CN107486249A - A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method - Google Patents
A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method Download PDFInfo
- Publication number
- CN107486249A CN107486249A CN201610407231.3A CN201610407231A CN107486249A CN 107486249 A CN107486249 A CN 107486249A CN 201610407231 A CN201610407231 A CN 201610407231A CN 107486249 A CN107486249 A CN 107486249A
- Authority
- CN
- China
- Prior art keywords
- acid
- solution
- preparation
- catalyst
- organic
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of preparation method of hydrogenation catalyst and its catalyst obtained by this method, the preparation method include dipping solution is contacted with carrier, then through drying, be calcined or be not calcined, obtain the hydrogenation catalyst, characterized in that, the preparation method of the dipping solution comprises the following steps：(1) the first solution of the compound containing at least one metal containing group VIII and at least one compound containing the first vib metal is prepared；(2) the first solution is subjected to atmospheric activating processing, treatment temperature is 65~100 DEG C, and the time is 0.5 36 hours；(3) after the first solution temperature after processing to be activated is down to room temperature~50 DEG C, at least one compound for containing second of vib metals is introduced thereto, obtains the dipping solution.Compared with prior art, hydrogenation catalyst provided by the invention, hydrofinishing or hydrotreating performance significantly improve.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst and the hydrogenation catalyst obtained by this method.
Background technology
Hydrogenation catalyst is a kind of very important catalyst in petroleum refining field, is widely used in petroleum refining field
Various hydrogenation processes, for producing clean fuel, improving oil refining process feed properties and improving oil product yield and quality.Hydrogenation
Catalyst has hydrogenating function, and its Hydrogenation is influenceed by many factors such as active metal, carrier and preparation methods.Hydrogenation
Active metal in catalyst is generally loaded using the group vib in the periodic table of elements and group VIII metal, these active metals more
In on the carrier with loose structure.Common method active metal being carried in catalyst carrier is dipping method, that is, is used
Dipping solution containing active metal component is contacted with carrier, active metal component is entered carrier surface or duct
In, so as to realize the purpose of supported active metals.In this course.The preparation of dipping solution is a considerable ring
Section, different preparation methods may cause the existing forms of metal component in resulting dipping solution, dipping solution materialization
The difference of matter, and and then have influence on using dipping method prepare hydrogenation catalyst performance.Therefore, dipping solution preparation method
Improvement and optimization, it is possible to as improve hydrogenation catalyst performance an important channel, in recent years by increasing
Pay attention to.
CN 96109702 discloses a kind of co-impregnated solution for being used to prepare hydrocracking catalyst, consisting of：25-65g
WO3/ 100ml solution, 3-20g NiO/100ml solution, wherein also at least containing a kind of organic acid or ammonium salt, content 0.5-
15g/100ml solution.The maceration extract by the way that ammonium metatungstate and nickel nitrate are dissolved in deionized water, afterwards add organic acid or
Obtained after ammonium salt dissolving.
CN 201010211884 discloses a kind of dipping solution of hydrogenation catalyst and preparation method thereof, the dipping solution
Contain water miscible group vib metal, the acylate of water miscible group VIII metal and water-soluble organic additive.Carry simultaneously
Contacted for a kind of using the maceration extract with catalyst carrier so as to prepare the preparation method of hydrogenation catalyst.For dipping solution
Preparation method there is no particular limitation, as long as each component of the dipping solution of the hydrogenation catalyst is well mixed i.e.
Can.
CN 201110317245 provides a kind of maceration extract of hydrogenation catalyst and preparation method thereof, and this method includes, will
Group VIII metallic compound and the first organic complexing agent are configured to water solution A；Vib metals compound is configured to water-soluble
Liquid B；The water solution A and aqueous solution B are mixed；Wherein, at least containing coordination in the ligand of first organic complexing agent
Atom N.
CN 00110464 is related to a kind of preparation method of hydrorefining catalyst for hydrocarbon, and the catalyst uses one kind simultaneously
Containing group VIB, metal component of group VIII, organic carboxyl acid and polyalcohol mixing complexing agent and the dipping solution of auxiliary agent B through dipping,
Dry and be prepared by roasting.The compound method of wherein maceration extract is：By soluble VI B metallic compounds, organic carboxyl acid complexing agent,
Boron-containing compound is put into same beaker, is added deionized water, is dissolved by heating under agitation, and phosphoric acid and solubility are added after dissolving
Group VIII metallic compound, it is configured to total immersion solution.
CN 200510064751 provides a kind of hydrogenation catalyst and preparation method thereof.The catalyst contains Ni, Mo, W
Active metal component and alumina support.Do not limited for metal introducing method, preferable method includes individually or simultaneously using
The method of solution impregnation of alumina carrier containing Mo, Ni and W compound introduces, be dried after the completion of dipping, be calcined or
It is not calcined.For the preparation method of dipping solution, do not illustrate and limit.
Document (" W-Incorporated CoMo/ γ-Al2O3Hydrodesulfurization Catalyst ",
Journal of catalysis 1996, vol.159, p.212-218) report a kind of CoMoW/Al2O3The preparation of catalyst
Method, including W and CoMo are carried on alumina support using dipping method substep, W and CoMo impregnation sequence can change
Become, be dried and be calcined after dipping.
The content of the invention
The present invention provides a kind of preparation method of hydrogenation catalyst and catalyst obtained by this method.Methods described includes
Dipping solution is contacted with carrier, then through drying, roasting or be not calcined, obtain the hydrogenation catalyst, its feature exists
In the preparation method of the dipping solution comprises the following steps：(1) chemical combination containing at least one metal containing group VIII is prepared
First solution of thing and at least one compound containing the first vib metal；(2) the first solution is carried out at atmospheric activating
Reason, treatment temperature are 65~100 DEG C, hour time 0.5-36；(3) the first solution after activation process is cooled to room temperature~50
DEG C, afterwards, at least one compound for containing second of vib metals is introduced thereto, obtain the dipping solution.
Compared with prior art, hydrogenation catalyst provided by the invention, hydrofinishing or hydrotreating performance significantly improve.
For example, when urging straight bavin the progress hydrofinishing of bavin miscella, catalyst provided by the invention and comparative catalyst are contrasted
Evaluation, using the activity of comparative catalyst as 100%, the relative hydrodesulfurization activity of present invention offer catalyst is up to 130%, phase
To hydrodenitrogenationactivity activity up to 115%.
