CN109865519A - A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application - Google Patents
A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application Download PDFInfo
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Abstract
The invention discloses a kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application, ruthenium modified activated carbon supported nickel catalyst, the load capacity of nickel is 10~20wt%, and the load capacity of ruthenium is 0.5~1.5wt%, and surplus is active carbon.The application improves the reactivity worth of catalyst to reduce the acidity of catalyst surface by the way that the acidic functionality carboxy-silane baseization of activated carbon surface is modified, using acid H is played in organo-functional group replacement carboxyl；Meanwhile auxiliary agent Ru is introduced in activated carbon supported Raney nickel to improve the dispersion degree of Ni metallic particles enhance the activity of catalyst；Catalyst is applied to the selection of cyclopentadiene gas phase plus hydrogen prepares cyclopentene, the conversion ratio of cyclopentadiene is 91~100%, and the selectivity of cyclopentene is 85~98%.
Description
Technical field
The present invention relates to a kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its applications, belong to ring penta 2
The selection of alkene gas phase plus hydrogen preparation field.
Background technique
The fine chemicals of a variety of high added values can be produced using cyclopentene, these chemicals are widely used in pharmacy work
The fields such as industry, organic synthesis and synthetic rubber.The cyclopentanol prepared by cyclopentene, can be used for producing medicine intermediate and perfume (or spice)
Material, is the raw material for preparing cyclopentanone, bromocyclopentane, chlorocyclopentane, drug cyclopenthiazide and arcotic ketamine.Ring penta
Ketone is the raw material for preparing jasmine ketone fragrance, anxiolytic buspirone, agriculture chemicals fungicide Pencycuron, additionally, due to it to various
Resin has good solubility property, therefore is used widely in electronics industry as cleaning agent and solvent.By cyclopentene system
Standby glutaraldehyde is excellent tanning extracts, tissue curing agent, protein cross agent and efficient sterilization disinfectant, is widely used in
Medical and health, leather industry, petroleum industry, food industry etc..The cyclopentene methyl ether prepared by cyclopentene is a kind of excellent molten
Agent, the organic solvents such as alternative tetrahydrofuran, methyl tertiary butyl ether(MTBE).The pentamethylene prepared by cyclopentene, alternative fluorochlorohydrocarbon are used
Make refrigerator refrigerant, also can be used as solvent and used in the polymerisation in solutions such as polyisoprene rubber.By the penta 2 of cyclopentene preparation
Acid, can chemistry, building, medicine, in terms of be widely applied.By seven fluorine pentamethylene of cyclopentene preparation, octafluoro cyclopentene
Deng, it is pollution-free, the destruction of ozone layer is close to zero, is a kind of green, safety environment-friendly material.
There are mainly three types of the synthetic methods of cyclopentene: (1) earlier processes: with cyclopentanol at 380-400 DEG C, using aluminium oxide
Gas-phase dehydration is carried out for catalyst to produce, but due to cyclopentanol limited source, thus cannot use the method mass production；(2)BASF-
Erdchemie method: it is heated using the by-product C 5 fraction of petroleum cracking as raw material, make cyclopentadiene therein at bicyclic penta
Diene is handled with N-Methyl pyrrolidone extracting, then through being cracked to form cyclopentadiene, after being hydrogenated into cyclopentene by selection, is added
Into in the material containing cyclopentadiene, then through extracting, distillation and fractionation, obtain cyclopentene and isoprene.The method process is longer, process
It is complicated；(3) Bayer method: C 5 fraction is thermally treated, dicyclopentadiene is obtained, then be depolymerized to cyclopentadiene, most afterwards through catalytic hydrogenation
Into cyclopentene, using palladium series catalyst, Cr or Ti are co-catalyst, and Li-Al spinelle is carrier, which is industrial at present
The method mainly used, the disadvantage is that palladium series catalyst is expensive.
