CN106902854A - Ni3Application of the P bases catalyst in the reaction of phenol and its derivatives hydrogenation deoxidation - Google Patents
Ni3Application of the P bases catalyst in the reaction of phenol and its derivatives hydrogenation deoxidation Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- 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
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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
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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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
Ni3Application of the P bases catalyst in the reaction of phenol and its derivatives hydrogenation deoxidation.The invention belongs to bio-oil processing technique field, wherein described catalyst is with Ni3P, as main active component, can be non-loading type or support type.The hydrogenation deoxidation of its catalysis is reacted with the aqueous solution or oil solution of oxygen containing phenol and its derivatives as reaction raw materials, is carried out in the fixed bed reactors of continuous flowing.In the present invention, Ni3The hydrogenation deoxidation activity of P base catalyst is better than noble metal catalyst Pd/SiO2, stability is higher than conventional Ni2P base catalyst, has wide practical use in the hydrogenation deoxidation field of bio-oil.
Description
Technical field
The invention belongs to heterogeneous catalysis technology field, it is related to a class Ni3P bases catalyst is used for bio-oil hydrogenation deoxidation
Course of reaction.
Background technology
21 century, with the fast development of social economy, facing mankind social economy's growth, environmental protection, existence hair
Exhibition and the multiple contradiction and pressure of energy resource consumption.At present, the 75% of global total energy consumption is from fossil energy such as coal, oil, natural gases
Source, but, the exhausted of global fossil energy will be inevitable.Meanwhile, the carbon total amount that fossil energy is discharged is annual up to 6,000,000,000
The problems such as ton, greenhouse gases effect and environmental degradation of initiation, has seriously threatened the survival and development of the mankind.
In order to solve these problems, the exploitation of the regenerative resource with bio-oil as representative attract attention.Compare
In fossil energy, bio-oil has the characteristics that：(1) recyclability, biomass can be regenerated by the photosynthesis of plant,
Aboundresources, it is ensured that the continuous utilization of the energy；(2) there is carbon dioxide zero discharge characteristic during biomass economy, can has
Effect reduces greenhouse effects；(3) sulphur, nitrogen content are relatively low in biomass, and content of ashes is also little, SO after burningx、NOxWith the row of dust
Fossil fuel is high-volume far below, is a kind of clean fuel；(4) biomass resource distribution is wide, yield is big, transform mode is more；(5) it is raw
The content of oxygen and water is higher in material.
Substantial amounts of oxygenatedchemicals can cause some serious problems in bio-oil, and such as oil product calorific value is low, chemically stable
Property big, etching apparatus of poor, viscosity etc., seriously hinders its widely using as petrol and diesel oil alternative fuel, it is necessary to which it is taken off
Oxygen is refined.In hydrogenation deoxidation (HDO) catalyst, study it is more be petroleum refining industry Ni (Co) MoS/ γ-Al2O3Hydrogenation
Desulfurization (HDS) catalyst.However, in HDO courses of reaction, the sulphur atom on sulfide catalyst surface can be substituted with an oxygen and cause sulphur
Lose so as to cause the inactivation of sulfide catalyst.To avoid catalyst from inactivating, a small amount of sulfur-bearing chemical combination is generally added in the feed
Thing (such as H2S and CS2) lost with supplementing sulphur.But added sulfur-containing compound can not only reduce the HDO activity of catalyst, Er Qie
Harmful sulfur-containing compound, pollution products are generated in product.In addition, water content is larger in bio-oil, and HDO process reclaimed waters
It is accessory substance, transient metal sulfide can cause catalyst to lose by water oxygen metaplasia into corresponding sulfate during the course of the reaction
It is living.
