CN110465304A - A kind of preparation method of high activity hydrogenation and desulphurization catalyst - Google Patents
A kind of preparation method of high activity hydrogenation and desulphurization catalyst Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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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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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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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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- 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
Abstract
A kind of preparation method of high activity hydrogenation and desulphurization catalyst, this method are that it is modified that carbon-based material is carried out surface using carbon-based material as carrier；Preparation contains Ni, Mo or the hydrodesulfurization precursor solution containing Co, Mo or containing Ni, Mo active component, modified carbon-based material is impregnated in precursor solution, by activity component impregnation in carrier surface, then it is dried, calcines, obtain the carbon-based Hydrobon catalyst containing NiMo or CoMo or NiMo active component.The present invention is such as handled using oxidizing acid oxidation or oxidizing gas by carrying out the processing that comes to the surface to carbon material carrier, carbon support can be made rich in hydroxyl.By the modulation of degree for the treatment of, active component can be allowed to realize the change from Monolayer Dispersion to few layer and multilayer in carrier.And then the vulcanization that NiMo component may be implemented maximizes, and inherently improves the latent active of Hydrobon catalyst.
Description
Technical field
The present invention relates to hydrodesulfurization field more particularly to a kind of preparation methods of high activity hydrogenation and desulphurization catalyst.
Background technique
With the development of road transport cause and the harshness increasingly of environmental regulation, it is extensive that the production of clean fuel oil obtains people
Concern.Currently, hydrodesulfurization is still the optimal path for realizing industrialization clean fuel oil production.However, with stone in world wide
The problem of oily resource is increasingly depleted, and minable petroleum resources are faced with heaviness and in poor quality, so that hydrodesulfurization at present
Industrialized production faces bottleneck.Using the exploitation of high-effect industrial Hydrobon catalyst, to meet increasingly stringent environmental protection rule
Model has become the focus of countries in the world scientific research institutions close attention.
The active component of hydrodesulfurization industrial catalyst is generally based on transition metal element in VIB and VIII group, usually
It is combined for the binary or ternary of tetra- kinds of elements of Co, Ni, Mo, W, most commonly seen has Ni-Mo, Co-Mo, Ni-W system.Add hydrogen de-
Sulphur Industrial Catalysis agent carrier is usually aluminium oxide.Currently, high activity hydrogenation and desulphurization catalyst exploitation generally comprises active component
Modified and catalyst carrier is modified.Active component it is modified generally by using multi-element metal group subassembly (as using NiMoW,
NiCoMo, NiCoW or NiMoCoW etc.) or change active metal component (such as using noble metal) measure and improve its hydrogenation activity.
Support modification generallys use auxiliary agent addition (such as adding F, B, P in the carrier), the dissociation of Lai Tigao catalyst C-S key and desulfurization energy
Power.CN103316687A provides combination catalyst and the deep hydrodesulfurizationof of diesel oil side of a kind of deep hydrodesulfurizationof of diesel oil
Method.The active component of catalyst is the combination of two or three of metal in Co, Mo, Ni, W.First catalyst is selected from
TiO2、SiO2、Al2O3In two or three compound；Second catalyst carrier is selected from TiO2、SiO2、Al2O3In two kinds or
Three kinds with the compound of PY molecular sieve.Two kinds of catalyst utilize the temperature gradient in reaction process with certain proportion combination loading
The characteristics of variation gives full play to two kinds of catalyst, can make diesel oil sulfur content be down to 10 μ g/g or less.CN 103816914A is provided
A kind of preparation method of light fraction oil Hydrobon catalyst.γ-the Al of titaniferous is obtained by adding titanium in the carrier2O3It carries
Body uses the solution impregnation-calcination containing Ni, W and/or Mo later, obtains high activity hydrogenation and desulphurization catalyst, can be used for gasoline and evaporate
Divide and kerosene distillate hydrofinishing.
Since hydrodesulfurization activity component (Ni-Mo, Co-Mo, Ni-W) and aluminium oxide have stronger metallic carrier phase interaction
With, thus metal is generally in high dispersive in carrier surface, thus metal component state of cure (vulcanization) is not high (with aluminium oxide bound fraction
Cannot cure), commonly known as I class activated centre.And by support modification, weaken metal component by binding ability between carrier
Or when using more stringent vulcanization means, active metal component can be vulcanized by depth, and catalyst can have higher essence
Activity and referred to as II class activated centre.Therefore, with II class activated centre, based on Ni-Mo, Co-Mo, Ni-W etc.