Selective Hydrogenation of Cyclopentadiene prepares cyclopentene technique, can be divided into gas phase hydrogenation and liquid-phase hydrogenatin.It is industrial at present main
Cyclopentene, the technique although available high cyclopentene yield are produced using liquid-phase hydrogenatin technique, but catalyst difficulty recycles,
It is unable to continuous production, and reaction pressure is higher.Gas phase hydrogenation technique can operate under normal pressure, and energy continuous production, but
Have the shortcomings that catalyst preparation is complicated, the service life is short or active low.That therefore develops gas phase hydrogenation technique focuses on catalyst
Exploitation.
The catalyst of the selection of cyclopentadiene gas phase plus hydrogen preparing cyclopentene mainly has two kinds of palladium system and nickel system, palladium series catalyst valence
Lattice are expensive, and oxidizable inactivation in air at normal temperature.Nickel catalyst is cheap, mainly includes Raney Ni, support type
Crystalline state nickel and carried non-crystal Raney nickel, wherein Raney Ni catalyst preparation is complicated, and support type crystalline state Raney nickel adds
Hydrogen activity is lower, and carried non-crystal Raney nickel hydrogenation activity is higher, is a kind of Raney nickel of focus development.
Common Pd/C hydrogenation catalyst industrial at present, using activated carbon as carrier.Active carbon specific surface with higher
Long-pending and pore structure abundant.But activated carbon surface acid oxygen-containing functional group rich in, such as carboxyl, carboxylic acid anhydrides and lactone group,
Wherein carboxyl acidity is most strong, and lactone group is taken second place, and phenolic hydroxyl group is faintly acid.Research shows that the acidity of catalyst surface is to hydrogenation reaction
Be it is unfavorable, common modulating method is that alkaline assistant is added in the catalyst.But the addition of auxiliary agent can reduce active metal and exist
The dispersion degree of carrier surface reduces the reactivity worth of catalyst.
Summary of the invention
The present invention provides a kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application, by will be active
The acidic functionality carboxy-silane baseization of carbon surface is modified, using the H for playing acidity in organo-functional group replacement carboxyl, thus
The acidity for reducing catalyst surface, improves the reactivity worth of catalyst.Meanwhile auxiliary agent is introduced in activated carbon supported Raney nickel
Ru enhances the activity of catalyst to improve the dispersion degree of Ni metallic particles.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of ruthenium modified activated carbon supported nickel catalyst, the load capacity of nickel are 10~20wt%, the load capacity of ruthenium is 0.5~
1.5wt%, surplus are active carbon.
Applicants have found that introducing minute quantity ruthenium in nickel-base hydrogenation catalyst, the reduction degree of NiO can be reduced, is improved
The dispersion degree of Ni metallic particles, and the Ni metallic particles of high dispersive is advantageous the hydrogenation activity for improving catalyst, while right
Sintering and carbon distribution have certain inhibiting effect.Wt refers to weight percent.
The preparation method of above-mentioned ruthenium modified activated carbon supported nickel catalyst, including the following steps being connected in order:
(1) active carbon is put in a solvent, sonic oscillation；
(2) under stirring condition, silylating agent is slowly added dropwise into step (1) resulting material；
(3) by sonic oscillation under step (2) resulting material high frequency；
(4) step (3) resulting material is filtered, and obtained solid alcohol is washed, is dried under vacuum condition；
(5) nickel salt aqueous solution is configured；
(6) step (4) resulting material is placed on room temperature volumetric stirring dipping in nickel salt solution obtained by step (5)；
(7) solid in step (6) resulting material is dried；
(8) ruthenium chloride aqueous solution is configured；
(9) step (7) resulting material is placed on room temperature volumetric stirring leaching in ruthenium chloride aqueous solution obtained by step (8)
Stain；
(10) by solid drying, the calcining, prereduction in step (9) resulting material, ruthenium modified activated carbon nickel-loaded is obtained
Catalyst.
In step (1), solvent is benzene, ether or perchloroethylene, and the dosage of active carbon relative solvent is 0.15~0.35g/
mL.It can be further improved the reactivity worth of gained catalyst in this way.