Embodiment
The present invention provides a kind of preparation method of hydrogenation catalyst, and methods described includes being connect dipping solution and carrier
Touch, then through drying, roasting or be not calcined, obtain the hydrogenation catalyst, it is characterised in that the preparation side of the dipping solution
Method comprises the following steps：(1) prepare the compound containing at least one metal containing group VIII and it is at least one containing the first the
First solution of the compound of vib metal；(2) the first solution being subjected to atmospheric activating processing, treatment temperature is 65~100 DEG C,
Hour time 0.5-36；(3) the first solution after activation process is cooled to room temperature~50 DEG C, afterwards, introduced thereto at least
A kind of compound for containing second of vib metals, obtain the dipping solution.
According to the method described in the present invention, the carrier is selected from the various carriers for being suitable for preparing hydrogenation class catalyst.
The carrier can be in shaping or unformed heat-resistant inorganic oxide, inorganic silicate and molecular sieve and its mixture.
The present invention without particular/special requirement, is referred to prior art progress to the species of the heat-resistant inorganic oxide, such as
Can be aluminum oxide, silica, titanium oxide, magnesia, silica-alumina, alumina-silica magnesium, silica-magnesias,
Silica-zirconia, silica thoria, silica-berylias, silica-titania, titania-zirconia, silica-
Alumina-thorias, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia,
One or more in natural zeolite, clay, wherein, preferably aluminum oxide and/or silica.
The present invention, without particular/special requirement, can be one kind in zeolite or non-zeolitic molecular sieves to the species of the molecular sieve
It is or a variety of.The zeolite molecular sieve can be erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolites,
ZSM-22 zeolites, ZSM-23 zeolites, ZSM-35 zeolites, L zeolite, y-type zeolite, X-type zeolite, ZSM-3 molecular sieves, ZSM-4 molecules
Sieve, ZSM-18 molecular sieves, ZSM-20 molecular sieves, ZSM-48 zeolites, ZSM-57 zeolites, faujasite, Beta zeolites and omega zeolite
In one or more.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, HTS and SAPO (such as SAPO)
One or more in molecular sieve.According to the present invention, the molecular sieve is preferably hydrogen type molecular sieve, and the hydrogen type molecular sieve can be with
It is commercially available, conventional method can also be used to prepare.For example, the conventional ammonium ion exchange process of sodium form molecular sieve can be entered
Row ion exchange and drying, form ammonium type molecular sieve, then fired formation hydrogen type molecular sieve.
According to the preparation method of the hydrogenation catalyst of the present invention, clay can also be contained in the catalyst carrier, it is described
The species of clay can root need to be selected, preferably kaolin, halloysite, montmorillonite, diatomite, galapectite, soap
One or more in stone, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
According to the preparation method of the hydrogenation catalyst of the present invention, it can also contain modified additive, institute in the catalyst carrier
Modified additive compound is stated to be preferably siliceous compound, fluorine-containing compound, the compound of titaniferous, phosphorous compound and contain
One or more in the compound of boron.The method for introducing auxiliary agent is referred to prior art progress, such as can be closed in carrier
Into or forming process in introduce, also catalyst carrier can be introduced by the method that impregnates or mix.Those skilled in the art are to this
It can know, will not be repeated here.
According to the preparation method of the hydrogenation catalyst of the present invention, the catalyst carrier can be powder, cloverleaf pattern, butterfly
It is shape, cylinder, hollow cylindrical, quatrefoil, asymmetric quatrefoil, five leaf or spherical.
According to the preparation method of the hydrogenation catalyst of the present invention, optional wider range of the condition of the contact, for this
Invention, the condition preferably contacted include：The temperature of contact be room temperature to 80 DEG C, be preferably room temperature to 60 DEG C；Time is 0.1-24
Hour, preferably 0.5-10h.The method of the contact can be the known spraying of art technology, impregnate, adsorption method, excellent
Elect dipping and absorption as.Using infusion process in the embodiment of the present invention.
The present invention can be the various impregnation methods of prior art without particular/special requirement to the mode of the dipping, such as can
Think spray dipping, saturation dipping or excessive liquid dipping.
According to the preparation method of the hydrogenation catalyst of the present invention, under preferable case, method of the invention also include filtering or
Do not filter (can be without filtering when general saturation dipping, those skilled in the art equal can know to this), Ran Houjin
The step of row is dried or dried and is calcined.
The present invention, without particular/special requirement, is referred to prior art progress to the drying, the condition being calcined.It is for example, described
Dry temperature is generally 60-250 DEG C, preferably 90-180 DEG C, and the time is 1-24 hours, preferably 2-12 hours；Roasting
Temperature is generally 300-700 DEG C, preferably 300-550 DEG C, and the time is 0.5-12 hours, preferably 1-8 hours.
In order to realize the present invention, it is necessary to dipping solution of the present invention be prepared, below to the specific preparation side of dipping solution
Method is described in detail.
According to the preparation method of the dipping solution of hydrogenation catalyst provided by the invention, the group VIII metal is selected from it
In base metal, such as can be the one or more in nickel, cobalt and iron, preferably one or both of nickel, cobalt.
According to dipping solution preparation method provided by the invention, the vib metals can be chromium, molybdenum, tungsten, preferably
A kind of vib metals are molybdenum, and second of vib metals is tungsten.
The group VIII metal and vib component can be introduced molten by the form of the compound containing respective metal
Liquid.Wherein, the group VIII metallic compound be selected from its nitrate, carbonate, subcarbonate, phosphate, phosphite,
One or more in hypophosphites, organic carboxylate.The compound containing vib metals is selected from its oxide, inorganic
One or more in acid, inorganic acid salt.When vib metals are molybdenum, the compound containing molybdenum is selected from molybdenum trioxide, molybdenum
One or more in acid, para-molybdic acid, phosphomolybdic acid, phosphomolybdate, molybdate, paramolybdate, two molybdates, four molybdates.
In salt containing molybdenum, further preferred ammonium salt containing molybdenum；When vib metals are tungsten, the compound of the tungstenic is water-soluble tungsten
Compound, preferably wolframic acid, metatungstic acid, ethyl metatungstic acid, phosphotungstic acid, silico-tungstic acid, tungstates, phosphotungstate, silicotungstate, ethyl are inclined
At least one of tungstates, metatungstate, in tungsten salt, the ammonium salt of further preferred tungstenic.