, the exploitation of high activity hydrogenation and desulphurization catalyst is just becoming industry bright spot.CN 104117362A provides a kind of raising NiMo bavin
The catalyst and preparation method of oily Hydrobon catalyst hydrogenation activity.Metal component is Ni, Mo and atomic ratio is adjustable.In metal
Citric acid chelating is added when preparation can greatly improve NiMo/ γ-Al2O3The hydrogenation activity of hydrogenation catalyst.CN 110064403
A discloses a kind of preparation method of hydrotreating catalyst with denitrification activity.Its method is similar with CN104117362A, carries
Body is the porous material based on aluminium oxide or phosphorus-containing alumina material.Catalyst dipping, which uses, has a kind of and two classes activity
The NiMoP solution or CoMoP solution at center.Wherein, two class activated centre metallic solutions by being added organic additive in the solution
It realizes.CN106669860A discloses a kind of vulcanization start-up method of Hydrobon catalyst.To there are two class activated centres
Oxidation state Hydrobon catalyst soaks catalyst bed after being dried, being airtight.Later, sulfurized oil is introduced, and respectively 180
~240 DEG C, 250~330 DEG C of progress post-cures have more high activity after hydrogenation catalyst can be made to vulcanize.CN 102407148
A discloses a kind of activation method of Hydrobon catalyst for efficiently using metal carbides.This method adds hydrogen for oxidation state
Desulphurization catalyst organic matter or organic solution dipping, drying are simultaneously calcined, the Hydrobon catalyst being carbonized.Exist later
Reduction-sulfurization 2-15h in reaction unit.This method can partially improve metal and the interaction of carrier alkali, realize mentioning for reactivity
It rises.
In addition to carrying alumina is external, people also carry out hydrodesulfurization as carrier using the material weak with metallic cohesion and grind
Study carefully, the relatively high Hydrobon catalyst of available intrinsic reactivity.CN 108568309A discloses a kind of oil product depth and adds
Hydrogen desulphurization catalyst and preparation method thereof.By specific multiple emulsion system, 15 carrier material of hollow ball shape SBA is prepared, is adopted
Being modified with aluminium improves (main component the is silica) hydrothermal stability of SBA 15 and improves its acid bit quantity, then use etc.
Volume impregnation method loads to metal active constituent on carrier, prepared NiMo/SBA 15SP catalyst, not only have be suitable for
MoS2Dispersion degree and B, L acidity bit quantity also have excellent DBT reaction molecular diffusion, can be improved its general reaction
Rate evaluates dibenzothiophenes (DBT) hydrodesulfurization reaction activity, shows excellent DBT desulfurization conversion frequency TOF
And rate constant.
It it was noticed that carbon-based material is since it with metal is only capable of being bonded with weak bond, thus is the day in II class activated centre
So construction is preferred.Adjustable space cellular structure, surface functional group enrich, weak metal-support interaction, low green coke trend, resist
The advantages such as nitrogen ability is strong and metal easily recycles make carbon-based material become the new research hotspot in hydrodesulfurization field.At the same time,
The diversity of carbon-based material pattern and configuration also provides various possibility for the modulation of catalyst.Related activated carbon, activated carbon fiber,
Carbon nano-fiber, carbon nanotube, graphene nanobelt, mesoporous carbon and level porous carbon materials are in hydrodesulfurization catalytic reaction
Application also when have been reported that.However, preparing catalyst by carrier of carbon-based material at present, and it is used for hydrodesulfurization reaction
It reports actually rare.CN 107413329A discloses a kind of metal oxide-loaded method for preparation of active carbon.Biomass is passed through
It crushes and screens, high temperature carbonization, soda acid boiling reflux decontamination, filtration washing to neutrality.It is born using metal salt compounding agent solution
Carry metal oxide modified biomass active Carbon Materials.But the new catalytic material does not refer to the application in hydrodesulfurization field.
CN1436591A provides a kind of preprocess method of the absorbent charcoal carrier of supported precious metal catalyst, can prepare carbon-supported expensive
The carrier of metallic catalyst.But since noble metal loses activity in conjunction with sulphur in sulfur feed stock, thus it is dfficult to apply to add hydrogen
Desulphurization reaction.CN 106423161A discloses a kind of preparation method of hydrogenation catalyst.The catalyst is Pd/CeO2/ activity
Pd/carbon catalyst.But the catalyst is commonly used in the component of sulfur-bearing does not add hydrogen in charging.