In step (2), silylating agent is in trim,ethylchlorosilane, chlorotriethyl silane or trimethoxy chlorosilane
The volume mass ratio of at least one, silylating agent and active carbon is 0.1~0.5mL/g, the dropwise addition speed of silylating agent
Rate is 0.3~1mL/min.It can be further improved the reactivity worth of gained catalyst in this way.
In step (3), the sonic oscillation time is 1.5~4h under high frequency, and frequency is 1.7~2.4MHZ；In step (4), alcohol
Washing reagent is anhydrous methanol or dehydrated alcohol；Drying temperature is 100~150 DEG C, and the time is 4~10h.It can be further improved in this way
The reactivity worth of gained catalyst.
In step (5), nickel salt is nickel nitrate, nickel acetate or nickel chloride, and the concentration of nickel is 0.086~0.196g/ in nickel salt
mL；The dip time of step (6) and step (9) is 3~6h.It can be further improved the reactivity worth of gained catalyst in this way.
In step (8), ruthenium concentration is 0.004~0.015g/mL.It can be further improved the hydrogenation activity of catalyst in this way.
In step (10), drying temperature is 100~150 DEG C, and the time is 3~6h；Calcination atmosphere is nitrogen or argon gas, temperature
It is 400~500 DEG C, the time is 3~7h；Prereduction using hydrogen make also Primordial Qi, 400~500 DEG C of reduction temperature, the recovery time 4
~8h.It can be further improved the hydrogenation activity of catalyst in this way.
When the application catalyst is applied to cyclopentadiene gas phase selection dehydrogenation preparing cyclopentene, reaction temperature is 90~130
DEG C, hydrogen-hydrocarbon ratio is 0.8~1.2, and cyclopentadiene liquid air speed is 4~9h-1.The conversion ratio of cyclopentadiene is 91~100%, ring penta
The selectivity of alkene is 85~98%.
When catalyst is applied to cyclopentadiene gas phase selection dehydrogenation preparing cyclopentene, equipment therefor includes: ice bath slot, ring penta
Diene storage tank, metering pump, high-purity H2Steel cylinder, high-purity N2Steel cylinder, the first mass flowmenter, the second mass flowmenter, the first pressure regulation
Valve, the second pressure regulator valve, reaction tube, heat transfer oil heater, heat exchanger, high-temperature circulator, drainer and knockout drum；Ring penta 2
Alkene storage tank is located in ice bath slot, and cyclopentadiene storage tank, metering pump and reaction tube are sequentially communicated by pipeline；High-purity H2Steel cylinder,
One mass flowmenter, the first pressure regulator valve and reaction tube are sequentially communicated by pipeline；High-purity N2Steel cylinder, the second mass flowmenter,
Two pressure regulator valves and reaction tube are sequentially communicated by pipeline；Reaction tube is located in heat transfer oil heater, heat transfer oil heater, heat exchange
Device, high-temperature circulator and heat transfer oil heater are sequentially communicated by pipeline, form circulation；Reaction tube, drainer and gas-liquid separation
Tank is sequentially communicated by pipeline；
Reaction tube is by heat-conducting oil heating, and for conduction oil by high-temperature circulator heat cycles, absorbing reaction is exothermic thermally conductive
Oil withdraws the heat of absorption through heat exchanger, and the fast of catalyst exotherm can be realized by adjusting thermally conductive oil flow rate and heat exchange rate
Speed transfer, to reach the continuous controllable purpose of catalyst reaction temperatures；The selection of cyclopentadiene gas phase plus hydrogen preparing cyclopentene method
For Catalyst packing is passed through high pure nitrogen in reaction tube, opens high-temperature circulator and carries out circulating-heating to setting to conduction oil
Then temperature starts to be pumped into cyclopentadiene reaction, adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain setting temperature
Degree, then empties knockout drum, collects product again, after stablizing reaction 0.5h, carries out gas phase point to the product collected again
Analysis, after reaction, is switched to high pure nitrogen by high-purity hydrogen for feeding gas.