According to dipping solution preparation method provided by the invention, at least one inorganic assistant, institute can be contained in the solution
State inorganic assistant and be selected from inorganic acid or the mixture of inorganic acid and inorganic acid salt, the inorganic acid can be nitric acid, hydrochloric acid, phosphorus
At least one of acid, hypophosphorous acid, phosphorous acid, boric acid, it is preferable that the inorganic acid is phosphoric acid, hypophosphorous acid, phosphorous acid and boric acid
At least one of.Preferably, the inorganic acid salt is the ammonium salt of aforementioned inorganic acid, it is highly preferred that the inorganic acid salt is selected from
In ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphite, hypophosphorous acid ammonium dihydrogen, ammonium borate, ammonium metaborate, tetraboric acid ammonium
At least one.When containing inorganic acid and inorganic acid salt simultaneously in solution, the mol ratio of preferably inorganic acid and inorganic acid salt is big
In 1.In the preferred case, the mol ratio of the inorganic assistant and the compound containing the first vib metals for 0.05~
3.0, more preferably 0.1~2.5.
According to dipping solution preparation method provided by the invention, contain at least one organic additive in the dipping solution.
The part purpose for adding the organic additive is hydrotropy and stablizing solution.Preferably, the first kind organic additive is selected from and had
Machine acid, the mixture of organic acid and ammonium salt organic acid, one kind of nonacid oxygen-bearing organic matter containing C-O keys and/or C=O keys
Or it is several, it is furthermore preferred that the organic additive is the mixture of organic acid and Organic Alcohol.
The organic acid includes ammonia carboxylic acid, alkyl carboxylic acid, containing aldehydic acid, hydroxyl carboxylic acid.It is more specifically, described organic
Acid is 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, aminotriacetic acid, ethylenediamine tetra-acetic acid, citric acid, oxalic acid, acetic acid, formic acid, second
One or more in aldehydic acid, hydroxyacetic acid, maleic acid, tartaric acid, salicylic acid and malic acid etc..The ammonium salt organic acid includes
One or more in the ammonium salt of above-mentioned organic acid.The nonacid oxygen-bearing organic matter containing C-O keys and/or C=O keys is selected from
Water miscible organic alcohols, material of organic ethers, organic ketone, organosilane ester and its mixture.It is highly preferred that second class is organic
Auxiliary agent is selected from water miscible organic alcohols.It is particularly preferred that this kind of organic additive is selected from C1-C8 Organic Alcohol and/or divided equally again
Son amount is 120-4000 polyethylene glycol, is selected from methanol, ethanol, ethylene glycol, diethylene glycol (DEG), Diethylene Glycol, propyl alcohol, different
It is propyl alcohol, glycerine, butanol, butanediol, amylalcohol, pentanediol, hexanol, hexylene glycol, octanol, methyl cyclohexanol, cyclohexanediol, two sweet
Alcohol, sorbierite and weight average molecular weight are the one or more in 200-1000 polyethylene glycol.
In the preferred case, the dosage of the organic additive causes organic additive and group VIII metallic compound in solution
Mol ratio be 0.05~5, it is highly preferred that the mol ratio of the organic additive and group VIII metallic compound is 0.1~4.
According to dipping solution preparation method provided by the invention, the dipping solution is preferably the aqueous solution.The solution
Compound method is noted by those skilled in the art, to this without specifically describing.
According to dipping solution preparation method provided by the invention, including a step that activation process is carried out to the first solution
Suddenly.The activation process is carried out at ambient pressure, treatment temperature be 65~100 DEG C, preferably 70~95 DEG C, processing time 0.5-
36 hours, preferably 1-24 hours.In activated process, because solvent may volatilize, such as supplementing solvent can be passed through
Or backflow cooling method make liquor capacity before the reaction after volume be held essentially constant.Affiliated solution system is open system
Or Semi-open system, the open system mean that solution system is completely exposed to atmospheric environment, the Semi-open system, mean Sheng
Putting the container of solution system has small opening to be connected with atmospheric environment.
The present inventor speculates that described reaction can promote the further reaction in the first solution between each component,
So as to the existing forms and combination of each component in solution is changed.
According to dipping solution preparation method provided by the invention, in addition to introduce and contain into the first solution after activation process
The step of compound of second vib metals.Can be by water miscible second of vib metals compound and optional
The second class organic additive be directly added into the first solution after activation process and dissolved or will contained second
The aqueous solution of group vib metal is mixed with the first solution after activation process, so as to obtain final dipping solution.
According to dipping solution preparation method provided by the invention, introduce the compound containing second of vib metals it
It is preceding, it is necessary to cool to the first solution after activation process, it is room temperature~50 DEG C to make the solution temperature, it is preferable that makes institute
It is room temperature~45 DEG C to state solution temperature.Heretofore described room temperature refers to the environment temperature in place where preparing dipping solution,
Under the room temperature condition, dipping liquid energy exists with solution state.After previous reaction terminates, can by natural cooling or
The mode of forced cooling realizes above-mentioned purpose.The reason for being controlled to the temperature of the first solution is, when the first solution temperature
When too high, second of vib metals compound of addition is possible to that precipitation reaction occurs with the metallic compound of the first solution,
So as to destroy the stability of solution.
According to dipping solution preparation method provided by the invention, defined is down in treated first solution temperature
After temperature, the step of being further introduced into organic additive may also include.The organic additive can introduce second of vib gold
Before category, simultaneously, afterwards introduce, can be directly added into the form of organic additive compound or with organic additive
Aqueous solution form add.The organic additive is selected from organic acid, Organic Alcohol.Organic acid and the preferred of Organic Alcohol can refer to above
Statement, will not be repeated here.The mol ratio of group VIII metallic compound in the organic additive and solution that are introduced into the step
For 0~4, it is preferable that the mol ratio of the organic additive that is introduced in the step and group VIII metallic compound for 0.05~
2.5。
The invention provides the hydrogenation catalyst that a kind of preparation method of the hydrogenation catalyst by the present invention is prepared.
The catalyst obtained according to the method for the invention, in preparation process, the dosage of carrier and metal component causes
On the basis of final catalyst, and in terms of oxide, group VIII tenor is 1~9 weight %, the first vib metal
Content is 1~30 weight %, and second of weight % of vib metal 2~36, surplus is carrier.Wherein, group VIII metal is preferred
For at least one of Co and Ni, the first vib metal is preferably Mo, and second of vib metals are preferably W.
