CN103084180B - Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring - Google Patents

Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring Download PDF

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CN103084180B
CN103084180B CN201310062690.9A CN201310062690A CN103084180B CN 103084180 B CN103084180 B CN 103084180B CN 201310062690 A CN201310062690 A CN 201310062690A CN 103084180 B CN103084180 B CN 103084180B
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aromatic ring
catalyst
nickel
autoclave
amorphous metal
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CN103084180A (en
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魏贤勇
亓士超
李占库
王玉高
李鹏
柳方景
宗志敏
樊星
赵云鹏
赵炜
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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Priority to PCT/CN2013/074457 priority patent/WO2014131232A1/en
Priority to JP2015559403A priority patent/JP6068683B2/en
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Abstract

The invention relates to a preparation method of a supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of an aromatic ring, belonging to a preparation method of a catalyst for realizing catalytic full hydrogenation of an aromatic ring. The method comprises the following steps: sequentially adding 10-1000 milliliters of organic solvent ether, 1-40 grams of catalyst carrier and 1-100 milliliters of nickel carbonyl into a high-pressure reaction kettle of which a cover is opened, and the closing the cover; enabling high-purity nitrogen gas to slowly flow in through a gas inlet and then flow out through a gas outlet, then slowing introducing high-purity hydrogen gas into the high-pressure reaction kettle to 2-8 MPa through the gas inlet, and then closing a valve of the gas inlet; starting a motor to drive a magnetic stirrer, and sufficiently stirring and mixing at room temperature; and then, quickly heating while fast stirring, keeping the temperature when rising to 70-280 DEG C, and enabling the nickel carbonyl adsorbed on the surface of the carrier to be resolved into elementary nickel substances and attached onto the surface of the carrier, thus preparing the supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of an aromatic ring. The invention has the following advantages: the catalytic full hydrogenation conversion rate of aromatic hydrocarbon substances is remarkable, the hydrogenation operation is thorough, and the catalytic effect is extremely rare, efficient and excellent.

Description

The preparation method of the full hydrogenation carried type, super-fine of catalysis aromatic ring amorphous metal Raney nickel
Technical field
Content of the present invention relates to the preparation method of the full hydrogenation catalyst of a kind of catalysis aromatic ring, particularly the preparation method of the full hydrogenation carried type, super-fine of a kind of catalysis aromatic ring amorphous metal Raney nickel.
Background technology
Due to by oil shortage and the oil serious puzzlement of the problem such as heaviness, in poor quality increasingly that can refine, produce in recent years the technology progressive and development just rapidly of liquid fuel with coal direct coal liquefaction and indirect liquefaction in China.How to solve DCL/Direct coal liquefaction obtain portion of product---high concentration aromatic hydrocarbons deep hydrogenation is converted into light components; How solving ICL for Indirect Coal Liquefaction and prepare the accessory substance obtaining in ethanol petrol process---heavy benzol effectively hydrogenation is converted into high-quality cleaning liquid fuel; How to solve and reduce the quality of aromatic ring content in oil product, raising liquid fuel and improve the series of problems such as quality of air environment by perhydrogenate, be related to key point in the urgent need to address in China's national economy benign development process by being.And the core technology addressing these problems and bottleneck problem mainly concentrate on effectively develop catalytic hydrogenation effect significantly, be suitable for large-scale production and preparation is simple, cheap, non-noble metal catalyst.
From Shell since within 1992, setting up First two-stage hydrogenation treating apparatus and going into operation, in the world numerous well-known PETROLEUM PROCESSING companies as: the companies such as shell, BP, A Moke, A Ke, Castrol, Nippon oil company and PetroChina Company Limited., China Petrochemical Industry follow the tracks of aromatic ring two-stage hydrogenation technique and the technology of having researched and developed series of new in succession.The core content of this technology comprises that first paragraph has adopted with CoNi, NiMo or NiCo/ γ-Al 2o 3support type is as catalyst, greatly about 310-410 oC, harsher hydroconversion condition under pressure 8-14 MPa, second segment has adopted filling Pd or Pt noble metal catalyst, greatly about 200-300 oC, under pressure 8-14 MPa, but two-step catalyzing hydrogenation only realized arene content and has been down to the limit object of 9 wt%, and not finally makes the complete saturated naphthenic non-aromatics that is converted into of catalysis aromatic ring.
