method of catalyst carrier for hydrgenating heavy oil according to claim 1, which is characterized in that the peptizing agent is molten
Liquid is nitric acid, acetic acid, formic acid or hydrochloric acid solution.
4. the preparation method of catalyst carrier for hydrgenating heavy oil according to claim 1, which is characterized in that layered clay
For the natural or artificial synthesized rule natural or artificial synthesized with the smectite class clay of expansile single-storeyed mineral structure
Then interstratified minerals structure clay.
5. the preparation method of catalyst carrier for hydrgenating heavy oil according to claim 1, which is characterized in that layered clay
For montmorillonite, Hectorite, beidellite, rectorite, mica-smectite, glauconite-smectite and chlorite-smectite institute group
At one or more of group.
6. catalyst carrier prepared by the preparation method of catalyst carrier for hydrgenating heavy oil described in any one of claim 1 to 5.
7. catalyst carrier prepared by the preparation method of catalyst carrier for hydrgenating heavy oil according to claim 6, feature
It is, 0.40~0.90mL/g of Kong Rongwei of the catalyst carrier, specific surface area is 150~450m2/g。
8. a kind of preparation method of heavy-oil hydrogenation catalyst, which is characterized in that the preparation method is：
VIB and/or group VIII metal salting liquid are prepared, the method sprayed using saturation is sprayed metal salt solution with spray pattern
Be dipped in catalyst carrier prepared by the preparation method of the catalyst carrier for hydrgenating heavy oil described in claim 6, then 80~
It is 1~8 hour dry at 150 DEG C, at 300~650 DEG C, roasts 2~6 hours, be prepared into heavy-oil hydrogenation catalyst；
Wherein, on the basis of catalyst quality, for the load capacity of metal in terms of oxide, vib metal oxide is 3.0 in catalyst
~20.0% and/or group VIII metal oxide 2.0~8.0%.
9. the preparation method of heavy-oil hydrogenation catalyst according to claim 8, which is characterized in that the VIB and/or VIII
Race's metal salt solution is made of the salting liquid of one or more of group metal molybdenum, tungsten, nickel and cobalt.
10. catalyst prepared by the preparation method of the heavy-oil hydrogenation catalyst described in claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710073142.4A CN108404897B (en) | 2017-02-10 | 2017-02-10 | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710073142.4A CN108404897B (en) | 2017-02-10 | 2017-02-10 | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108404897A true CN108404897A (en) | 2018-08-17 |
| CN108404897B CN108404897B (en) | 2021-03-09 |
Family
ID=63124922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710073142.4A Active CN108404897B (en) | 2017-02-10 | 2017-02-10 | Heavy oil hydrogenation catalyst carrier, preparation method thereof, catalyst using heavy oil hydrogenation catalyst carrier and preparation method of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108404897B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185223A (en) * | 2018-11-15 | 2020-05-22 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN112237908A (en) * | 2020-09-30 | 2021-01-19 | 山东公泉化工股份有限公司 | Catalyst carrier, hydrotreating catalyst, preparation method and application |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1353012A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing laminated clay column catalyst |
| CN1388213A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of petroleum hydrocarbon cracking catalyst |
| CN1727442A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for petroleum hydrocarbon, and preparation method |
| CN1854255A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of cracking catalyst for preventing from heavy metal pollution |
| JP2007181777A (en) * | 2006-01-06 | 2007-07-19 | Petroleum Energy Center | Catalytic cracking catalist and method for cracking hydrocarbon oil catalytically |
| CN102039140A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst as well as preparation method and application thereof |
| CN102527445A (en) * | 2011-12-21 | 2012-07-04 | 陕西煤化工技术工程中心有限公司 | Preparation method of low-abrasion fluidized bed microspherical catalyst |
| WO2013086767A1 (en) * | 2011-12-15 | 2013-06-20 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method therefor |
| CN103289735A (en) * | 2012-03-01 | 2013-09-11 | 中国石油天然气股份有限公司 | Catalyst-combined hydrotreating technique of inferior heavy oil |
| CN103447070A (en) * | 2012-06-01 | 2013-12-18 | 湖北赛因化工有限公司 | FCC (Fluid Cracking Catalyst) catalyst containing silicon binder and preparation method thereof |
| CN103623858A (en) * | 2012-08-21 | 2014-03-12 | 湖北赛因化工有限公司 | Catalytic cracking catalyst and preparation method |
| CN103785396A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for heavy oil |
| CN103920431A (en) * | 2014-04-24 | 2014-07-16 | 上海仙佳化工有限公司 | Microsphere fluidizing reagent for start debugging of fluidized bed reactor and preparation method of microsphere fluidizing reagent |
| KR20140110145A (en) * | 2013-03-04 | 2014-09-17 | 코아텍주식회사 | Complex adsorbent and manufacuring method of complex adsorbent |
| CN104549541A (en) * | 2013-10-25 | 2015-04-29 | 湖南长岭石化科技开发有限公司 | Heavy oil catalytic cracking catalyst carrier and catalyst and preparation method thereof |
| US20150165428A1 (en) * | 2012-06-01 | 2015-06-18 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| CN105772074A (en) * | 2014-12-25 | 2016-07-20 | 中国石油天然气股份有限公司 | Preparation method for heavy oil catalytic cracking catalyst |
| CN105983412A (en) * | 2015-02-03 | 2016-10-05 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with high denitrification performance and preparation method therefor |