The catalyst obtained according to the method for the invention, alternatively, containing at least one inorganic assistant, the no machine aided
Agent preferably is selected from phosphorus, boron, fluorine, titanium, silicon, on the basis of catalyst weight, and in terms of element, the content of the inorganic assistant for 0~
13 weight %, it is highly preferred that the content of inorganic assistant is 1-10 weight %.
The catalyst obtained according to the method for the invention, containing at least one organic additive, the organic additive is selected from
Organic acid, the mixture of organic acid and ammonium salt organic acid, the nonacid oxygen-bearing organic matter containing C-O keys and/or C=O keys.Its
In, on the basis of catalyst weight, and in terms of carbon, the content of organic additive is 0.5~10 weight %, preferably 1~8 weight
Measure %, more preferably 1~6 weight %.
According to the conventional method in this area, catalyst provided by the invention before the use, can generally exist in hydrogen
Under, at a temperature of 140-370 DEG C with sulphur, hydrogen sulfide or it is other carry out presulfurization containing sulfur feedstock, the presulfurization can be outside device
Progress can also be carried out in device it is In-situ sulphiding, to be translated into sulfide type, this can refer to prior art progress, this hair
Bright no particular/special requirement, will not be repeated here.
Compared with existing hydrogenation catalyst, catalyst provided by the invention has higher hydrofinishing activity, and this is urged
Agent is applied to oil, coal liquefaction fraction oil, the unifining process of bio-oil, or such as catalytic cracking of other catalytic process
The pretreatment of raw material of process and hydrocracking process.
The invention will be further described by the following examples, but not thereby limiting the invention.
The raw material sources prepared used in dipping solution are as follows：Citric Acid Mono (analyzes pure, Tianjin Heng Xing chemical reagents corporations
Product), phosphoric acid (analyzes pure, Beijing Chemical Plant's product), and aminotriacetic acid (analyzes pure, Beijing Heng Yezhongyuan Chemical Co., Ltd.s
Product), ethylenediamine tetra-acetic acid (analyzes pure, Shantou Xilong Chemical Factory product), the ammonium of the ethylenediamine tetra-acetic acid two (weight of purity 99%
Amount, Changzhou Yi Run Chemical Co., Ltd.s product), glycerine (analyzes pure, Beijing Chemical Plant's product), and (analysis is pure, north for diethylene glycol (DEG)
Capital Xin Dingpengfei developments in science and technology Co., Ltd product), ammonium dihydrogen phosphate (analyzes pure, Beijing chemical reagents corporation product), (alkali formula
Nickelous carbonate (gives birth to catalyst Co. product, the weight % of NiO contents 51 in Yixing City Shen), molybdenum trioxide (the limited public affairs of Tianjin four directions chemical industry
Take charge of product), ammonium paramolybdate (Chemical Reagent Co., Ltd., Sinopharm Group, analysis are pure), (Zhuzhou diamond tungsten product is limited for ammonium metatungstate
Products, WO3The weight % of content 91), basic cobaltous carbonate (Jiangxi Nuclear Industry Xingzhong Technology Co., Ltd.'s product, CoO contents 57
Weight %).
Prepare carrier source used in catalyst and property is as follows：
Carrier S 1：By 350 grams of alkaline silica sols (Beijing flying dragon horse Science and Technology Ltd. product, SiO2The weight % of content 30)
Mixed with 549 grams of boehmites (Sinopec catalyst Chang Ling branch company product, water content 28%), be extruded into circumscribed circle diameter
For 1.6 millimeters of trilobal bar, wet bar is dried 4 hours in 120 DEG C, and 600 DEG C of roastings obtain carrier S 1 in 4 hours.Titanium dioxide in S1
The content of silicon is 21 weight %, and alumina content is 79% weight.
Carrier S 2：By 493 grams of SB powder (German Sasol Products, water content 27%), 26.3 grams of USY (urge by Sinopec
Agent Chang Ling branch company, the weight % of water content 24) and 25.6 grams of ASA40 amorphous silicons aluminium powders (German Sasol Products, water
The weight % of content 22) mixing, it is 1.6 millimeters of trilobal bar to be extruded into circumscribed circle diameter, and wet bar dries 4 hours in 120 DEG C, 520
DEG C roasting obtains carrier S 2 for 4 hours, and the content of aluminum oxide is 90% in S2, and the content of USY molecular sieve is 5%, ASA40 content
For 5%.
Carrier S 3：By 31.4 grams of ammonium fluorides (analyzing pure, Jinan chemical plant product), (Tianjin is triumphant for 350 grams of titanium-contained aluminum oxide powder
Yi Te developments in science and technology Co., Ltd product, the weight % of content of titanium dioxide 15, water content 28%), 154.3 grams of boehmites
(Shandong Aluminium Industrial Corp's product, water content 30%) mixes, and is extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar is in 120
DEG C drying 4 hours, 560 DEG C of roastings obtain carrier S 3 in 4 hours.The content of fluorine (being counted using element) is 4 weight %, titanium dioxide in S3
Content is 13% weight, and alumina content is 83 weight %.
Carrier S 4：550 grams of boehmites (Sinopec catalyst Chang Ling branch company product, water content 29%) are mixed
Close, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar is dried 4 hours in 120 DEG C, and 650 DEG C of roastings obtain for 4 hours
Alumina support S4.
Embodiment 1
253 grams of Citric Acid Monos are added in the open containers for filling 600ml water, after stirring and dissolving, by 176.4 grams of alkali formulas
Added after nickelous carbonate and 60 grams of molybdenum trioxide mixing in above-mentioned solution, continue to stir and heat until dissolving, obtains the first solution.
Afterwards, by first solution under 95 DEG C and normal pressure activation process 2 hours, solution body is made by interval moisturizing in this process
Product is held essentially constant.Treat that solution temperature naturally cools to 30 DEG C after the completion of activation process, then add 659.1 grams of ammonium metatungstates
Enter in treated first solution, after stirring and dissolving, moisturizing makes liquor capacity to 1000ml, so as to which dipping solution be made.
Take 150 grams of S1 carriers, impregnate S1 carriers 1 hour with the above-mentioned dipping solutions of 123ml, to dry 6 after 120 DEG C small
When, catalyst C-1 is made, catalyst property parameter is shown in Table 1.