The result of study in many laboratories shows: the Pt noble metal catalyst perhydrogenate product of Phenanthrene is about 10%, the Pt precious metal alloys catalytic hydrogenation product naphthane of naphthalene is 70%; Under temperate condition, the Pt precious metal alloys catalyst perhydrogenate product of heavy benzol is only 27%; There is not yet and be reported in all hydrogenated effective example of durol catalysis under temperate condition.
Compared with noble metal catalyst, the achievement in research of base metal (being mainly nickel and nickel alloy) catalyst should more worthly have promotion and application, because base metal has better economic advantages and more wide in range source.NiW and NiMo remain the desirable double non-noble metal metallic catalyst combination of aromatic hydrogenation, Halachev has studied Ti-HMS mesoporous material load NiMo and the catalytic hydrogenation of NiW to naphthalene, compared with NiMo, NiW catalyst shows higher catalytic activity, and the decahydronaphthalene productive rate of Ni-W/Ti-HMS catalysis reaches 70%.Be subject to the reasons such as the restriction of catalyst preparation technology and changing effect be not good, relevant achievement in research is difficult to further promotion and application at present.
The above-mentioned noble who relates to or non-precious metal catalyst are all to utilize the conventional method preparations such as dipping, colloidal sol, sol-gel process and in-situ reducing substantially.These preparation methods and process and loaded down with trivial details, main cause is wherein all to relate to hydrogen reduction operating procedure.First to modulate slaine, the bimetallic salt complex of solubility or be immersed in the slaine on carrier, then after high-temperature roasting, also will utilize reducing atmosphere (hydrogen) to reduce and just may prepare the elemental metals catalyst with hydrogenation.Because any step that relates to roasting all can significantly reduce the metallic catalyst specific area of (comprising carrier), increase the melt polymerization of catalyst metals active principle or the chance of reunion simultaneously.Finally cause the serviceability temperature of catalyst low by (120-200 oC) may be not high, but the pretreated reduction temperature of catalyst is too high by (400 oc-700 oc) too high, lose time, waste energy.
Begin one's study and apply at the 1980's metal carbonyl, the people such as Mahajan finds to utilize the ultrasonic wave can decomposing metal carbonyl compound and obtain nano metal particles afterwards.The people such as Redel, by the carbonyls of the metals such as thermal decomposition cobalt, rhodium, iridium, obtain corresponding nano-metal particle in ionic liquid.But utilize, directly to prepare metallic catalyst after metal carbonyl or its load be not to be still easy to thing, because the volatilization temperature of most metal carbonyl is significantly less than decomposition temperature.
The gasification temperature of carbonyl nickel is 42.5 oc, be heated to 130 othere is decomposition and be converted into ultra-fine metallic nickel simple substance in C.The metallic nickel particle adding after thermal decomposition can keep higher metal catalytic activity and be easy to control size and the bulk density of particle, and the carbonyl nickel after carbonyl nickel, particularly load is expected to the presoma as desirable metallic catalyst.Compared with conventional method, the catalyst of preparation not only can omit the step of nickel salt solution roasting pretreatment like this, key is that need under exacting terms relatively, again not utilize hydrogen reducing oxidation state nickel be the process with the metallic nickel simple substance of catalytic activity, greatly optimize, simplified preparation and the operating procedure of catalyst, in process, be also easy to the apparent parameter of the various physics of catalyst of adjusting and controlling simultaneously.
Summary of the invention
The object of the invention is to provide that a kind of preparation process and technique are extremely simple, the preparation method of safety, convenience, the feasible full hydrogenation carried type, super-fine of catalysis aromatic ring amorphous metal Raney nickel.