CN 105990588A discloses a kind of difunctional Pd/Ni Mo/C composite catalyst and preparation method thereof, feature
Be precious metals pd part covering NiMo particle carbon supported catalyst, but its be more have efficient catalytic oxygen reduction,
The economic benefits and social benefits elctro-catalyst of oxygen evolution reaction.
The above analysis is as it can be seen that can obtain by using the carrier weaker with NiMo, CoMo, NiW active force has essence
II high class activated centre Hydrobon catalyst of activity, and carbon material is the very effective carrier for preparing this catalyst.
But it is few at present to be reported by the preparation method of the hydrodesulfurization catalytic new material of carrier of carbon.If the surface for passing through carbon material
It is modified, carrier and intermetallic interaction force are adjusted, with high depth vulcanization characteristics, II class of high activity will be prepared and lived
Property center hydrodesulfurization catalytic new material, meet clean fuel oil production and environmental protection specification, it is significant.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of high activity hydrogenation and desulphurization catalyst, especially with a kind of carbon
Material is carrier, can realize active component and the Hydrobon catalyst preparation method that carrier in combination promotes simultaneously.Invention passes through
Surface is carried out to the carrier of porous carbon to be modified, and on the basis of not destroying carbon material cellular structure itself, adjusts metal active group
The interaction with carbon material is divided to obtain the bis- class activated centre NiMo, CoMo, NiMo, so that metal can be anchored to carrier surface
And it can be vulcanized by depth.The catalysis material has high hydrodesulfurization latent active, is remarkably improved sulfur component and distillate
Hydrodesulfurization reaction performance.
To achieve the above object, the present invention is implemented with the following technical solutions:
A kind of preparation method of high activity hydrogenation and desulphurization catalyst, this method are using carbon-based material as carrier, by carbon substrate
It is modified that material carries out surface；It prepares molten containing Ni, Mo or the hydrodesulfurization presoma containing Co, Mo or containing Ni, Mo active component
Liquid impregnates modified carbon-based material in precursor solution, by activity component impregnation in carrier surface, is then done
Dry, calcining, obtains the carbon-based Hydrobon catalyst containing NiMo or CoMo or NiMo active component.
The carbon-based material includes activated carbon, activated carbon fiber, carbon nano-fiber, carbon nanotube, graphene nanobelt, Jie
Hole carbon.
It is oxidation processes, including the activation of acid oxidase, oxidizing gas, permanganic acid that carbon-based material, which carries out the modified method in surface,
Potassium oxidation.
Inorganic acid for acid oxidase includes nitric acid and/or sulfuric acid；Organic acid for acid oxidase includes carboxylic acid or carboxylic acid
Peroxide or hydrogen peroxide.
Gas for oxidizing gas activation includes one of oxygen, carbon monoxide, carbon dioxide and air or several
The mixture of one or more of kind or above-mentioned gas with inert gas.
Precursor solution containing Ni, Mo active component is the mixed solution containing Ni and Mo or contains single gold respectively
Belong to two kinds of solution of Ni, single metal Mo；Precursor solution containing Co, Mo active component is the mixed solution containing Co and Mo
Or contain two kinds of solution of single metal Co, single metal Mo respectively；Precursor solution containing Ni, Mo active component be containing
There is the mixed solution of Ni and Mo or contains two kinds of solution of single W metal, single metal Mo respectively.
Precursor solution is when containing two kinds of solution of single metal respectively, before carbon-based material and two kinds of single metals
It drives body water-soluble solution and carries out incipient impregnation or excessive dipping, dry, calcining respectively.
The drying include under air conditions it is dry, be dried in vacuo, inert gas shielding is dry, oxidizing gas is dry or
Reducibility gas is dry.
Using when drying, drying temperature is lower than 300 DEG C under air conditions；
When using vacuum drying, vacuum degree is -101.325Ka to 0, and vacuum drying temperature is in the vacuum degree boiling temperature
80% or more；
When dry using oxidizing gas, oxidizing gas includes one in oxygen, carbon monoxide, carbon dioxide and air
Mixture of one or more of the kind either above-mentioned gas with inert gas.