Comparative example 1
253 grams of Citric Acid Monos are added in the open containers for filling 600ml water, after stirring and dissolving, by 176.4 grams of alkali formulas
Added after nickelous carbonate and 60 grams of molybdenum trioxide mixing in above-mentioned solution, continue to stir and heat until dissolving, obtains the first solution.
Then 659.1 grams of ammonium metatungstates are added in above-mentioned solution, after stirring and dissolving, moisturizing makes liquor capacity to 1000ml, so as to make
Obtain dipping solution.
Take 150 grams of S1 carriers, impregnate S1 carriers 1 hour with the above-mentioned dipping solutions of 123ml, to dry 6 after 120 DEG C small
When, catalyst DC-1 is made, catalyst property parameter is shown in Table 1.
Comparative example 2
176.4 grams of basic nickel carbonates and 60 grams of molybdenum trioxides are added in the open containers for filling 600ml water, stirs and adds
Heat obtains the first solution until dissolving.659.1 grams of ammonium metatungstates are added through in above-mentioned solution afterwards, will be molten after stirring and dissolving
Liquid activation process 2 hours under 95 DEG C and normal pressure, are held essentially constant liquor capacity by interval moisturizing in this process.It is living
Treat that solution temperature naturally cools to 30 DEG C after the completion of change processing, moisturizing makes liquor capacity to 1000ml, so as to which dipping solution be made.
Take 150 grams of S1 carriers, impregnate S1 carriers 1 hour with the above-mentioned dipping solutions of 123ml, to dry 6 after 120 DEG C small
When, catalyst DC-2 is made, catalyst property parameter is shown in Table 1.
Embodiment 2
48.7 grams of phosphoric acid and 253 grams of Citric Acid Monos are added in the open containers for filling 600ml water, after stirring and dissolving,
Added after 176.4 grams of basic nickel carbonates and 60 grams of molybdenum trioxides are mixed in above-mentioned solution, continue to stir and heat up to dissolving,
Obtain the first solution.Afterwards, by first solution under 95 DEG C and normal pressure activation process 2 hours, in this process by
Moisturizing of having a rest is held essentially constant liquor capacity.Treat that solution temperature naturally cools to 30 DEG C after the completion of activation process, then will
659.1 grams of ammonium metatungstates are added in treated first solution, and after stirring and dissolving, moisturizing makes liquor capacity to 1000ml, from
And dipping solution is made.
Take 150 grams of S1 carriers, impregnate S1 carriers 1 hour with the above-mentioned dipping solutions of 123ml, to dry 6 after 120 DEG C small
When, catalyst C-2 is made, catalyst property parameter is shown in Table 1.
Comparative example 3
For preparation method with embodiment 2, difference is the step handled after having prepared the first solution without atmospheric activating
Suddenly, the catalyst obtained is DC-3, and catalyst property parameter is shown in Table 1.
Embodiment 3
52.4 grams of phosphoric acid and 206.6 grams of aminotriacetic acids are added in the open containers for filling 650ml water, stirring and dissolving
Afterwards, will 79.1 grams of basic nickel carbonates and 193.7 grams of molybdenum trioxides mix after add in above-mentioned solution, continue to stir and heat up to
Dissolving, obtains the first solution.Afterwards, by first solution under 70 DEG C and normal pressure activation process 15 hours, in this process
Liquor capacity is held essentially constant by interval moisturizing.Treat that solution temperature naturally cools to 45 DEG C after the completion of activation process, with
35.5 grams of ammonium metatungstates are added in treated first solution afterwards, after stirring and dissolving, moisturizing makes liquor capacity to 1000ml,
So as to which dipping solution be made.
Take 150 grams of S2 carriers, impregnate S2 carriers 1 hour with the above-mentioned dipping solutions of 114ml, to dry 2 after 200 DEG C small
When, catalyst C-3 is made, catalyst property parameter is shown in Table 1.
Comparative example 4
For preparation method with embodiment 3, difference is the step handled after having prepared the first solution without atmospheric activating
Suddenly, the catalyst obtained is DC-4, and catalyst property parameter is shown in Table 1.
Comparative example 5
52.4 grams of phosphoric acid and 206.6 grams of aminotriacetic acids are added in the open containers for filling 650ml water, stirring and dissolving
Afterwards, will 79.1 grams of basic nickel carbonates and 226.0 grams of molybdenum trioxides mix after add in above-mentioned solution, continue to stir and heat up to
Dissolving, obtains the first solution.Afterwards, by first solution under 95 DEG C and normal pressure activation process 2 hours, lead in this process
Crossing interval moisturizing is held essentially constant liquor capacity.Treat that solution temperature naturally cools to 30 DEG C after the completion of activation process, moisturizing
Make liquor capacity to 1000ml, so as to which dipping solution be made.
Take 150 grams of S2 carriers, impregnate S2 carriers 1 hour with the above-mentioned dipping solutions of 114ml, to dry 2 after 200 DEG C small
When, catalyst DC-5 is made, catalyst property parameter is shown in Table 1.
Comparative example 6
52.4 grams of phosphoric acid and 206.6 grams of aminotriacetic acids are added in the open containers for filling 650ml water, stirring and dissolving
Afterwards, will 79.1 grams of basic nickel carbonates and 193.7 grams of molybdenum trioxides mix after add in above-mentioned solution, continue to stir and heat up to
Dissolving, obtains the first solution.Afterwards, first solution is handled 2 hours under 95 DEG C and normal pressure, in this process by
Moisturizing of having a rest is held essentially constant liquor capacity.Treat that solution temperature naturally cools to 30 DEG C after the completion of processing, then by 39.9 grams
Ammonium paramolybdate, which adds moisturizing in treated first solution, makes liquor capacity to 1000ml, so as to which dipping solution be made.
Take 150 grams of S2 carriers, impregnate S2 carriers 1 hour with the above-mentioned dipping solutions of 114ml, to dry 2 after 200 DEG C small
When, catalyst DC-6 is made, catalyst property parameter is shown in Table 1.