Drainer is equipped with condensate liquid import and condensate outlet, bottom in and top out；Knockout drum discharges equipped with liquid
Mouthful.
The unmentioned technology of the present invention is referring to the prior art.
A kind of ruthenium modified activated carbon supported nickel catalyst of the present invention, by by the acidic functionality carboxyl silicon of activated carbon surface
Alkylation modification is mentioned using acid H is played in organo-functional group replacement carboxyl to reduce the acidity of catalyst surface
The reactivity worth of high catalyst；Meanwhile auxiliary agent Ru is introduced in activated carbon supported Raney nickel, to improve point of Ni metallic particles
Divergence enhances the activity of catalyst.
Detailed description of the invention
Fig. 1 is the selection of the application cyclopentadiene gas phase plus hydrogen preparing cyclopentene apparatus structure schematic diagram；
In figure, 1 ice bath slot, 2 cyclopentadiene storage tanks, 3 metering pumps, 4 high-purity H2Steel cylinder, 5 first pressure regulator valves, 6 first mass
Flowmeter, 7 high-purity Ns2Steel cylinder, 8 second pressure regulator valves, 9 second mass flowmenters, 10 reaction tubes, 11 heat transfer oil heaters, 12 heat exchange
Device, 13 high-temperature circulators, 14 condensate liquid imports；15 condensate outlets；16 drainers, 17 offgas outlets；18 knockout drums；19
Liquid outlet.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In each embodiment, when catalyst is applied to cyclopentadiene gas phase selection dehydrogenation preparing cyclopentene, equipment therefor such as Fig. 1
It is shown, comprising: ice bath slot, cyclopentadiene storage tank, metering pump, high-purity H2Steel cylinder, high-purity N2Steel cylinder, the first mass flowmenter, second
Mass flowmenter, the first pressure regulator valve, the second pressure regulator valve, reaction tube, heat transfer oil heater, heat exchanger, high-temperature circulator, drainer
And knockout drum；Cyclopentadiene storage tank is located in ice bath slot, and cyclopentadiene storage tank, metering pump and reaction tube pass through pipeline successively
Connection；High-purity H2Steel cylinder, the first mass flowmenter, the first pressure regulator valve and reaction tube are sequentially communicated by pipeline；High-purity N2Steel cylinder,
Second mass flowmenter, the second pressure regulator valve and reaction tube are sequentially communicated by pipeline；Reaction tube is located in heat transfer oil heater, is led
Hot oil heating furnace, heat exchanger, high-temperature circulator and heat transfer oil heater are sequentially communicated by pipeline, form circulation；It is reaction tube, cold
Solidifying tank and knockout drum are sequentially communicated by pipeline；
Reaction tube is by heat-conducting oil heating, and for conduction oil by high-temperature circulator heat cycles, absorbing reaction is exothermic thermally conductive
Oil withdraws the heat of absorption through heat exchanger, and the fast of catalyst exotherm can be realized by adjusting thermally conductive oil flow rate and heat exchange rate
Speed transfer, to reach the continuous controllable purpose of catalyst reaction temperatures；The selection of cyclopentadiene gas phase plus hydrogen preparing cyclopentene method
For Catalyst packing is passed through high pure nitrogen in reaction tube, opens high-temperature circulator and carries out circulating-heating to setting to conduction oil
Then temperature starts to be pumped into cyclopentadiene reaction, adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain setting temperature
Degree, then empties knockout drum, collects product again, after stablizing reaction 0.5h, carries out gas phase point to the product collected again
Analysis, after reaction, is switched to high pure nitrogen by high-purity hydrogen for feeding gas.
Ambient temperature is 25 DEG C in each example, and mixing speed is 60 revs/min.