The dry reducibility gas of reducibility gas includes a kind of in hydrogen, ammonia or carbon monoxide；It is either above to go back
The mixed gas of originality gas and inert gas, reducibility gas shared volume ratio in mixed gas is 0.5%-99.5%；
The inert gas includes nitrogen, argon gas, helium.
Calcination temperature is 150-1000 DEG C, and calcination time terminates since room temperature to calcining, and the time is 10 minutes -50
Hour.
Compared with prior art, the beneficial effects of the present invention are:
By carrying out the processing that comes to the surface to carbon material carrier, such as handled using oxidizing acid oxidation or oxidizing gas, it can
Make carbon support rich in hydroxyl.By the modulation of degree for the treatment of, active component can be allowed to realize in carrier from Monolayer Dispersion to less
The change of layer (forming 2-8 layers of NiMoS cluster) and multilayer (9 layers or more NiMoS clusters).And then the sulphur of NiMo component may be implemented
Change and maximize, inherently improves the latent active of Hydrobon catalyst.
Specific embodiment
It elaborates below to the present invention, but practical range of the invention is not limited only to embodiment disclosed below.
A kind of preparation method of high activity hydrogenation and desulphurization catalyst, this method are using carbon-based material as carrier, by carbon substrate
It is modified that material carries out surface；It prepares molten containing Ni, Mo or the hydrodesulfurization presoma containing Co, Mo or containing Ni, Mo active component
Liquid impregnates modified carbon-based material in precursor solution, by activity component impregnation in carrier surface, is then done
Dry, calcining, obtains the carbon-based Hydrobon catalyst containing NiMo or CoMo or NiMo active component.
The carbon-based material includes activated carbon, activated carbon fiber, carbon nano-fiber, carbon nanotube, graphene nanobelt, Jie
Hole carbon.
It is oxidation processes, including the activation of acid oxidase, oxidizing gas, permanganic acid that carbon-based material, which carries out the modified method in surface,
Potassium oxidation.
Acid oxidase therein includes inorganic acid and organic acid oxidation.
Inorganic acid for acid oxidase includes nitric acid and/or sulfuric acid；Organic acid for acid oxidase includes carboxylic acid or carboxylic acid
Peroxide or hydrogen peroxide.
Inorganic acid for acid oxidase can be the concentrated nitric acid either concentrated sulfuric acid of 16-18mol/L of 14-16mol/L, or
Person is their mixture.It is also possible to diluted sulfuric acid and nitric acid.When using diluted sulfuric acid and when nitric acid, concentrated acid and water
Ratio is 1:50~50:1, preferably 1:20~20:1.
Gas for oxidizing gas activation includes one of oxygen, carbon monoxide, carbon dioxide and air or several
The mixture of one or more of kind or above-mentioned gas with inert gas.
When using oxidizing gas and other gas mixings, oxidizing gas ratio should ensure safety (explosion limit
Outside).When oxidizing gas is mixed with inert gas, volume ratio shared by oxidizing gas is 0.5%-99.5%, relatively good
It is 1%-95%, is preferably 5%-80%.
Precursor solution containing Ni, Mo active component is the mixed solution containing Ni and Mo or contains single gold respectively
Belong to two kinds of solution of Ni, single metal Mo；Precursor solution containing Co, Mo active component is the mixed solution containing Co and Mo
Or contain two kinds of solution of single metal Co, single metal Mo respectively；Precursor solution containing Ni, Mo active component be containing
There is the mixed solution of Ni and Mo or contains two kinds of solution of single W metal, single metal Mo respectively.
NiMo precursor mixed solution includes NiMoP solution, NiMo ammonia etc..
The presoma water-soluble solution of single metal is the nitrate containing Ni or Mo or Co or W, ammonium salt, chloride, sulphur
Hydrochlorate, phosphate.
Precursor solution is when containing two kinds of solution of single metal respectively, before carbon-based material and two kinds of single metals
It drives body water-soluble solution and carries out incipient impregnation or excessive dipping, dry, calcining respectively.
The drying include under air conditions it is dry, be dried in vacuo, inert gas shielding is dry, oxidizing gas is dry,
Reducibility gas is dry.
Drying temperature should be controlled 80% or more of dipping solution (including water and organic solution) boiling point under air conditions, be protected
Card solution is released effectively.Usual drying temperature should be preferably 80 DEG C or more at 40 DEG C or more.
