CN110064403A - A kind of preparation method of the hydrotreating catalyst with denitrification activity - Google Patents
A kind of preparation method of the hydrotreating catalyst with denitrification activity Download PDFInfo
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- CN110064403A CN110064403A CN201810063949.4A CN201810063949A CN110064403A CN 110064403 A CN110064403 A CN 110064403A CN 201810063949 A CN201810063949 A CN 201810063949A CN 110064403 A CN110064403 A CN 110064403A
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- 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
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of preparation methods of hydrotreating catalyst with denitrification activity, comprising the following steps: step 1, prepares a kind of porous carrier based on aluminium oxide or phosphorus-containing alumina material；Step 2, the porous carrier is impregnated with I metalloid solution, curing, drying roasting obtain catalyst precarsor, and the I metalloid solution is the NiMoP solution containing Ni, Mo and P element or is the CoMoP solution containing Co, Mo and P element；Step 3, catalyst precarsor is impregnated into the II metalloid solution containing organic additive, is then cured, dried, without roasting process, obtains final catalyst；The II metalloid solution is the NiMoP solution containing Ni, Mo and P element or is the CoMoP solution containing Co, Mo and P element, and I metalloid solution and II metalloid solution are not NiMoP solution or CoMoP solution simultaneously.The catalyst of the method for the present invention preparation has high denitrification activity.
Description
Technical field
The present invention relates to a kind of preparation method of high-activity hydrogenation catalyst more particularly to a kind of NiCoMo high activity denitrogenations
Catalyst and the preparation method and application thereof.
Background technique
The presence of sulphur, nitrogen and metal impurities not only will affect the oxidation stability of product oil, but also meeting in distillate
Discharge SO2、NO2Equal pernicious gases.Removing the impurity in distillate by hydroprocessing processes is very important measure.Fraction
Oily hydroprocessing objectives are exactly by organic sulfur conversion in raw material into hydrogen sulfide, and organic nitrogen is converted to ammonia.Distillate hydrogenation processing
It is under certain temperature and pressure condition, distillate and hydrogen are contacted with catalyst, the process of imurity-removal and aromatic hydrocarbons saturation.Cause
This, is manufactured the preparation method of hydrotreating catalyst and is important with the catalyst for obtaining high activity.
Now, two-stage method, i.e. first segment hydrodesulfurization is usually used in the method for diesel oil distillate desulfurization, denitrogenation and Porous deproteinized bone
And denitrogenation, second segment are hydrogenation aromatics-removings.Conventional hydrodesulfurization and denitrification catalyst is usually by carrier and to load on it
The group VIB and/or group VIII active metal component in face form, the most commonly used is vib metals molybdenum and tungsten, the
Group VIII metal nickel and cobalt, also often containing auxiliary agents such as phosphorus, boron in catalyst.The preparation method of the catalyst is usually by active group
Divide and be supported on carrier, such as infusion process, then is allowed to be changed into oxidation state by dry and high-temperature roasting.For adding at hydrogen
Before reason, catalyst will pass through presulfurization, be allowed to be changed into sulphided state.The a large amount of energy is not only wasted in this way, causes to be catalyzed
Agent cost improves, and due to pass through high-temperature roasting after supported active metals, it is low even without activity to form some activity
Non-ideal phase, reduce catalyst performance.
It is impregnated on porous carrier, produces more high living it is reported that organic compound is added in metal impregnation liquid
Property II class activity phase, while catalyst loss of activity caused by accumulation of metal during high temperature vulcanized can be prevented, to mention
The activity of high hydrotreating catalyst.Many patents disclose the use of a variety of organic compounds, as oxygen-containing organic compound is more
First alcohol or its etherate (WO96/41848, US3954673, US4012340).
Patent JP 04166231 discloses the preparation method of hydrotreating catalyst, and porous carrier and metallic solution are soaked
It is dry under conditions of being not higher than 200 DEG C after stain, after the carrier after drying is contacted with polyol, then undergo primary drying
The step of catalyst is made.
EP 0601722 discloses a kind of preparation method of catalyst, it is characterised in that porous alumina carrier is with containing two
The aqueous metal solution of first alcohol impregnates, and the carrier after dipping passes through primary drying step, but prepares finished product without roasting process and urge
Agent.
US 6218333 discloses the catalyst that porous carrier is had in conjunction with active metal component with formation to volatile matter
The method that precursor prepares hydrotreating catalyst.With sulfur-containing compound handle catalyst precarsor, in dry conditions volatile matter from
It is released in the catalyst precarsor.However, these are improved can not meet the increasingly strict demanded fuel in refinery enough.