Embodiment 1
12g active carbon is placed in 80mL ether sonic oscillation 10min under 0.5MHZ.Under stirring condition, delay into liquid
It is slow that chlorotriethyl silane 1.2mL, drop rate 0.3mL/min is added dropwise.Liquid is placed in supersonic cleaning instrument, under 1.7MHZ under
Sonic oscillation 1.5h.Liquid is filtered, solid is washed with anhydrous methanol, then the vacuumizing and drying 4h at 100 DEG C.It is dense to configure nickel
Degree is the nickel chloride aqueous solution 13mL of 0.086g/mL.The 10g active carbon dried is placed on room temperature volumetric in nickel salt solution to stir
Mix dipping 3h.By 100 DEG C of drying 3h of solid.Configure the ruthenium chloride aqueous solution 13mL that ruthenium concentration is 0.004g/mL.After nickel-loaded
Active carbon be placed in ruthenium chloride aqueous solution room temperature volumetric stirring dipping 3h.By the first 100 DEG C of drying 3h of solid, then in nitrogen
The lower 400 DEG C of calcinings 3h of atmosphere, last solid 400 DEG C of prereduction 4h in a hydrogen atmosphere, obtains nickel loading 10%, ruthenium load capacity
0.5% ruthenium modified activated carbon supported nickel catalyst.
Prepared catalyst 5mL is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 6.51L/h opens high temperature and follows
Ring device carries out circulating-heating to 86 DEG C to conduction oil, then starts to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity 20mL/h
(16g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 90 DEG C, then empties knockout drum, again
Product is collected, after stablizing reaction 0.5h, gas phase analysis is carried out to the product collected again.The result shows that at 90 DEG C of reaction temperature,
Hydrogen-hydrocarbon ratio 1.2, cyclopentadiene liquid volume air speed 4h-1Under the conditions of, the conversion ratio of cyclopentadiene is 91%, and cyclopentene is selectively
85%.
Embodiment 2:
14g active carbon is placed in 40mL perchloroethylene sonic oscillation 10min under 0.5MHZ.Under stirring condition, to liquid
In trimethoxy chlorosilane 7mL, drop rate 1mL/min is slowly added dropwise.Liquid is placed in supersonic cleaning instrument, under 2.0MHZ
Sonic oscillation 4h.Liquid is filtered, solid is washed with dehydrated alcohol, then the vacuumizing and drying 10h at 150 DEG C.It is dense to configure nickel
Degree is the nickel acetate aqueous solution 13mL of 0.196g/mL.The 10g active carbon dried is placed on room temperature volumetric in nickel salt solution to stir
Mix dipping 6h.Solid is in 150 DEG C of drying 6h.Configure the ruthenium chloride aqueous solution 13mL that ruthenium concentration is 0.015g/mL.After nickel-loaded
Active carbon be placed in ruthenium chloride aqueous solution room temperature volumetric stirring dipping 6h.By the first 150 DEG C of drying 6h of solid, then in nitrogen
The lower 500 DEG C of calcinings 7h of atmosphere, last solid 450 DEG C of prereduction 8h in a hydrogen atmosphere, obtains nickel loading 20%, ruthenium load capacity
1.5% ruthenium modified activated carbon supported nickel catalyst.
Prepared catalyst 5mL is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 9.76L/h opens high temperature and follows
Ring device carries out circulating-heating to 122 DEG C to conduction oil, then starts to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity 45mL/h
(36g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 130 DEG C, then empties knockout drum, again
Product is collected, after stablizing reaction 0.5h, gas phase analysis is carried out to the product collected again.The result shows that in reaction temperature 130
DEG C, hydrogen-hydrocarbon ratio 0.8, cyclopentadiene liquid air speed 9h-1Under the conditions of, the conversion ratio of cyclopentadiene is 100%, and cyclopentene is selectively
89%.