Transition metal phosphide is the general designation of the covalent compound that phosphorus is formed with transition metal (Co, Ni, Mo and W etc.).Cross
Crossing metal phosphide can be divided into rich metal phosphide (M/P >=1) and rich phosphorus phosphide according to the stoichiometric proportion of metal (M) and phosphorus
(M/P<1) two class.The latter is unstable, and rich ganometallic transition metal phosphide quality is hard and with good thermodynamics and chemistry
Stability, can be used as catalyst.With Ni2P、MoP、WP、Co2P and CoP are a series of transition metal phosphides of representative with it
High activity and stability has wide application preceding in fields such as hydrogenation, dehydrogenation, hydrodesulfurization, hydrodenitrogeneration and hydrogenation deoxidations
Scape.In these transition metal phosphides, Ni2P is conventional catalyst, but its less stable (Energ.Fuel., 2011,
25:854-863), have much room for improvement.(Cryst.Res.Technol., 2014,49 from terms of the finding of document:178-189；
J.Alloys Compd.,2007,437:289-297；J.Mater.Sci.,2017,52:804-814；
J.Mater.Chem.A.,2014,4:10925-10932), the Ni for reporting at present3Being used as anti-corrosion, wear-resisting, waterproof material P more
And evolving hydrogen reaction catalyst, not yet have been reported that and apply in the hydrogenation deoxidation of phenol compound is refined.
The content of the invention
It is an object of the invention to provide Ni3A kind of new application process of P base catalyst, i.e. Ni3P base catalyst is in benzene
Application in phenol and its reaction of derivative hydrogenation deoxidation.The application, that is, one kind uses Ni3The phenol of P base catalyst and its
The method of derivative hydrogenation deoxidation reaction.
In application of the present invention, described phenol and its derivatives include phenol and fortified phenol, described substitution
Phenol is arbitrarily replaced by following radicals：Methyl (- CH3), hydroxyl (- OH) or methoxyl group (- OCH3).In the present invention, " appoint when addressing
During meaning substitution ", represent on the premise of the general principles of chemistry are met, to replacing the number and the position of substitution of base without specific
Limitation.Above-mentioned fortified phenol then includes by any number of methyl (- CH3), hydroxyl (- OH) or methoxyl group (- OCH3) in phenol
The substitution of optional position on phenyl ring or phenolic hydroxyl group.The obtained compound of substitution can illustrate but be not limited to：Phenol, methyl phenyl ethers anisole,
Orthoresol, catechol and guaiacol.
In the phenol and its derivatives as reaction substrate applied, the chemical combination that preferably phenol or unitary replace
Thing (including the substitution on phenolic hydroxyl group).Wherein, and particularly preferably the unitary that phenol and ortho position (o-) or meta (m-) replace takes
Substituting phenol.
It is described comprising the hydrogenation deoxidation reaction with phenol and its derivatives as reaction substrate in application of the present invention
Hydrogenation deoxidation reaction can be reacted using fixed bed reactors continuous feed.The reaction temperature of described hydrogenation deoxidation reaction is
100-400 DEG C, more preferably preferably 250-350 DEG C, 300-350 DEG C；Reaction pressure is 1.0-5.0MPa.
More specifically consider, described hydrogenation deoxidation reaction can be carried out in the reaction medium of water phase or oil phase, point
Not Wei aqueous phase reactions or oil phase reaction, wherein：The reaction medium of aqueous phase reactions is deionized water, and the mass fraction of reaction substrate is
1-10%, product is dried after being extracted with dichloromethane with anhydrous magnesium sulfate；The reaction medium of oil phase reaction is decahydronaphthalene, reacts bottom
The mass fraction of thing is 0.1-5%, and product can be applied directly after reaction.
Further, in application of the present invention, described Ni3P bases catalyst activity is mutually Ni3P, is support type or non-
Loaded catalyst.It is such as the former, then the carrier of the loaded catalyst is SiO2Or HZSM-5, the load capacity of metal is to urge
The 5-45% of agent quality.
Specifically, described Ni3P bases catalyst is prepared by following methods：
(1) catalyst precarsor that Ni/P mol ratios are 3 is prepared；
Specifically, coprecipitation is used to prepare the unsupported catalyst precursor that Ni/P mol ratios are for 3, using isometric common
Infusion process prepares the supported catalyst precursor that Ni/P mol ratios are 3：
The preparation method of supported catalyst precursor can further be specifically described as：Nickel nitrate and diammonium hydrogen phosphate are dissolved in
It is supported on carrier in dust technology, after standing and drying, 500 DEG C of calcination process (or saving the step) are calcined (or burning)
Catalyst precarsor；The preparation method of unsupported catalyst precursor can further be specifically described as：By ammonium dibasic phosphate solution
Formation precipitation in nickel nitrate solution is added drop-wise to, is dried after evaporating moisture, 500 DEG C of calcination process (or saving the step) obtain
It is calcined the catalyst precarsor of (or burning).