Embodiment 4
117.6 grams of phosphoric acid, 59.1 grams of ammonium dihydrogen phosphates and 195.3 grams of citric acids are added to the opening appearance for filling 600ml water
In device, after stirring and dissolving, add in above-mentioned solution, continue after 243.6 grams of basic nickel carbonates and 190.5 grams of molybdenum trioxides are mixed
Stirring and heating are until dissolving, is subsequently added into 38.2 grams of glycerine, so as to obtain the first solution.Afterwards, by first solution
Activation process 10 hours, is held essentially constant liquor capacity by interval moisturizing in this process under 80 DEG C and normal pressure.It is living
Treat that solution temperature naturally cools to 40 DEG C after the completion of change processing, 227.5 grams of ammonium metatungstates are then added treated first
In solution, after stirring and dissolving, moisturizing makes liquor capacity to 1000ml, so as to which dipping solution be made.
Take 150 grams of S3 carriers, impregnate S3 carriers 1 hour with the above-mentioned dipping solutions of 105ml, to dry 3 after 120 DEG C small
When, catalyst C-4 is made, catalyst property parameter is shown in Table 1.
Comparative example 7
For preparation method with embodiment 4, difference is the step handled after having prepared the first solution without atmospheric activating
Suddenly, the catalyst obtained is DC-7, and catalyst property parameter is shown in Table 1.
Embodiment 5
By 76.4 grams of phosphoric acid, 28.8 grams of ethylenediamine tetra-acetic acids, 10.7 grams of ammoniums of ethylenediamine tetra-acetic acid two and 96.4 grams of alkali formula carbon
Sour cobalt is added in the open containers for filling 600ml water, and after heating stirring dissolving, 313.9 grams of molybdenum trioxides are added into above-mentioned solution
In, continue to stir and heat until dissolving, obtains the first solution.Afterwards, first solution is activated under 85 DEG C and normal pressure
Processing 5 hours, is held essentially constant liquor capacity by interval moisturizing in this process.Treat solution temperature certainly after the completion of processing
35 DEG C so are cooled to, is then added 86.2 grams of ammonium metatungstates in the solution, after stirring and dissolving, moisturizing makes liquor capacity extremely
1000ml, so as to which dipping solution be made.
Take 150 grams of S4 carriers, impregnate S4 carriers 1 hour with the above-mentioned dipping solutions of 140ml, to dry 4 after 150 DEG C small
When, catalyst C-5 is made, catalyst property parameter is shown in Table 1.
Comparative example 8
For preparation method with embodiment 5, difference is the step handled after having prepared the first solution without atmospheric activating
Suddenly, the catalyst obtained is DC-8, and catalyst property parameter is shown in Table 1.
Embodiment 6
177 grams of phosphoric acid and 59.3 grams of Citric Acid Monos are added in the open containers for filling 600ml water, after stirring and dissolving,
Added after 124.6 grams of basic nickel carbonates and 436 grams of molybdenum trioxides are mixed in above-mentioned solution, continue to stir and heat until molten
Solution, obtains the first solution.Afterwards, by first solution under 90 DEG C and normal pressure activation process 4 hours, pass through in this process
Interval moisturizing is held essentially constant liquor capacity.Treat that solution temperature naturally cools to room temperature after the completion of activation process, then will
55.3 grams of ammonium metatungstates and 98.8 grams of diethylene glycol (DEG)s are added in the first solution Jing Guo activation process, and after stirring and dissolving, moisturizing makes molten
Liquid product is to 1000ml, so as to which dipping solution be made.
Take 150 grams of S4 carriers, impregnate S4 carriers 1 hour with the above-mentioned dipping solutions of 140ml, to dry 4 after 120 DEG C small
When, catalyst C-6 is made, catalyst property parameter is shown in Table 1.
Comparative example 9
For preparation method with embodiment 6, difference is the step handled after having prepared the first solution without atmospheric activating
Suddenly, the catalyst obtained is DC-9, and catalyst property parameter is shown in Table 1.
Table 1
Catalytic activity of the embodiment 7~12 for illustrating present invention offer hydrogenation catalyst C-1~C-6, comparative example 10~
18 catalytic activity for illustrating comparative catalyst DC-1~DC-9.
Evaluation method one：This method is used for the catalytic diesel oil hydrotreating performance for evaluating catalyst and contrast medium, specific side
Method is：By catalyst breakage into 2-4 mm granules, catalyst, raw materials used oil and evaluation are evaluated on 30 milliliters of hydrogenation plants
Condition is shown in Table 2.The assay method of sulphur is SH/T 0689-2000, and the assay method of nitrogen is SH/T 0657-2007.Catalyst
Hydrodesulfurization activity is calculated by 1.65 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction.Involved calculation formula is such as
Under.
Table 2
| Raw material oil nature | Catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 0.9242 |
| S, ppm | 6800 |
| N, ppm | 902 |
| Reaction condition | |
| Hydrogen dividing potential drop, Mpa | 6.0 |
| Catalyst volume, ml | 30 |
| Temperature, DEG C | 340 |
| Volume space velocity, h-1 | 2.0 |
| Hydrogen-oil ratio, v/v | 300 |
Embodiment 7,8 and comparative example 10~12 are carried out according to evaluation method one, to illustrate catalyst C-1, C-2 and contrast
Agent DC-1~DC-3 hydrodesulfurization and hydrodenitrogenationactivity activity, evaluation result are shown in Table 3.
Table 3
The result of table 3 shows：Hydrogenation catalyst hydrodesulfurization provided by the invention and hydrodenitrogeneration performance are substantially better than pair
Compare catalyst.
Evaluation method two：This method is used for the residual hydrocracking performance for evaluating catalyst and contrast medium, and specific method is：
By catalyst breakage into 2-4 mm granules, react and carried out on 250 milliliters of hydrogenation plants, feedstock oil uses the normal slag in the Middle East, and sulphur contains
Measure as 4.7%, nitrogen content 0.29%, carbon residue 12.6%.Reaction condition is：385 DEG C of reaction temperature, 15.0 MPas of hydrogen dividing potential drop,
Volume space velocity 0.5h-1.The analysis method of carbon residue is GB/T17144-1997, and removal of ccr by hydrotreating activity is calculated by 1 order reaction, involved
And calculation formula it is as follows.
Embodiment 9 and comparative example 13~15
Carried out according to evaluation method two, to illustrate catalyst C-3 and contrast medium DC-4, DC-5, DC-6 residual hydrogenation
De- carbon residue performance, evaluation result are shown in Table 4.