The object of the present invention is achieved like this: the preparation method of this catalyst comprises apparatus and method, described method: under temperate condition, the preparation method's of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring concrete steps are as follows:
One, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of preparation catalysis aromatic ring:
Add successively organic solvent 10-1000 milliliter ether to opening in the autoclave of lid, the carrier 1-40g of catalyst, the upper cover of autoclave on carbonyl nickel 1-100 milliliter bonnet, and be bolted sealing; Open gas inlet on autoclave body and the valve of gas outlet, then the high pure nitrogen slowly flowing into from gas inlet flows out from gas outlet again, displaces the inner a small amount of air of autoclave body; Adopt identical operation to carry out nitrogen replacement three times, then the valve of opening the gas inlet of reactor and closing gas outlet, in slowly from gas inlet to autoclave, pass into high-purity hydrogen, show that to the Pressure gauge on autoclave first pressing is the valve of closing air inlet after 2-8MPa;
Described organic solvent is one or more mixed solvents in methyl alcohol, ethanol, ether, cyclohexane, benzinum, n-hexane; Described catalyst carrier is α-Al 2o 3, β-Al 2o 3, γ-Al 2o 3, SiO 2, TiO 2, one or more mixed carriers in 4A molecular sieve, ZSM-5 zeolite, MCM-41; Described carbonyl nickel is Ni (CO) 4or Ni (CO) 5or the mixture of both arbitrary proportions;
Under hydrogen atmosphere, by adjusting the parameter of control panel, to open motor and drive magnetic stirring apparatus, the slowly organic solvent in agitated autoclave body, catalyst carrier and carbonyl nickel solution mixture, is at room temperature fully uniformly mixed 0.1-5 hour; Then improve mixing speed, under rapid stirring speed and rapidly, heat, temperature is raised to 70 oc-280 oc, under the condition that maintains stirring, keep high pressure temperature in the kettle 1-8 hour, during this time in high pressure hydrogen reducing atmosphere, being attracted to carbonyl nickel on carrier surface, decomposition in situ fast, fully occurs is nickel simple substance, and be attached to equably on the surface of carrier with ultra-fine, amorphous particle form, so just prepare the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring;
The device of realizing method for preparing catalyst includes: motor, magnetic stirring apparatus, air inlet, gas outlet, nut, autoclave body, thermocouple, Pressure gauge, stirring arm, control panel and electric furnace; Motor is connected with magnetic stirring apparatus by sleeve, and the bottom of magnetic stirring apparatus is connected with stirring arm; The upper cover of autoclave body is connected with autoclave body by nut, is connected with Pressure gauge upper covering, and is inserted with thermocouple by upper cover, is connected with respectively two and gathers around valvular pipeline upper covering, and pipeline is connected with air inlet and gas outlet respectively; Autoclave body is placed in electric furnace, and electric furnace is connected with control panel.
Beneficial effect, owing to having used such scheme, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring prepared by the inventive method can be under gentle condition, make completely benzene, toluene, naphthalene, anthracene, phenanthrene, heavy benzol (polyalkylbenzene mixture) and even catalytic hydrogenation and difficulty durol in the whole catalytic hydrogenations of unsaturated phenyl ring, generate all hydrogenated full saturated rings alkane or alkyl and replace full saturated rings alkane.
Owing to having adopted the technology of high pressure, reducing atmosphere, original position directional decomposition, the presoma of catalyst---be immersed in the active ingredient nickle atom that can fully be deposited catalyst in carbonyl nickel system in carrier hole, on carrier, all nickle atoms can farthest be brought into play its catalytic hydrogenation activity simultaneously;
Be attached to the structure of nickle atom on carrier and belong to indefiniteness state, noncrystalline arrangement because the structure (being learnt by characterization parameter) of catalyst has, the nickle atom of these nano level superfines and showing do not reunite, fine and close, scattered architectural feature, can realize catalyst active ingredient nickel element consumption completely few, the object of the cheap catalyst of preparation that cost is low.
Because the preparation process of catalyst does not need to pass through high-temperature roasting again, traditional complex steps and the preparation condition such as hydrogen reducing is comparatively gentle again, thoroughly improve and greatly simplified method of operating and the process of traditional catalyst, be easier to extension application because the device of Kaolinite Preparation of Catalyst is simple, easy and simple to handle, save time, save the energy, preparation method and technology.
Advantage: utilize the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring of preparing in content of the present invention can be under comparatively gentle condition, realize the full hydrogenation of all phenyl ring catalysis in the full hydrogenation of catalysis, heavy benzol compound (Multi substituted benzenes mixture) of all unsaturated rings in the condensing polyaromatic hydrocarbons such as the full hydrogenation of coal alkyl phenyl ring catalysis, model naphthalene and there is not yet the durol catalytic hydrogenation of report, can under very gentle condition, realize durol in the full hydrogenation of phenyl ring catalysis.The full hydrogenation conversion of catalysis of above-mentioned aromatic hydrocarbon substance is remarkable, hydrogenation thoroughly, be the full hydrogenation catalyst of very rarely seen, efficient, the remarkable arenes catalytic of a kind of catalytic effect.
Brief description of the drawings
Fig. 1 is structure drawing of device of the present invention.