To ensure that carbon carrier does not cause to aoxidize because drying under air conditions, when using being dried under air conditions, drying temperature
Lower than 300 DEG C；220 DEG C should be usually lower than.
When using vacuum drying, vacuum degree is -101.325Ka to 0, and vacuum drying temperature is in the vacuum degree boiling temperature
80% or more；Inert gas can carry out when dry under vacuum state, normal pressure state and pressurized state, required for above-mentioned state
Temperature be at least under the state, 80% or more dipping solution boiling temperature.
When dry using oxidizing gas, oxidizing gas includes one in oxygen, carbon monoxide, carbon dioxide and air
Mixture of one or more of the kind either above-mentioned gas with inert gas.
The dry reducibility gas of reducibility gas includes one of hydrogen, ammonia and carbon monoxide；More than either
The mixed gas of reducibility gas and inert gas, reducibility gas shared volume ratio in mixed gas is 0.5%-
99.5%, it is preferable to 1%-95%, are preferably 5%-80%.
Calcination temperature and calcination time ensure the abundant decomposition of precursor salt, and calcination temperature is 150-1000 DEG C, usually may be used
With 300-800 DEG C；Calcination time terminates since room temperature to calcining, and the time is -50 hours 10 minutes.Preferably 1 is small
When -24 hours.
In preparation process, calcining usually may include conventional calcination and atmosphere calcining, and conventional calcination, which refers to, does not add any atmosphere, lead to
It can often be carried out in Muffle furnace.
Atmosphere calcining refers to the calcination process under certain atmosphere, can usually carry out in tube furnace.
The inert gas includes nitrogen, argon gas, helium.
When being calcined using oxidizing gas, oxidizing gas includes one in oxygen, carbon monoxide, carbon dioxide and air
The mixture of one or more of kind or several or above-mentioned gas with inert gas.
With embodiment, the present invention is described in detail below.Embodiment 1-5 is the preparation of porous carbon-based NiMo catalyst.
Embodiment 6 is the reaction evaluating of catalyst.
Embodiment 1: traditional NiMo/C catalyst preparation is labeled as comparative example NiMo/C-1.
By 10g, 10-20 mesh coal base porous carbon is put into 100ml beaker, and 10ml is added and is prepared in advance containing 12wt%Mo,
The NiMoP solution of 3wt%Ni, 0.5wt%P.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred to
In 250ml Rotary Evaporators, it is heated to 85 DEG C and is evaporated dipping liquor.It pours into another dry beaker, stands overnight.General
It dries 6 hours for 120 DEG C, takes out in logical drying box.
Catalyst precursor calcining carries out in tube furnace.Tube furnace internal diameter 60mm, long 1000mm.Quartz ampoule in tube furnace
Diameter 55mm is about 1400mm, constant temperature zone 400mm.NiMo/C material after drying is packed into long 100mm, wide 30mm quartz boat
It is interior.Above-mentioned quartz boat is pushed into quartz ampoule middle section, is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected
Cutting ferrule makes front end cutting ferrule be connected with air inlet, and cutting ferrule outlet end is connected with absorption bottle.It is passed through nitrogen, air inlet gas is by mass flow
Meter control, flow velocity 400ml/min.After airtight test is errorless, start to warm up.Reaction temperature is risen to 3 DEG C/min from room temperature
500 DEG C, constant temperature 4 hours.It was taken out after the near room temperature of reaction temperature after second day, catalyst is labeled as NiMoC-1.
The preparation of embodiment 2:NiMo/C-2 catalyst, the precursor solution in the embodiment are single W metal, Mo
Water-soluble solution.
It measures 50ml 6M dilute nitric acid solution (concentrated nitric acid is mixed with deionized water by 1:1), is placed in 250ml beaker.It weighs
20g, 10-20 mesh coal base porous carbon.Porous carbon is soaked in solution, is ultrasonically treated 10 minutes, displaces bubble.Continue to impregnate
It is taken out after 2 hours, washing to cleaning solution is PH=7.
Coal base porous carbon after 10g is activated is put into 100ml beaker, and the 12wt% molybdenum that 10ml is prepared in advance is added
Acid ammonium solution.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred in 250ml Rotary Evaporators, heated
Dipping liquor is evaporated to 85 DEG C.It pours into another dry beaker, stands overnight.80 DEG C of bakings 12 are small in vacuum oven
When, it takes out.