The hydrotreating catalyst of high activity can make hydroprocessing technique condition mitigate such as reaction temperature low, or in phase
Quality more preferably product is obtained under conditions of.Therefore, the hydrotreating catalyst for how developing a kind of high activity becomes this
The target that field technical staff constantly pursues.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of hydrotreating catalyst with denitrification activity.
To achieve the above object, the present invention provides a kind of preparation method of hydrotreating catalyst with denitrification activity,
The following steps are included:
Step 1, a kind of porous carrier based on aluminium oxide or phosphorus-containing alumina material is prepared；
Step 2, the porous carrier is impregnated with I metalloid solution, curing, drying roasting obtain catalyst precarsor, described
I metalloid solution is the NiMoP solution containing Ni, Mo and P element or is the CoMoP solution containing Co, Mo and P element；
Step 3, catalyst precarsor is impregnated into the II metalloid solution containing organic additive, is then cured, dried, no
By roasting process, final catalyst is obtained；The II metalloid solution is the NiMoP solution containing Ni, Mo and P element or is
CoMoP solution containing Co, Mo and P element, I metalloid solution and II metalloid solution are not NiMoP solution or CoMoP simultaneously
Solution.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, there is machine aided described in step 2
Agent includes alcohols and/or organic acid.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, there is machine aided described in step 3
Agent dosage are as follows: on the basis of II metalloid solution, every active metal contains 0.01~3 mole of organic additive.
After II type catalyst introduces organic additive, the metal particle size of generation is small, therefore activity is high.But if simple use
II type catalyst, acts on weak between metal and carrier, the stability of catalyst cannot be guaranteed, cause denitrification activity bad.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, dry in step 3 is ability
The common drying means in domain, such as vacuum drying or constant pressure and dry, and without particular determination, it can be repeatedly dry for primary or substep
It is dry.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, drying temperature is low in step 3
In 260 DEG C.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, drying temperature is in step 3
100~260 DEG C
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, the alcohols organic additive are
Polyethylene glycol.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, the organic acid have machine aided
Agent is citric acid.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, I class active sites in catalyst
The proportional region with II class active site is put in 0.1~0.5.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity dries temperature described in step 2
Degree is 100~300 DEG C, and maturing temperature is 400~550 DEG C.
The beneficial effects of the present invention are:
Provide a kind of hydrotreating catalyst with dissimilar metals combination, different type activity bit combination, tool
There is high denitrification activity.
Detailed description of the invention
Fig. 1 is the production technological process of catalyst in the embodiment of the present invention 1；
Fig. 2 is the production technological process of catalyst in the embodiment of the present invention 2.
Specific embodiment
Technical solution of the present invention is described in detail below in conjunction with specific embodiment, to be easier to understand the present invention
Purpose, technology contents, and cited embodiment only make illustrate be used, be not intended as limitation of the invention.
A kind of preparation method of the hydrotreating catalyst with denitrification activity, comprising the following steps:
Step 1, a kind of porous carrier based on aluminium oxide or phosphorus-containing alumina material is prepared；
Step 2, the porous carrier is impregnated with I metalloid solution, curing, drying roasting obtain catalyst precarsor, described
I metalloid solution is the NiMoP solution containing Ni, Mo and P element or is the CoMoP solution containing Co, Mo and P element；
Step 3, catalyst precarsor is impregnated into the II metalloid solution containing organic additive, is then cured, dried, no
By roasting process, final catalyst is obtained；The II metalloid solution is the NiMoP solution containing Ni, Mo and P element or is
CoMoP solution containing Co, Mo and P element, I metalloid solution and II metalloid solution are not NiMoP solution or CoMoP simultaneously
Solution.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, there is machine aided described in step 2
Agent includes alcohols and/or organic acid.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, there is machine aided described in step 3
Agent dosage are as follows: on the basis of II metalloid solution, every active metal contains 0.01~3 mole of organic additive.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, dry in step 3 is ability
The common drying means in domain, such as vacuum drying or constant pressure and dry, and without particular determination, it can be repeatedly dry for primary or substep
It is dry.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, drying temperature is low in step 3
In 260 DEG C.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, drying temperature is in step 3
100~260 DEG C
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, the alcohols organic additive are
Polyethylene glycol.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, the organic acid have machine aided
Agent is citric acid.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity, I class active sites in catalyst
The proportional region with II class active site is put in 0.1~0.5.
The preparation method of hydrotreating catalyst of the present invention with denitrification activity dries temperature described in step 2
Degree is 100~300 DEG C, and maturing temperature is 400~550 DEG C.