In figure, 1, motor; 2, magnetic stirring apparatus; 3, air inlet; 4, gas outlet; 5, nut; 6, autoclave body; 7, thermocouple; 8, Pressure gauge; 9, stirring arm; 10, control panel.
Detailed description of the invention
Performance indications and the catalytic effect of preparation method, operating condition and the catalyst of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring:
Embodiment 1:
1, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring:
In the autoclave of opening lid, add successively 40 milliliters of benzinums, the β-Al of catalyst 2o 3carrier 4g, carbonyl nickel (CO) 4after 100 milliliters, cover autoclave kettle 6, and by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass into high pure nitrogen in kettle 0.1 hour for replacing the air in former still.Adopt identical operation after nitrogen replacement, to open gas inlet 3 valves of reactor the valve of closing gas outlet 4 in triplicate, slowly pass into high-purity hydrogen to the Pressure gauge 8 autoclave from gas inlet 3 and show that first pressing is to close air inlet 3 valves after 8MPa.
Under hydrogen atmosphere, by adjusting the parameter of control panel 10, open motor 1 and drive magnetic stirring apparatus 2, slowly stir organic solvent, catalyst carrier and carbonyl nickel solution mixture in kettle 6, at room temperature system is fully uniformly mixed 0.1 hour.Then improve fast under mixing speed and be heated to rapidly 140 oc, autoclave insulation 2 hours under the condition that maintains stirring, during this time in high pressure hydrogen reducing atmosphere, being attracted to carbonyl nickel on carrier surface, decomposition in situ fast, fully occurs is nickel simple substance, and be attached to equably on the surface of carrier with ultra-fine, amorphous particle form, so just prepare the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring.
The device of realizing method for preparing catalyst includes: motor 1, magnetic stirring apparatus 2, air inlet 3, gas outlet 4, nut 5, autoclave body 6, thermocouple 7, Pressure gauge 8, stirring arm 9, control panel 10 and electric furnace 11; Motor 1 is connected with magnetic stirring apparatus 2 by sleeve, and the bottom of magnetic stirring apparatus 2 is connected with stirring arm 9; The upper cover of autoclave body 6 is connected with autoclave body 6 by nut 5, is connected with Pressure gauge 8 upper covering, and is inserted with thermocouple 7 by upper cover, is connected with respectively two and gathers around valvular pipeline upper covering, and pipeline is connected with air inlet 3 and gas outlet 4 respectively; Autoclave body 6 is placed in electric furnace 11, and electric furnace 11 is connected with control panel 10.
Fast autoclave is taken out from add electrothermal furnace 11 afterwards, and autoclave is placed in frozen water to quenching 1 hour, then open gas outlet 3 and slowly emit mist (will carry out exhaust aftertreatment) in reactor 6 to the air inlet 3 of opening again reactor after Pressure gauge 8 is shown as normal pressure, slowly pass in still high pure nitrogen 1 hour by the valve of gas inlet 3, all the time under nitrogen protection from the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of autoclave body 6 interior taking-up catalysis aromatic ring, the catalyst newly preparing is placed in air dry under nitrogen atmosphere and after 1 hour, puts into that to be filled with the drier of nitrogen atmosphere stand-by.
2, the performance indications of catalyst and catalytic effect:
Open and in the autoclave of lid, add successively 20 milliliters of the interior n-hexanes of autoclave kettle 6, new system carried type, super-fine amorphous metal Raney nickel 0.5g and the reactant toluene 0.6g for the full hydrogenation of catalysis aromatic ring, cover can kettle cover after by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass in kettle 5 minutes for replacing the valve of closing gas outlet 4 after the high-purity hydrogen of air in former still, continue to pass into high-purity hydrogen to the Pressure gauge 8 on autoclave and show that first pressing is the valve of closing air inlet 3 after 5MPa.Dial 10 makes it control motor 1 drive magnetic stirring apparatus 9 and heating system, control simultaneously programming rate in 20 minutes to 120 oafter C, constant temperature keeps 10 hours, fast autoclave body 6 is taken out from add electrothermal furnace 11 afterwards, and autoclave body 6 is placed in frozen water to quenching 1 hour.
Utilize gas chromatograph/mass spectrum (GC/MS) to learn with the result of variations of combining analytical system reactant and product: toluene is 150 oc can be converted into unique product---the hexahydrotoluene of the whole hydrogenation of aromatic ring completely.By with traditional benzene hydrogenating catalyst comparison, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring prepared by this method has the whole hydrogenation of unsaturated phenyl ring that significantly make in toluene under temperate condition, effect is very remarkable.