Catalyst precursor calcining carries out in tube furnace.Tube furnace internal diameter 60mm, long 1000mm.Quartz ampoule in tube furnace
Diameter 55mm is about 1400mm, constant temperature zone 400mm.Mo/C material after drying is packed into long 100mm, in wide 30mm quartz boat.
Above-mentioned quartz boat is pushed into quartz ampoule middle section, is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected into card
Set, makes front end cutting ferrule be connected with air inlet, is passed through nitrogen, air inlet gas is controlled by mass flowmenter, flow velocity 400ml/min.Gas
After close property inspection is errorless, start to warm up.Reaction temperature rises to 500 DEG C, constant temperature 4 hours from room temperature with 3 DEG C/min.It is anti-to second day
Temperature is answered to be cooled to room temperature taking-up.
Porous carbon after above-mentioned dipping Mo is reentered into 100ml beaker, it is molten that the nickel nitrate that 10ml is prepared in advance is added
Liquid.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred in 250ml Rotary Evaporators, are heated to 85 DEG C
Dipping liquor is evaporated.It pours into another dry beaker, stands overnight.It dries 12 hours for 80 DEG C, takes out in vacuum oven.
Catalyst precursor calcining carries out in tube furnace.It is identical when reaction condition is with calcining ammonium molybdate presoma.It is airtight
Property check it is errorless after, start to warm up.Reaction temperature rises to 500 DEG C, constant temperature 4 hours from room temperature with 3 DEG C/min.It was reacted to second day
It is taken out after the near room temperature of temperature, catalyst number is NiMoC-2.
The preparation of embodiment 3:NiMo/C-3 catalyst
It measures the dilute sulphur liquid of 50ml 9mol/L (concentrated sulfuric acid is mixed with deionized water by 1:1), is placed in 250ml beaker.It weighs
20g 10-20 mesh coal base porous carbon.Porous carbon is soaked in solution, is ultrasonically treated 10 minutes, displaces bubble.Continue to impregnate
It is taken out after 6 hours, washing to cleaning solution is PH=7.
Coal base porous carbon after 10g is activated is put into 100ml beaker, and 10ml 12wt%Mo, 3wt%Ni is added,
The NiMoP solution of 0.5wt%P.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred to 250ml rotation to steam
It sends out in instrument, is heated to 85 DEG C and is evaporated dipping liquor.It pours into another dry beaker, stands overnight.In vacuum oven
80 DEG C are dried 12 hours, are taken out.
Catalyst precursor calcining carries out in tube furnace.Tube furnace internal diameter 60mm, long 1000mm.Quartz ampoule in tube furnace
Diameter 55mm is about 1400mm, constant temperature zone 400mm.NiMo/C material after drying is packed into long 100mm, wide 30mm quartz boat
It is interior.Above-mentioned quartz boat is pushed into quartz ampoule middle section, is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected
Cutting ferrule makes front end cutting ferrule be connected with air inlet, and cutting ferrule outlet end is connected with absorption bottle.It is passed through nitrogen, air inlet gas is by mass flow
Meter control, flow velocity 400ml/min.After airtight test is errorless, start to warm up.Reaction temperature is risen to 3 DEG C/min from room temperature
500 DEG C, constant temperature 4 hours.It was taken out after the near room temperature of reaction temperature after second day, catalyst is labeled as NiMoC-3.
The preparation of embodiment 4:NiMo/C-4 catalyst
It measures 10g potassium permanganate to be placed in 100ml deionized water, dissolve by heating.Solution is placed in 250ml beaker.Claim
Take 20g 10-20 mesh coal base porous carbon.Porous carbon is soaked in solution, is ultrasonically treated 10 minutes, displaces bubble.Continue to soak
It steeps and takes out afterwards overnight (12 hours), washing to cleaning solution is PH=7.
Coal base porous carbon after 10g is activated is put into 100ml beaker.Basic nickel carbonate, ammonium molybdate are dissolved in ammonia
NiMo ammonia solution is prepared in water.Taking-up contains 2.4wt%Mo, the NiMo ammonia solution 50ml of 0.6wt%Ni, using excessive dipping side
Method impregnates above-mentioned porous carbon.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred to 250ml rotary evaporation
In instrument, it is heated to 85 DEG C and is evaporated dipping liquor.It pours into another dry beaker, stands overnight.