| CN106040217A (en) * | 2016-05-25 | 2016-10-26 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking aid containing pseudo-boehmite |
-
2017
- 2017-02-10 CN CN201710073142.4A patent/CN108404897B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1353012A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing laminated clay column catalyst |
| CN1388213A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of petroleum hydrocarbon cracking catalyst |
| CN1727442A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for petroleum hydrocarbon, and preparation method |
| CN1854255A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of cracking catalyst for preventing from heavy metal pollution |
| JP2007181777A (en) * | 2006-01-06 | 2007-07-19 | Petroleum Energy Center | Catalytic cracking catalist and method for cracking hydrocarbon oil catalytically |
| CN102039140A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst as well as preparation method and application thereof |
| WO2013086767A1 (en) * | 2011-12-15 | 2013-06-20 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method therefor |
| CN102527445A (en) * | 2011-12-21 | 2012-07-04 | 陕西煤化工技术工程中心有限公司 | Preparation method of low-abrasion fluidized bed microspherical catalyst |
| CN103289735A (en) * | 2012-03-01 | 2013-09-11 | 中国石油天然气股份有限公司 | Catalyst-combined hydrotreating technique of inferior heavy oil |
| CN103447070A (en) * | 2012-06-01 | 2013-12-18 | 湖北赛因化工有限公司 | FCC (Fluid Cracking Catalyst) catalyst containing silicon binder and preparation method thereof |
| US20150165428A1 (en) * | 2012-06-01 | 2015-06-18 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| CN103623858A (en) * | 2012-08-21 | 2014-03-12 | 湖北赛因化工有限公司 | Catalytic cracking catalyst and preparation method |
| CN103785396A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for heavy oil |
| KR20140110145A (en) * | 2013-03-04 | 2014-09-17 | 코아텍주식회사 | Complex adsorbent and manufacuring method of complex adsorbent |
| CN104549541A (en) * | 2013-10-25 | 2015-04-29 | 湖南长岭石化科技开发有限公司 | Heavy oil catalytic cracking catalyst carrier and catalyst and preparation method thereof |
| CN103920431A (en) * | 2014-04-24 | 2014-07-16 | 上海仙佳化工有限公司 | Microsphere fluidizing reagent for start debugging of fluidized bed reactor and preparation method of microsphere fluidizing reagent |
| CN105772074A (en) * | 2014-12-25 | 2016-07-20 | 中国石油天然气股份有限公司 | Preparation method for heavy oil catalytic cracking catalyst |
| CN105983412A (en) * | 2015-02-03 | 2016-10-05 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with high denitrification performance and preparation method therefor |
| CN106040217A (en) * | 2016-05-25 | 2016-10-26 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking aid containing pseudo-boehmite |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185223A (en) * | 2018-11-15 | 2020-05-22 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN111185223B (en) * | 2018-11-15 | 2023-02-24 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN112237908A (en) * | 2020-09-30 | 2021-01-19 | 山东公泉化工股份有限公司 | Catalyst carrier, hydrotreating catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108404897B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101927176B (en) | Hydrogenation catalyst showing gradient increase distribution of concentration of active metal and acid additive and preparation method thereof | |
| CN101928593B (en) | Graded composition of heavy oil hydrogenation catalysts | |
| CN101927196B (en) | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof | |
| CN104114273B (en) | Silica containing alumina support, catalyst prepared therefrom and its application method | |
| CN101927197B (en) | Hydrogenation catalyst with gradient descending distribution of active metal and acidic assistant concentration and preparation method thereof | |
| CN104549328B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN1854260A (en) | Heavy fractional oil hydrogenation catalyst and production thereof | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| CN108187709B (en) | Preparation method of deep hydrodesulfurization catalyst and application of catalyst | |
| CN102343270A (en) | Hydrogenation catalyst with active metal ingredient in layering distribution and preparation method thereof | |
| CN102641739B (en) | Hydrogenation catalyst of a kind of alkalinous metal and the equal distribution gradient of active metal component concentration and preparation method thereof | |
| CN105289683B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN109304183B (en) | Hydrotreating catalyst for treating inferior oil and its prepn and application | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN102049289A (en) | Superdeep hydrodesulfurization catalyst and preparation method thereof | |
| CN108404897A (en) | A kind of catalyst carrier for hydrgenating heavy oil, preparation method, using its catalyst and catalyst preparation method | |
| CN109772387B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN102049264A (en) | Hydrodesulphurization catalyst and preparation method thereof | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN105233848A (en) | Ni, W and P loaded hydrofining catalyst with three-peak type pore size distribution for anthracene oil, and preparation method and application | |
| CN105983412B (en) | The hydrogenation catalyst and preparation method thereof of high nitrogen removal performance | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| JP3545943B2 (en) | Hydrorefining catalyst | |
| CN1211157C (en) | Hydrocracking after-treatment catalyst and preparing method thereof | |
| CN112717965B (en) | Hydrogenation pretreatment catalyst, and preparation method and application thereof |
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 |