The sign of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring is as follows:
Results of elemental analyses shows: except the carrier components of ZSM-5 catalyst, effective element nickel is 100%; XRD analysis result shows: on carrier surface nickel diffraction maximum be all almost amorphous, without the state of crystallization; TEM high-definition picture analysis result shows: clearly observe nickel and be deposited on ZSM-5 inner surface with high degree of dispersion degree, non-particulate accumulation, form even, fine and close, amorphous lattice, the diameter of figure spherical metal particle is approximately less than 20 nm.BET analysis result shows: utilize average semiaperture data < 2 nm after ZSM-5 load carbonyl nickel, can think that the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring has relatively advanced microcellular structure and abundant specific area.
For driving the motor 1 of agitator to be directly connected 2 with sleeve magnetic stirring apparatus; On autoclave, cover and be connected with respectively two and gather around valvular pipeline, for regulating and control the air inlet 3 of inert nitrogen gas and reactor feed gas hydrogen and the gas outlet 4 of release reaction system; Temperature in course of reaction, pressure show and stir and can set and manual operation at control panel 10, is respectively thermocouple 7, Pressure gauge 8 and stirring arm 9 for realizing the transmission part of relevant data; The pressure that reaction system needs come from extraneous initial Hydrogen Vapor Pressure and reactor is airtight be heated after the interior pressure that produces of mass expanded.
Embodiment 2:
1, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring:
In the autoclave of opening lid, add successively 200 milliliters of ether, the ZSM-5 zeolite carrier 10g of catalyst, carbonyl nickel (CO) 4on 60 milliliters of bonnets in autoclave kettle 6, and by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass into high pure nitrogen in kettle 0.1 hour for replacing the air in former still.Adopt identical operation after nitrogen replacement, to open gas inlet 3 valves of reactor the valve of closing gas outlet 4 in triplicate, slowly pass into high-purity hydrogen to the Pressure gauge 8 autoclave from gas inlet 3 and show that first pressing is 5MPaafter close air inlet 3 valves.
Under hydrogen atmosphere, by adjusting the parameter of control panel 10, open motor 1 and drive magnetic stirring apparatus 2, slowly stir organic solvent, catalyst carrier and carbonyl nickel solution mixture in kettle 6, at room temperature system is fully uniformly mixed 3 hours.Then improve fast under mixing speed and be heated to rapidly 180 oc, autoclave insulation 2 hours under the condition that maintains stirring, during this time in high pressure hydrogen reducing atmosphere, being attracted to carbonyl nickel on carrier surface, decomposition in situ fast, fully occurs is nickel simple substance, and be attached to equably on the surface of carrier with ultra-fine, amorphous particle form, so just prepare the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring.
Fast autoclave is taken out from add electrothermal furnace 11 afterwards, and autoclave is placed in frozen water to quenching 0.5 hour, then open gas outlet 3 and slowly emit mist (will carry out exhaust aftertreatment) in reactor 6 to the air inlet 3 of opening again reactor after Pressure gauge 8 is shown as normal pressure, slowly pass in still high pure nitrogen 0.5 hour by the valve of gas inlet 3, all the time under nitrogen protection from the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of autoclave body 6 interior taking-up catalysis aromatic ring, the catalyst newly preparing is placed in air dry under nitrogen atmosphere and after 0.5 hour, puts into that to be filled with the drier of nitrogen atmosphere stand-by.
2, the performance indications of catalyst and catalytic effect:
Open and in the autoclave of lid, add successively 20 milliliters of the interior n-hexanes of autoclave kettle 6, new system carried type, super-fine amorphous metal Raney nickel 0.5g and the reactant naphthalene 0.6g for the full hydrogenation of catalysis aromatic ring, cover can kettle cover after by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass in kettle 5 minutes for replacing the valve of closing gas outlet 4 after the high-purity hydrogen of air in former still, continue to pass into high-purity hydrogen to the Pressure gauge 8 on autoclave and show that first pressing is the valve of closing air inlet 3 after 5MPa.Dial 10 makes it control motor 1 drive magnetic stirring apparatus 9 and heating system, control simultaneously programming rate in 20 minutes to 220 oafter C, constant temperature keeps 20 hours, fast autoclave body 6 is taken out from add electrothermal furnace 11 afterwards, and autoclave body 6 is placed in frozen water to quenching 1 hour.