The drying and calcination of catalyst carry out all in tube furnace.Tube furnace internal diameter 60mm, long 1000mm.Stone in tube furnace
English pipe diameter 55mm is about 1400mm, constant temperature zone 400mm.NiMo/C material is packed into long 100mm, in wide 30mm quartz boat.It will
Above-mentioned quartz boat is pushed into quartz ampoule middle section, is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected into cutting ferrule,
Front end cutting ferrule is set to be connected with air inlet, cutting ferrule outlet end is connected with absorption bottle.It is passed through nitrogen, air inlet gas is by mass flowmenter control
System, flow velocity 400ml/min.After airtight test is errorless, start to warm up.Under nitrogen atmosphere, risen to 5 DEG C/min from room temperature
After 120 degree, constant temperature 4 hours, continue to rise to 500 DEG C, constant temperature 4 hours from room temperature with 3 DEG C/min.It is near to second day reaction temperature
It is taken out after room temperature, catalyst is labeled as NiMoC-4.
The preparation of embodiment 5:NiMo/C-5 catalyst
Activation, drying and calcination in catalyst preparation process carry out all in tube furnace.Tube furnace internal diameter 60mm, it is long
1000mm.Quartz tube 55mm in tube furnace is about 1400mm, constant temperature zone 400mm.The quartz boat of coal base porous carbon will be housed
It is pushed into quartz ampoule middle section, is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected into cutting ferrule, make front end cutting ferrule
It is connected with air inlet, cutting ferrule outlet end is connected with absorption bottle.It is passed through oxidizing gas (oxidizing gas CO2With the mixed gas of nitrogen,
Wherein CO2Account for 5% volume), air inlet gas is controlled by mass flowmenter, flow velocity 400ml/min.After airtight test is errorless,
It starts to warm up.600 DEG C of activation are risen to from room temperature with 3 DEG C/min, constant temperature 2 hours.It was taken after the near room temperature of reaction temperature after second day
Out.
Coal base porous carbon after 10-20 mesh 10g is activated is put into 100ml beaker, and 10ml is added and contains 12wt%
The NiMoP solution of Mo, 3wt%Ni, 0.5wt%P.Ultrasonic treatment 30 minutes is stood.Above-mentioned carbon material and maceration extract are transferred to
In 250ml Rotary Evaporators, it is heated to 85 DEG C and is evaporated dipping liquor.It pours into another dry beaker, stands overnight.
NiMo/C material is reloaded into long 100mm, in wide 30mm quartz boat.Quartz boat is pushed into quartz ampoule middle part
Point, it is allowed to be located in diamond heating flat-temperature zone.Quartz ampoule both ends are connected into cutting ferrule, so that front end cutting ferrule is connected with air inlet, cutting ferrule
Outlet end is connected with absorption bottle.It is passed through nitrogen, air inlet gas is controlled by mass flowmenter, flow velocity 400ml/min.Air-tightness inspection
Look into it is errorless after, start to warm up.Under nitrogen atmosphere, after rising to 120 degree, constant temperature 4 hours from room temperature with 5 DEG C/min, continue with 3 DEG C/
Min rises to 500 DEG C, constant temperature 4 hours from room temperature.It was taken out after the near room temperature of reaction temperature after second day, catalyst is labeled as
NiMoC-5。
6 catalyst HDS reaction evaluating of embodiment
Present case is the reaction evaluating of the catalyst in embodiment 1-5.
The reaction evaluating of catalyst is completed in fixed bed type reactor.0.5g, 1.0g, 1.5g are weighed respectively every time,
2.0g, 3.0g NiMo/C catalyst, are placed in the constant temperature zone of fixed bed reactors, to 180 DEG C of drying and dehydratings and are kept by room temperature
60min is passed through decahydronaphthalene solvent later to soak catalyst, raw material is come into full contact with when entering with catalyst.To ten
Hydrogen naphthalene penetrates catalytic bed, starts to warm up to 230 DEG C and is passed through vulcanizing agent, starts preliminary presulfurization.After preliminary vulcanization 120min,
360 DEG C of beginning depth vulcanizations are warming up to, depth prevulcanisation time is 8 hours.After vulcanization, reaction temperature is maintained 350
DEG C, reaction velocity 3h-1, Hydrogen Vapor Pressure 4.0MPa, hydrogen-oil ratio 500:1 after stablizing 24 hours, start sampling analysis.By adding hydrogen
It is analog raw material oil that desulphurization reaction, which evaluates raw material, and solvent is decahydronaphthalene, and simulated sulfuration object is dibenzothiophenes, and concentration is 1000 μ
g/L.Embodiment 1-5 comparing result is shown in Table 1.