Embodiment 3:
10g active carbon is placed in 40mL benzene sonic oscillation 10min under 0.5MHZ.Under stirring condition, slowly into liquid
Trim,ethylchlorosilane 4mL, drop rate 0.8mL/min is added dropwise.Liquid is placed in supersonic cleaning instrument, ultrasound vibration under 2.3MHZ
Swing 2h.Liquid is filtered, solid is washed with dehydrated alcohol, then the vacuumizing and drying 6h at 120 DEG C.Configuring nickel concentration is
The nickel nitrate aqueous solution 13mL of 0.148g/mL.The 10g active carbon dried is placed on room temperature volumetric stirring leaching in nickel salt solution
Stain 4h.Solid is in 120 DEG C of drying 4h.Configure the ruthenium chloride aqueous solution 13mL that ruthenium concentration is 0.0093g/mL.After nickel-loaded
Active carbon is placed on room temperature volumetric stirring dipping 4h in ruthenium chloride aqueous solution.By the first 120 DEG C of drying 4h of solid, then in nitrogen gas
The lower 500 DEG C of calcinings 5h of atmosphere, last solid 500 DEG C of prereduction 5h in a hydrogen atmosphere, obtains nickel loading 16%, ruthenium load capacity
1% ruthenium modified activated carbon supported nickel catalyst.
Prepared catalyst 5mL is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 9.49L/h opens high temperature and follows
Ring device carries out circulating-heating to 114 DEG C to conduction oil, then starts to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity 35mL/h
(28g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 120 DEG C, then empties knockout drum, again
Product is collected, after stablizing reaction 0.5h, gas phase analysis is carried out to the product collected again.The result shows that in reaction temperature 120
DEG C, hydrogen-hydrocarbon ratio 1.0, cyclopentadiene liquid air speed 7h-1Under the conditions of, the conversion ratio of cyclopentadiene is 100%, and cyclopentene is selectively
98%.
Embodiment 4:
Catalyst 5mL prepared by embodiment 3 is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 9.49L/h is beaten
It opens high-temperature circulator and circulating-heating is carried out to 121 DEG C to conduction oil, then start to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity
35mL/h (28g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 128 DEG C, then empties gas-liquid separation
Tank collects product again, after stablizing reaction 0.5h, carries out gas phase analysis to the product collected again.The result shows that in reaction temperature
128 DEG C of degree, hydrogen-hydrocarbon ratio 1.0, cyclopentadiene liquid air speed 7h-1Under the conditions of, the conversion ratio of cyclopentadiene is 100%, cyclopentene choosing
Selecting property is 94.2%.
Embodiment 5:
Catalyst 5mL prepared by embodiment 3 is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 9.49L/h is beaten
It opens high-temperature circulator and circulating-heating is carried out to 91 DEG C to conduction oil, then start to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity
35mL/h (28g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 97 DEG C, then empties gas-liquid separation
Tank collects product again, after stablizing reaction 0.5h, carries out gas phase analysis to the product collected again.The result shows that in reaction temperature
97 DEG C of degree, hydrogen-hydrocarbon ratio 1.0, cyclopentadiene liquid air speed 7h-1Under the conditions of, the conversion ratio of cyclopentadiene is 94.7%, cyclopentene choosing
Selecting property is 96.2%.
Embodiment 6:
Catalyst 5mL prepared by embodiment 3 is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 11.39L/h is beaten
It opens high-temperature circulator and circulating-heating is carried out to 114 DEG C to conduction oil, then start to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity
35mL/h (28g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 121 DEG C, then empties gas-liquid separation
Tank collects product again, after stablizing reaction 0.5h, carries out gas phase analysis to the product collected again.The result shows that in reaction temperature
121 DEG C of degree, hydrogen-hydrocarbon ratio 1.2, cyclopentadiene liquid air speed 7h-1Under the conditions of, the conversion ratio of cyclopentadiene is 100%, cyclopentene choosing
Selecting property is 93.8%.
Embodiment 7:
Catalyst 5mL prepared by embodiment 3 is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 12.20L/h is beaten
It opens high-temperature circulator and circulating-heating is carried out to 117 DEG C to conduction oil, then start to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity
45mL/h (36g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 120 DEG C, then empties gas-liquid separation
Tank collects product again, after stablizing reaction 0.5h, carries out gas phase analysis to the product collected again.The result shows that in reaction temperature
120 DEG C of degree, hydrogen-hydrocarbon ratio 1.0, cyclopentadiene liquid air speed 9h-1Under the conditions of, the conversion ratio of cyclopentadiene is 96.7%, cyclopentene choosing
Selecting property is 93.3%.