Utilize gas chromatograph/mass spectrum (GC/MS) to learn with the result of variations of combining analytical system reactant and product: naphthalene is 220 oc can be converted into unique product---the decahydronaphthalene of the whole hydrogenation of aromatic ring completely.By with traditional many cyclophanes ring hydrogenation catalyst comparison, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of many rings catalysis aromatic ring prepared by this method has and significantly makes di pah under temperate condition---and all whole hydrogenation of unsaturated ring in naphthalene, effect is very remarkable.
The sign of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring is as follows:
Results of elemental analyses shows: except the carrier components of ZSM-5 catalyst, effective element nickel is 100%; XRD analysis result shows: on carrier surface nickel diffraction maximum be all almost amorphous, without the state of crystallization; TEM high-definition picture analysis result shows: clearly observe nickel and be deposited on ZSM-5 inner surface with high degree of dispersion degree, non-particulate accumulation, form even, fine and close, amorphous lattice, the diameter of figure spherical metal particle is approximately less than 20 nm.BET analysis result shows: utilize average semiaperture data < 2 nm after ZSM-5 load carbonyl nickel, can think that the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring has flourishing microcellular structure and abundant specific area.
Embodiment 3:
1, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring:
In the autoclave of opening lid, add successively 100 milliliters of methyl alcohol, the TiO of catalyst 2zeolite support 20g, carbonyl nickel (CO) 40on 10 milliliters of bonnets in autoclave kettle 6, and by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass into high pure nitrogen in kettle 1 hour for replacing the air in former still.Adopt identical operation after nitrogen replacement, to open the gas inlet 3 of reactor the valve of closing gas outlet 4 in triplicate, slowly from gas inlet 3 pass into high-purity hydrogen to the Pressure gauge 8 autoclave show first pressing be close after 2MPa till air inlet 3.
Under hydrogen atmosphere, by adjusting the parameter of control panel 10, open motor 1 and drive magnetic stirring apparatus 2, slowly stir organic solvent, catalyst carrier and carbonyl nickel solution mixture in kettle 6, at room temperature system is fully uniformly mixed 2 hours.Then improve fast under mixing speed and be heated to rapidly 220 oc, autoclave insulation 2 hours under the condition that maintains stirring, during this time in high pressure hydrogen reducing atmosphere, being attracted to carbonyl nickel on carrier surface, decomposition in situ fast, fully occurs is nickel simple substance, and be attached to equably on the surface of carrier with ultra-fine, amorphous particle form, so just prepare the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring.
Fast autoclave is taken out from add electrothermal furnace 11 afterwards, and autoclave is placed in frozen water to quenching 2 hours, then open gas outlet 3 and slowly emit mist (will carry out exhaust aftertreatment) in reactor 6 to the air inlet 3 of opening again reactor after Pressure gauge 8 is shown as normal pressure, slowly pass in still high pure nitrogen 0.5 hour by the valve of gas inlet 3, all the time under nitrogen protection from the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of autoclave body 6 interior taking-up catalysis aromatic ring, the catalyst newly preparing is placed in air dry under nitrogen atmosphere and after 0.5 hour, puts into that to be filled with the drier of nitrogen atmosphere stand-by.
2, the performance indications of catalyst and catalytic effect:
Open and in the autoclave of lid, add successively 20 milliliters of the interior n-hexanes of autoclave kettle 6, new system carried type, super-fine amorphous metal Raney nickel 0.5g and heavy benzol (Multi substituted benzenes mixture) 0.6g for the full hydrogenation of catalysis aromatic ring, cover can kettle cover after by bolt 5 fixing seals.Open the gas inlet 3 of reactor and the valve of gas outlet 4, slowly pass in kettle 5 minutes for replacing the valve of closing gas outlet 4 after the high-purity hydrogen of air in former still, continue to pass into high-purity hydrogen to the Pressure gauge 8 on autoclave and show that first pressing is the valve of closing air inlet 3 after 5MPa.Dial 10 makes it control motor 1 drive magnetic stirring apparatus 9 and heating system, control simultaneously programming rate in 20 minutes to 180 oafter C, constant temperature keeps 20 hours, fast autoclave body 6 is taken out from add electrothermal furnace 11 afterwards, and autoclave body 6 is placed in frozen water to quenching 1 hour.