Embodiment 1 prepares I/II type Ni/CoMo catalyst C1 (according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier；
It step 2, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP solution is added in the above-mentioned carrier of 70g, enables extrudate cure 6 at room temperature after dipping small
When, 120 DEG C are dried overnight, and 450 DEG C roast 3 hours, obtain I type catalyst precarsor；
It step 3, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.Before CoMoP-CA (citric acid) (citric acid/Mo=0.1, molar ratio) mixed solution is impregnated above-mentioned catalyst
After body, at room temperature cure 6 hours, 100 DEG C drying 6 hours, acquisition I/II type Ni/CoMo catalyst C1.
Embodiment 2 prepares I/II type Co/NiMo catalyst C2 (according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier；
It step 2, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.CoMoP mixed solution is added in the above-mentioned carrier of 70g, enables extrudate cure 6 at room temperature after dipping
Hour, 100 DEG C of dryings, 450 DEG C roast 3 hours, obtain I type catalyst precarsor.
It step 3, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP-CA (citric acid) (citric acid/Mo=0.1, molar ratio) mixed solution is impregnated into above-mentioned catalyst
After precursor, at room temperature cure 6 hours, 260 DEG C drying 6 hours, acquisition I/II type Co/NiMo catalyst C2.
Embodiment 3 prepares I/II type Ni/CoMo catalyst C3 (according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier；
It step 2, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP solution is added in the above-mentioned carrier of 70g, enables extrudate cure 6 at room temperature after dipping small
When, 200 DEG C are dried overnight, and 450 DEG C roast 3 hours, obtain I type catalyst precarsor；
It step 3, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.CoMoP-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo=0.01, molar ratio) is mixed molten
After liquid impregnates above-mentioned catalyst precarsor, cure 6 hours at room temperature, 200 DEG C drying 6 hours, acquisition I/II type Ni/CoMo catalyst
C3。
Embodiment 4 prepares I/II type Co/NiMo catalyst C4 (according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier；
It step 2, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.CoMoP mixed solution is added in the above-mentioned carrier of 70g, enables extrudate cure 6 at room temperature after dipping
Hour, 120 DEG C of dryings, 400~550 DEG C roast 4 hours, obtain catalyst precarsor.
It step 3, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP-CA-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo=0.01, molar ratio) is mixed
Close after solution impregnates above-mentioned catalyst precarsor, cure 6 hours at room temperature, 100~260 DEG C drying 6 hours, acquisition I/II type Co/
NiMo catalyst C4.
Embodiment 5 prepares I/II type Co/NiMo catalyst C5 (according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier；
It step 2, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.CoMoP mixed solution is added in the above-mentioned carrier of 70g, enables extrudate cure 6 at room temperature after dipping
Hour, 120 DEG C of dryings, 400~550 DEG C roast 4 hours, obtain catalyst precarsor.
It step 3, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP-CA-PEG (polyethylene glycol, molecular weight 600, polyethylene glycol/Mo=0.01, molar ratio) is mixed
Close after solution impregnates above-mentioned catalyst precarsor, cure 6 hours at room temperature, 100~260 DEG C drying 6 hours, acquisition I/II type Co/
NiMo catalyst C5.
Comparative example 1: preparation I type NiCoMo catalyst C1 (not according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier.
It step 2, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP solution is added in the above-mentioned carrier of 70g, extrudate is enabled to cure at room temperature after dipping 6 hours,
120 DEG C are dried overnight.
It step 3, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.After CoMoP solution is impregnated above-mentioned catalyst precarsor, cure 6 hours at room temperature, 120 DEG C are dried overnight, and 450
DEG C roasting 3 hours, obtain the catalyst DC1 of roasting.
Comparative example 2: preparation II type NiCoMo catalyst DC2 (not according to the present invention)
Step 1, using boehmite extrusion, drying, roasting, the A1 of clover shape is made2O3Carrier.
It step 2, is heat of solution molybdenum trioxide (24g), basic nickel carbonate (5g) in 85% hot phosphoric acid solution (8g) in concentration,
Prepare NiMoP solution.NiMoP-CA (citric acid) mixed solution is added in the above-mentioned carrier of 70g, enables extrudate exist after dipping
It cures 6 hours at room temperature, 120 DEG C of dryings.