Embodiment 8:
12g active carbon is placed in 40mL benzene sonic oscillation 10min under 0.5MHZ.Under stirring condition, slowly into liquid
Trim,ethylchlorosilane 3.6mL, drop rate 0.6mL/min is added dropwise.Liquid is placed in supersonic cleaning instrument, it is ultrasonic under 2.4MHZ
Vibrate 3h.Liquid is filtered, solid is washed with dehydrated alcohol, then the vacuumizing and drying 5h at 130 DEG C.Configuring nickel concentration is
The nickel nitrate aqueous solution 13mL of 0.149g/mL.The 10g active carbon dried is placed on room temperature volumetric stirring leaching in nickel salt solution
Stain 4h.Solid is in 120 DEG C of drying 4h.Configure the ruthenium chloride aqueous solution 13mL that ruthenium concentration is 0.013g/mL.By the work after nickel-loaded
Property charcoal be placed in ruthenium chloride aqueous solution room temperature volumetric stirring dipping 4h.By the first 120 DEG C of drying 4h of solid, then in nitrogen atmosphere
Lower 500 DEG C of calcinings 5h, last solid 500 DEG C of prereduction 5h in a hydrogen atmosphere, obtains nickel loading 16%, ruthenium load capacity
1.4% ruthenium modified activated carbon supported nickel catalyst.
Prepared catalyst 5mL is seated in reaction tube, hydrogen is passed through, hydrogen flow rate 9.49L/h opens high temperature and follows
Ring device carries out circulating-heating to 113 DEG C to conduction oil, then starts to be pumped into cyclopentadiene reaction, cyclopentadiene flow velocity 35mL/h
(28g/h), adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain 120 DEG C, then empties knockout drum, again
Product is collected, after stablizing reaction 0.5h, gas phase analysis is carried out to the product collected again.The result shows that in reaction temperature 120
DEG C, hydrogen-hydrocarbon ratio 1.0, cyclopentadiene liquid air speed 7h-1Under the conditions of, the conversion ratio of cyclopentadiene is 100%, and cyclopentene is selectively
95.7%.
Claims (10)
1. a kind of ruthenium modified activated carbon supported nickel catalyst, it is characterised in that: the load capacity of nickel is 10~20wt%, the load of ruthenium
Amount is 0.5~1.5wt%, and surplus is active carbon.
2. the preparation method of ruthenium modified activated carbon supported nickel catalyst described in claim 1, it is characterised in that: including sequence phase
The following steps connect:
(1) active carbon is put in a solvent, sonic oscillation；
(2) under stirring condition, silylating agent is slowly added dropwise into step (1) resulting material；
(3) by sonic oscillation under step (2) resulting material high frequency；
(4) step (3) resulting material is filtered, and obtained solid alcohol is washed, is dried under vacuum condition；
(5) nickel salt aqueous solution is configured；
(6) step (4) resulting material is placed on room temperature volumetric stirring dipping in nickel salt solution obtained by step (5)；
(7) solid in step (6) resulting material is dried；
(8) ruthenium chloride aqueous solution is configured；
(9) step (7) resulting material is placed on room temperature volumetric stirring dipping in ruthenium chloride aqueous solution obtained by step (8)；
(10) by solid drying, the calcining, prereduction in step (9) resulting material, the catalysis of ruthenium modified activated carbon nickel-loaded is obtained
Agent.
3. preparation method as claimed in claim 2, it is characterised in that: in step (1), solvent be benzene, ether or perchloroethylene,
The dosage of active carbon relative solvent is 0.15~0.35g/mL.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that: in step (2), silylating agent is trimethyl
At least one of chlorosilane, chlorotriethyl silane or trimethoxy chlorosilane, the volume matter of silylating agent and active carbon
For amount than being 0.1~0.5mL/g, the drop rate of silylating agent is 0.3~1mL/min.