Utilize gas chromatograph/mass spectrum (GC/MS) to learn with the result of variations of combining analytical system reactant and product: heavy benzol (Multi substituted benzenes mixture) is 180 oc can be converted into the alkyl cyclohexane product mixtures (polysubstituted cyclohexane mixture) of the whole hydrogenation of a series of aromatic rings completely.By with traditional alkyl phenyl ring hydrogenation catalyst comparison, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring prepared by this method has under temperate condition significantly makes the whole hydrogenation of unsaturated phenyl ring all in heavy benzol (Multi substituted benzenes mixture), and effect is very remarkable.
The sign of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring is as follows:
Results of elemental analyses shows: except the carrier components of ZSM-5 catalyst, effective element nickel is 100%; XRD analysis result shows: on carrier surface nickel diffraction maximum be all almost amorphous, without the state of crystallization; TEM high-definition picture analysis result shows: clearly observe nickel and be deposited on ZSM-5 inner surface with high degree of dispersion degree, non-particulate accumulation, form even, fine and close, amorphous lattice, the diameter of figure spherical metal particle is approximately less than 20 nm.BET analysis result shows: utilize average semiaperture data < 2 nm after ZSM-5 load carbonyl nickel, can think that the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of freshly prepd catalysis aromatic ring has flourishing microcellular structure and abundant specific area.

Claims (1)

1. a preparation method for the full hydrogenation carried type, super-fine of catalysis aromatic ring amorphous metal Raney nickel, is characterized in that: described method: under temperate condition, the preparation method's of the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring concrete steps are as follows:
One, the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of preparation catalysis aromatic ring:
Add successively organic solvent 10-1000 milliliter ether to opening in the autoclave of lid, the carrier 1-40g of catalyst, the upper cover of autoclave on carbonyl nickel 1-100 milliliter bonnet, and be bolted sealing; Open gas inlet on autoclave body and the valve of gas outlet, then the high pure nitrogen slowly flowing into from gas inlet flows out from gas outlet again, displaces the inner a small amount of air of autoclave body; Adopt identical operation to carry out nitrogen replacement three times, then the valve of opening the gas inlet of reactor and closing gas outlet, in slowly from gas inlet to autoclave, pass into high-purity hydrogen, show that to the Pressure gauge on autoclave first pressing is the valve of closing air inlet after 2-8MPa;
Described organic solvent is one or more mixed solvents in methyl alcohol, ethanol, ether, cyclohexane, benzinum, n-hexane; Described catalyst carrier is α-Al 2o 3, β-Al 2o 3, γ-Al 2o 3, SiO 2, TiO 2, one or more mixed carriers in 4A molecular sieve, ZSM-5 zeolite, MCM-41; Described carbonyl nickel is Ni (CO) 4or Ni (CO) 5or the mixture of both arbitrary proportions;
Under hydrogen atmosphere, by adjusting the parameter of control panel, to open motor and drive magnetic stirring apparatus, the slowly organic solvent in agitated autoclave body, catalyst carrier and carbonyl nickel solution mixture, is at room temperature fully uniformly mixed 0.1-5 hour; Then improve mixing speed, under rapid stirring speed and rapidly, heat, temperature is raised to 70 DEG C-280 DEG C, under the condition that maintains stirring, keep high pressure temperature in the kettle 1-8 hour, during this time in high pressure hydrogen reducing atmosphere, being attracted to carbonyl nickel on carrier surface, decomposition in situ fast, fully occurs is nickel simple substance, and is attached to equably on the surface of carrier with ultra-fine, amorphous particle form, has so just prepared the carried type, super-fine amorphous metal Raney nickel of the full hydrogenation of catalysis aromatic ring;
The device of realizing method for preparing catalyst includes: motor, magnetic stirring apparatus, air inlet, gas outlet, nut, autoclave body, thermocouple, Pressure gauge, stirring arm, control panel and electric furnace; Motor is connected with magnetic stirring apparatus by sleeve, and the bottom of magnetic stirring apparatus is connected with stirring arm; The upper cover of autoclave body is connected with autoclave body by nut, is connected with Pressure gauge upper covering, and is inserted with thermocouple by upper cover, is connected with respectively two and gathers around valvular pipeline upper covering, and pipeline is connected with air inlet and gas outlet respectively; Autoclave body is placed in electric furnace, and electric furnace is connected with control panel.
CN201310062690.9A 2013-02-28 2013-02-28 Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring Expired - Fee Related CN103084180B (en)

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