Table 1 compares the reactivity of each catalyst.
Can be seen that from embodiment and comparative example, using in this patent implementation method acid oxidase and gas aoxidize to carbon substrate
Material carries out surface and is modified, and can improve the interaction of metal component Yu carbon material carrier.By modified carbon-based material uniform
NiMoP solution or the respectively solution containing single Mo and single Ni carry out distribution dipping, drying, the obtained catalyst ratio of calcining
The similar carbon-based NiMo catalyst of traditional handicraft preparation has higher hydrodesulfurization reaction activity.
Claims (10)
1. a kind of preparation method of high activity hydrogenation and desulphurization catalyst, which is characterized in that this method be using carbon-based material as carrier,
It is modified that carbon-based material is subjected to surface；Preparation contains Ni, Mo or the hydrodesulfurization containing Co, Mo or containing Ni, Mo active component
Precursor solution impregnates modified carbon-based material in precursor solution, by activity component impregnation in carrier surface, then
It is dried, calcines, obtain the carbon-based Hydrobon catalyst containing NiMo or CoMo or NiMo active component.
2. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 1, which is characterized in that the carbon
Sill includes activated carbon, activated carbon fiber, carbon nano-fiber, carbon nanotube, graphene nanobelt, mesoporous carbon.
3. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 1, which is characterized in that carbon substrate
It is oxidation processes, including the activation of acid oxidase, oxidizing gas, potassium permanganate oxidation that material, which carries out the modified method in surface,.
4. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 3, which is characterized in that for acid
The inorganic acid of oxidation includes nitric acid and/or sulfuric acid；Organic acid for acid oxidase includes the peroxide or peroxide of carboxylic acid or carboxylic acid
Change hydrogen.
5. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 3, which is characterized in that be used for oxygen
The gas of the property changed gas activation includes one or more of oxygen, carbon monoxide, carbon dioxide and air or above-mentioned gas
The mixture of one or more of body and inert gas, the inert gas include nitrogen, argon gas, helium.
6. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 1, which is characterized in that contain
The precursor solution of Ni, Mo active component is the mixed solution containing Ni and Mo or contains single W metal, single gold respectively
Belong to two kinds of solution of Mo；Precursor solution containing Co, Mo active component is the mixed solution containing Co and Mo or contains respectively
There are two kinds of solution of single metal Co, single metal Mo；Precursor solution containing Ni, Mo active component is to contain Ni's and Mo
Mixed solution or respectively two kinds of solution containing single W metal, single metal Mo.
7. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 6, which is characterized in that work as forerunner
Liquid solution is when containing two kinds of solution of single metal respectively, by carbon-based material and two kinds of single metal precursor water-soluble solutions
Incipient impregnation or excessive dipping, dry, calcining are carried out respectively.
8. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 1, which is characterized in that described dry
Dry includes dry, vacuum drying under air conditions, inert gas shielding is dry, oxidizing gas is dry or reducibility gas is dry
It is dry.
9. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 8, which is characterized in that using empty
When dry under the conditions of gas, drying temperature is lower than 300 DEG C；
Using vacuum drying when, vacuum degree be -101.325Ka to 0, vacuum drying temperature in the vacuum degree boiling temperature 80%
More than；
When dry using oxidizing gas, oxidizing gas include one of oxygen, carbon monoxide, carbon dioxide and air or
Person is the mixture of one or more of above-mentioned gas with inert gas；
The dry reducibility gas of reducibility gas includes a kind of in hydrogen, ammonia or carbon monoxide；The either above reproducibility
The mixed gas of gas and inert gas, reducibility gas shared volume ratio in mixed gas is 0.5%-99.5%；
The inert gas includes nitrogen, argon gas, helium.
10. a kind of preparation method of high activity hydrogenation and desulphurization catalyst according to claim 1, which is characterized in that calcining
Temperature is 150-1000 DEG C；Calcination time terminates since room temperature to calcining, and the time is -50 hours 10 minutes.
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