Table 4
| Numbering | Catalyst | With respect to removal of ccr by hydrotreating activity, % |
| Embodiment 9 | C-3 | 116 |
| Comparative example 13 | DC-4 | 100 |
| Comparative example 14 | DC-5 | 108 |
| Embodiment 15 | DC-6 | 105 |
Result in table 4 shows that catalyst C-3 provided by the invention residual hydrogenation takes off carbon residue activity higher than contrast catalysis
Agent DC-4, DC-5 and DC-6.
Evaluation method three：This method is used for the liquefied coal coil hydrotreating performance for evaluating catalyst and contrast medium, specific side
Method is：By catalyst breakage into 2-4 mm granules, catalyst is evaluated on 250 milliliters of hydrogenation plants, raw materials used oil nature,
Reaction condition is shown in Table 5.The hydrodesulfurization activity of catalyst is calculated by 1.65 order reactions, and hydrodenitrogenationactivity activity presses 1 order reaction
Calculate, its calculation formula and sulphur, the analysis method of nitrogen are the same as method one.
Table 5
| Raw material oil nature | Liquefied coal coil |
| Density (20 DEG C), g/cm3 | 0.9934 |
| S, ppm | 133 |
| N, ppm | 3500 |
| Colloid, m% | 8.0 |
| Reaction condition | |
| Hydrogen dividing potential drop, MPa | 12.0 |
| Catalyst volume, mL | 100 |
| Temperature, DEG C | 380 |
| Volume space velocity, h-1 | 1.4 |
Embodiment 10 and comparative example 16
Carried out according to evaluation method three, to illustrate catalyst C-4 and contrast medium DC-7 hydrodenitrogeneration and hydrodesulfurization
Activity, evaluation result are shown in Table 6.
Table 6
Result in table 6 shows that catalyst C-4 of the present invention liquefied coal coil hydrotreating performance is substantially better than contrast catalysis
Agent DC-7.
Evaluation method four：This method is used for the wax tailings hydrotreating performance for evaluating catalyst and contrast medium, specific side
Method is：By catalyst breakage into 2-4 mm granules, catalyst is evaluated on 250 milliliters of hydrogenation plants, raw materials used oil nature,
Reaction condition is shown in Table 7.
Table 7
| Raw material oil nature | Wax tailings |
| Density (20 DEG C), g/cm3 | 0.9205 |
| S, ppm | 8300 |
| N, ppm | 6100 |
| MCR, m% | 0.32 |
| Reaction condition | |
| Hydrogen dividing potential drop, MPa | 10.0 |
| Catalyst volume, mL | 100 |
| Temperature, DEG C | 365 |
| Volume space velocity, h-1 | 1.4 |
| Hydrogen-oil ratio, v/v | 600 |
The assay method of sulphur is SH/T 0689-2000, and the assay method of nitrogen is SH/T 0704-2001.Catalyst adds
Hydrogen is desulphurizing activated to be calculated by 1.5 order reactions, and involved calculation formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction,
Calculation formula is the same as embodiment 7.
Embodiment 11 and comparative example 17
Carried out according to evaluation method four, to illustrate catalyst C-5 and contrast medium DC-8 hydrodenitrogeneration and hydrodesulfurization
Activity, evaluation result are shown in Table 8.
Table 8
Result in table 8 shows that catalyst C-5 of the present invention wax tailings hydrotreating performance is substantially better than contrast catalysis
Agent DC-8.
Evaluation method five：This method is used for the mixed diesel hydrofinishing performance for evaluating catalyst and contrast medium, specific side
Method is：By catalyst breakage into 2-4 mm granules, catalyst is evaluated on 250 milliliters of hydrogenation plants, raw materials used oil nature,
Reaction condition is shown in Table 9.The hydrodesulfurization activity of catalyst is calculated by 1.65 order reactions, and hydrodenitrogenationactivity activity presses 1 order reaction
Calculate, its calculation formula and sulphur, the analysis method of nitrogen are the same as method one.
Table 9
| Raw material oil nature | Straight bavin/urge bavin miscella |
| Density (20 DEG C), g/cm3 | 0.8630 |
| S, ppm | 9800 |
| N, ppm | 390 |
| Reaction condition | |
| Hydrogen dividing potential drop, MPa | 6.4 |
| Catalyst volume, mL | 100 |
| Temperature, DEG C | 355 |
| Volume space velocity, h-1 | 2.0 |
Embodiment 12 and comparative example 18
Carried out according to evaluation method five, to illustrate catalyst C-6 and contrast medium DC-9 hydrodenitrogeneration and hydrodesulfurization
Activity, evaluation result are shown in Table 10.
Table 10
Result in table 10 shows that catalyst C-6 of the present invention mixed diesel hydrofinishing performance is substantially better than contrast and urged
Agent DC-9.
Claims (18)
1. a kind of preparation method of hydrogenation catalyst, including dipping solution is contacted with carrier, then through drying, roasting or
It is not calcined, obtains the hydrogenation catalyst, it is characterised in that the preparation method of the dipping solution comprises the following steps：
(1) compound containing at least one metal containing group VIII is prepared and containing at least one containing the first vib metal
First solution of compound；
(2) the first solution is subjected to atmospheric activating processing, treatment temperature is 65~100 DEG C, hour time 0.5-36；
(3) the first solution after activation process is cooled to room temperature~50 DEG C, afterwards, introduces at least one contain second thereto
The compound of vib metal, obtain the dipping solution.
2. preparation method according to claim 1, it is characterised in that the operating condition of the contact includes：Temperature is room
For temperature to 80 DEG C, time of contact is 0.1~24 hour.
3. preparation method according to claim 1, it is characterised in that the operating condition of the drying includes：Temperature is 60-
250 DEG C, the time is 1-24 hours；The operating condition of the roasting includes：Temperature is 300-700 DEG C, and the time is 0.5-12 hours.
4. according to the preparation method described in claim 1-3 any one, it is characterised in that the group VIII metal is selected from
At least one of Fe, Co, Ni.
5. according to the preparation method described in claim 1-3 any one, it is characterised in that the change of the metal containing group VIII
One or more of the compound in its nitrate, carbonate, subcarbonate, phosphate, hypophosphites, organic carboxylate.
6. according to the preparation method described in claim 1-3 any one, it is characterised in that the first described vib metal is
Molybdenum, second of vib metals are tungsten.