5. preparation method as claimed in claim 2 or claim 3, it is characterised in that: in step (3), the sonic oscillation time is under high frequency
1.5~4h, frequency are 1.7~2.4MHZ；In step (4), it is anhydrous methanol or dehydrated alcohol that alcohol, which washes reagent,；Drying temperature is
100~150 DEG C, the time is 4~10h.
6. preparation method as claimed in claim 2 or claim 3, it is characterised in that: in step (5), nickel salt be nickel nitrate, nickel acetate or
Nickel chloride, the concentration of nickel is 0.086~0.196g/mL in nickel salt；The dip time of step (6) and step (9) is 3~6h.
7. preparation method as claimed in claim 2 or claim 3, it is characterised in that: in step (8), ruthenium concentration be 0.004~
0.015g/mL。
8. preparation method as claimed in claim 2 or claim 3, it is characterised in that: in step (10), drying temperature is 100~150
DEG C, the time is 3~6h；Calcination atmosphere be nitrogen or argon gas, 400~500 DEG C of temperature, 3~7h of time；Prereduction is made using hydrogen
Also Primordial Qi, 400~500 DEG C of reduction temperature, 4~8h of recovery time.
9. the application method of activated carbon supported Raney nickel described in claim 1, it is characterised in that: catalyst is applied to ring
When pentadiene gas phase selects dehydrogenation preparing cyclopentene, reaction temperature is 90~130 DEG C, and hydrogen-hydrocarbon ratio is 0.8~1.2, cyclopentadiene liquid
Body air speed is 4~9h-1。
10. application method as claimed in claim 9, it is characterised in that: it is de- that catalyst is applied to the selection of cyclopentadiene gas phase
When hydrogen preparing cyclopentene, equipment therefor includes: ice bath slot, cyclopentadiene storage tank, metering pump, high-purity H2Steel cylinder, high-purity N2Steel cylinder,
One mass flowmenter, the second mass flowmenter, the first pressure regulator valve, the second pressure regulator valve, reaction tube, heat transfer oil heater, heat exchanger,
High-temperature circulator, drainer and knockout drum；Cyclopentadiene storage tank is located in ice bath slot, cyclopentadiene storage tank, metering pump and
Reaction tube is sequentially communicated by pipeline；High-purity H2Steel cylinder, the first mass flowmenter, the first pressure regulator valve and reaction tube by pipeline according to
Secondary connection；High-purity N2Steel cylinder, the second mass flowmenter, the second pressure regulator valve and reaction tube are sequentially communicated by pipeline；Reaction tube is set
In heat transfer oil heater, heat transfer oil heater, heat exchanger, high-temperature circulator and heat transfer oil heater are successively connected by pipeline
Logical, formation circulation；Reaction tube, drainer and knockout drum are sequentially communicated by pipeline；
Reaction tube passes through high-temperature circulator heat cycles, the exothermic conduction oil warp of absorbing reaction by heat-conducting oil heating, conduction oil
Heat exchanger withdraws the heat of absorption, and quickly turning for catalyst exotherm can be realized by adjusting thermally conductive oil flow rate and heat exchange rate
It moves, to reach the continuous controllable purpose of catalyst reaction temperatures；Cyclopentadiene gas phase selects to add hydrogen preparing cyclopentene method to urge
Agent is seated in reaction tube, is passed through high pure nitrogen, is opened high-temperature circulator and is carried out circulating-heating to set temperature to conduction oil,
Then start to be pumped into cyclopentadiene reaction, adjusting thermally conductive oil flow rate and heat exchange rate makes reaction temperature maintain set temperature, so
After empty knockout drum, collect product again, after stablizing reaction 0.5h, gas phase analysis carried out to the product collected again, instead
After answering, feeding gas is switched to high pure nitrogen by high-purity hydrogen.
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| CN117567227A (en) * | 2023-11-16 | 2024-02-20 | 广东新华粤石化集团股份公司 | Preparation method of high-purity dicyclopentadiene and derivatives |
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