It step 3, is heat of solution molybdenum trioxide (24g), cobalt hydroxide (6g) in 85% hot phosphoric acid solution (8g), system in concentration
Standby CoMoP solution.Before CoMoP-CA (citric acid, citric acid/Mo=0.1, molar ratio) mixed solution is impregnated above-mentioned catalyst
After body, at room temperature cure 6 hours, 100~260 DEG C drying 6 hours, acquisition II type catalyst DC2.
It evaluates used catalyst and is vulcanized 8 hours respectively with the aviation kerosine fraction containing carbon disulfide at 260 DEG C and 370 DEG C,
Stablize at reaction conditions after into feedstock oil and starts within 8 hours to carry out hydrodenitrogeneration reaction test.When evaluating catalyst, pass through adjusting
Reaction temperature makes denitrification percent 95w%, i.e., it is 0.007w% that control, which generates nitrogen content in oil, and the reaction temperature of catalyst is low just
This denitrification percent can be reached, show catalyst hydrodenitrogenationactivity activity with higher.It can be seen that 4 catalyst C4 of embodiment adds
Hydrogen denitrification activity highest.
Table 1: raw material oil nature
| Feedstock oil | VGO |
| Density, g/ml | 0.9 |
| Sulphur, w% | 0.51 |
| Nitrogen, w% | 0.15 |
| Carbon residue, w% | 0.05 |
| Boiling range, DEG C | |
| IBP/10% | 290/345 |
| 30%/50% | 360/390 |
| 70%/90% | 400/435 |
| 95%/EBP | 445/460 |
Table 2: hydrodenitrogeneration reaction process condition
| Reaction pressure, MPa | 7.0 |
| LHSV,h-1 | 1.0 |
| H2/ oil ratio, V/V | 1000 |
Table 3: catalyst hydrogenation denitrification activity compares
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 preparation method of the hydrotreating catalyst with denitrification activity, which comprises the following steps:
Step 1, a kind of porous carrier based on aluminium oxide or phosphorus-containing alumina material is prepared；
Step 2, the porous carrier is impregnated with I metalloid solution, curing, drying roasting obtain catalyst precarsor, the I class
Metallic solution is the NiMoP solution containing Ni, Mo and P element or is the CoMoP solution containing Co, Mo and P element；
Step 3, catalyst precarsor is impregnated into the II metalloid solution containing organic additive, is then cured, is dried, without
Roasting process obtains final catalyst；The II metalloid solution be the NiMoP solution containing Ni, Mo and P element or for containing
The CoMoP solution of Co, Mo and P element, I metalloid solution and II metalloid solution is not molten for NiMoP solution or CoMoP simultaneously
Liquid.
2. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that step
Organic additive described in rapid 2 includes alcohols and/or organic acid.
3. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that step
Organic additive dosage described in rapid 3 are as follows: on the basis of II metalloid solution, every active metal is organic containing 0.01~3 mole
Auxiliary agent.
4. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that step
Dry in rapid 3 is primary or repeatedly dry step by step.
5. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that step
Drying temperature is lower than 260 DEG C in rapid 3.
6. the preparation method of the hydrotreating catalyst according to claim 5 with denitrification activity, which is characterized in that step
Drying temperature is 100~260 DEG C in rapid 3.
7. the preparation method of the hydrotreating catalyst according to claim 2 with denitrification activity, which is characterized in that institute
Stating alcohols organic additive is polyethylene glycol.
8. the preparation method of the hydrotreating catalyst according to claim 2 with denitrification activity, which is characterized in that institute
Stating organic acid organic additive is citric acid.
9. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that urge
The proportional region of I class active site and II class active site is in 0.1~0.5 in agent.
10. the preparation method of the hydrotreating catalyst according to claim 1 with denitrification activity, which is characterized in that
Drying temperature described in step 2 is 100~300 DEG C, and maturing temperature is 400~550 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430003A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Hydrotreating method for lubricating oil base oil |
| CN113430004A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Inferior catalytic diesel oil hydrotreating method |
| CN113430002A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Inferior wax oil hydrotreating method |
| WO2021218982A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor and use thereof |
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| CN113430003A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Hydrotreating method for lubricating oil base oil |
| CN113430004A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Inferior catalytic diesel oil hydrotreating method |
| CN113430002A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Inferior wax oil hydrotreating method |
| CN113430004B (en) * | 2020-03-23 | 2023-02-28 | 中国石油天然气股份有限公司 | Inferior catalytic diesel oil hydrotreating method |
| CN113430003B (en) * | 2020-03-23 | 2023-02-28 | 中国石油天然气股份有限公司 | Hydrotreating method for base oil of lubricating oil |
| WO2021218982A1 (en) * | 2020-04-28 | 2021-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method therefor and use thereof |
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