7. preparation method according to claim 6, it is characterised in that the compound choosing containing the first vib metal
It is described from molybdenum trioxide, molybdic acid, para-molybdic acid, molybdate, phosphomolybdic acid, phosphomolybdate, paramolybdate, two molybdates, four molybdates
Compound containing second of vib metals is selected from wolframic acid, metatungstic acid, ethyl metatungstic acid, phosphotungstic acid, silico-tungstic acid, phosphotungstate, silicon
Tungstates, ethyl metatungstate, tungstates, metatungstate.
8. according to the preparation method described in claim 1-3 any one, it is characterised in that also containing extremely in first solution
The mixture of a kind of few inorganic acid or at least one inorganic acid and at least one inorganic acid salt.
9. preparation method according to claim 8, it is characterised in that the inorganic acid is selected from nitric acid, hydrochloric acid, phosphoric acid, Asia
At least one of phosphoric acid, hypophosphorous acid, boric acid, the inorganic acid salt are selected from the ammonium salt of aforementioned inorganic acid.
10. according to the preparation method described in claim 1-3 any one, it is characterised in that also contain in first solution
At least one organic additive, the organic additive are the one or more in organic acid, Organic Alcohol, ammonium salt organic acid.
11. preparation method according to claim 10, it is characterised in that the organic acid be selected from ammonia carboxylic acid, alkyl carboxylic acid,
Containing the one or more in aldehydic acid, hydroxyl carboxylic acid, Organic Alcohol is selected from C1-C8 Organic Alcohol and/or weight average molecular weight is
One or more in 120-4000 polyethylene glycol, one kind or several in ammonium salt of the ammonium salt organic acid selected from foregoing organic acid
Kind.
12. according to the preparation method described in claim 1-3 any one, it is characterised in that the dipping solution is the aqueous solution.
13. according to the preparation method described in claim 1-3 any one, the reaction response temperature of first solution is 70 DEG C
~95 DEG C, the time is 2-15 hours.
14. according to the preparation method described in claim 1-3 any one, it is characterised in that to after reaction in the step (3)
The first solution in introduce the mode of the compound containing second vib metal to be introduced directly into or drawing in form of an aqueous solutions
Enter.
15. preparation method according to claim 1, it is described introduce containing second group vib metal compound when, through cooling
The temperature of the first solution afterwards is room temperature~45 DEG C.
16. preparation method according to claim 1, it is characterised in that can be also further introduced into the step (3) organic
Auxiliary agent, the organic additive introduce prior to, concurrently with, or after the compound containing second of vib metals is introduced.
A kind of 17. hydrogenation catalyst that preparation method as described in claim 1-16 obtains.
18. catalyst according to claim 17, it is characterised in that in preparation process, the use of carrier and metal component
Amount make it that on the basis of final catalyst and in terms of oxide, group VIII tenor is 1~9 weight %, and the first the
Vib metal content is 1~30 weight %, and second of weight % of vib metal 2~36, surplus is carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610407231.3A CN107486249B (en) | 2016-06-12 | 2016-06-12 | Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610407231.3A CN107486249B (en) | 2016-06-12 | 2016-06-12 | Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107486249A true CN107486249A (en) | 2017-12-19 |
| CN107486249B CN107486249B (en) | 2019-12-27 |
Family
ID=60643177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610407231.3A Active CN107486249B (en) | 2016-06-12 | 2016-06-12 | Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107486249B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097539A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and hydrogenation catalyst |
| CN114829009A (en) * | 2019-12-20 | 2022-07-29 | 托普索公司 | Method for activating catalytically active material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082619A (en) * | 2003-09-04 | 2005-03-31 | Idemitsu Kosan Co Ltd | Method for preliminarily sulfurizing hydrogenation treatment catalyst and method for desulfurizing gas oil |
| CN102764658A (en) * | 2011-05-06 | 2012-11-07 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and its preparation method |
| CN105013499A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
-
2016
- 2016-06-12 CN CN201610407231.3A patent/CN107486249B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082619A (en) * | 2003-09-04 | 2005-03-31 | Idemitsu Kosan Co Ltd | Method for preliminarily sulfurizing hydrogenation treatment catalyst and method for desulfurizing gas oil |
| CN102764658A (en) * | 2011-05-06 | 2012-11-07 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and its preparation method |
| CN105013499A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097539A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and hydrogenation catalyst |
| CN114829009A (en) * | 2019-12-20 | 2022-07-29 | 托普索公司 | Method for activating catalytically active material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107486249B (en) | 2019-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055956B (en) | Maceration extract of hydrogenation catalyst and preparation method thereof and hydrogenation catalyst and preparation method thereof | |
| JP2002534581A (en) | Hydrorefining method using bulk Group VIII / VIB catalyst | |
| CN104128189B (en) | For hydrotreating or the preparation method for the catalyst based on molybdenum being hydrocracked | |
| CN106607039B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN106179382A (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN106179386B (en) | The preparation method of Hydrobon catalyst | |
| CN107029779B (en) | A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve | |
| CN105013498B (en) | A kind of hydrotreating catalyst and its application | |
| RU2626402C1 (en) | Method for preparing hydrotreatment catalyst of hydrocracking raw materials | |
| CN107486249A (en) | A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method | |
| CN105478172B (en) | A kind of hydrotreating catalyst and its application | |
| Silvy | Scale-up of a NiMoP/γAl2O3 catalyst for the hydrotreating and mild hydrocracking of heavy gasoil | |
| CN106179385B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN107159302A (en) | A kind of hydrotreating catalyst and its application | |
| CN106391105A (en) | Multi-level pore hydrocracking catalyst containing composite molecular sieve, and applications thereof | |
| CN107486251A (en) | A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method | |
| CN105013521B (en) | A kind of hydrocracking catalyst and its application | |
| CN103316687B (en) | The combination catalyst of diesel hydrogenation for removal sulphur and diesel oil hydrodesulphurizatiomethod method | |
| CN107486250A (en) | A kind of preparation method of dipping solution and dipping solution obtained by this method | |
| CN107486216A (en) | A kind of preparation method of dipping solution and dipping solution obtained by this method | |
| CN106179388A (en) | A kind of preparation method of hydrotreating catalyst | |
| CN106179383B (en) | The preparation method of hydrotreating catalyst | |
| CN104437579B (en) | Distillate-oil hydrofining catalyst, and preparation and application thereof | |
| RU2665486C1 (en) | Method for preparation of hydroprocessing catalyst of hydrocracking material | |
| CN105688978A (en) | Hydrogenation treatment catalyst, and applications 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 |