(2) catalyst precarsor is activated through hydrogen temperature programmed reduction or hydrogen plasma reduction is activated, wherein,
The condition of described temperature programmed reduction activation includes：Hydrogen flowing quantity 150mL/min, heating schedule be from room temperature with
After 2 DEG C/min rises to 400 DEG C, then rise to 500 DEG C with 1 DEG C/min and keep 120min, then cooling；
The condition of described hydrogen gas plasma reduction activation is hydrogen flowing quantity 150mL/min, using dielectric barrier discharge,
Discharge frequency is 10kHz, tube voltage 70V, reductase 12 h.
In the brand-new application described in the invention described above, it has been found that Ni3The water of P base catalyst Pyrogentisinic Acids is mutually hydrogenated with de-
Oxygen activity is better than precious metals pd/SiO2Catalyst and relative low price, stability is higher than conventional Ni2P catalyst.For benzene
Amphyl, Ni3P bases catalyst also has water phase very high and oil phase hydrogenation deoxidation activity, and with good stability.
Using the catalyst, continuously hydrogen adding deoxygenation is carried out with relatively mild reaction condition in fixed bed reactors, can be efficient
Realize the hydrogenation and removing of phenol and its derivatives in bio-oil.
Brief description of the drawings
The width of accompanying drawing of the present invention 5：
Fig. 1 is to use H2Roasting prepared by temperature-programmed reduction method and the unsupported Ni not being calcined3The XRD spectrums of P catalyst
Figure.
Fig. 2 is to use H2Roasting prepared by plasma method and the unsupported Ni not being calcined3The XRD spectra of P catalyst.
Fig. 3 is that H is respectively adopted2Temperature-programmed reduction method and H2Roasting prepared by plasma method and the SiO not being calcined2It is negative
Carry Ni3The XRD spectra of P catalyst.
Fig. 4 is that H is respectively adopted2Temperature-programmed reduction method and H2Roasting prepared by plasma method and the HZSM-5 not being calcined
Load Ni3The XRD spectra of P catalyst.
Before Fig. 5 is reaction, phenol water phase and the reacted TPR-C-Ni of oil phase hydrogenation deoxidation3The XRD spectra of P catalyst.
Specific embodiment
Specific embodiment of the invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Using H2Temperature-programmed reduction method prepares non-loading type Ni3P catalyst.
Weigh 13.212 grams of Ni (NO3)2·6H2O is made solution A in being dissolved in 10 ml deionized waters, then weighs 2 grams of (NH4)2HPO4Be dissolved in 5 ml deionized waters and be made solution B, be stirred continuously it is lower B is added dropwise over A in form green suspension.Steam
It is dry to dry 12h after 120 DEG C, non-firing precursor C is obtained.It is placed in again in Muffle furnace and is warming up to 500 DEG C with the speed of 4 DEG C/min,
Roasting 3h, is obtained firing precursor D.C and D are respectively placed in tubular reactor, in normal pressure, the bar of hydrogen flowing quantity 150mL/min
Under part, with the temperature programming of 2 DEG C/min to 400 DEG C again with the temperature programming of 1 DEG C/min to 500 DEG C, be obtained in 500 DEG C of reductase 12 h
Catalyst, is designated as TPR-NC-Ni respectively3P and TPR-C-Ni3P.By by the XRD spectra and Ni of these catalyst3P standard spectrograms
(PDF 65-1605) contrast (Fig. 1) is as can be seen that successfully prepare non-loading type Ni using temperature-programmed reduction method3P catalyst.
Embodiment 2
Using H2Plasma deoxidization method prepares non-loading type Ni3P catalyst.
Weigh C the or D precursors in 1g embodiments 1, it is ground, compressing tablet, broken and be sized to 20-40 mesh particles, it is loaded on
In reactor between electrode.Discharge frequency is fixed on 10kHz, input voltage 70V, H2Gas velocity is 150mL/min, normal pressure, reduction
2h is obtained catalyst, and PR-NC-Ni is designated as respectively3P and PR-C-Ni3P.By by the XRD spectra and Ni of these catalyst3P standards
Spectrogram (PDF 65-1605) contrast (Fig. 2) is as can be seen that use H2Plasma deoxidization method successfully prepares non-loading type Ni3P is urged
Agent.
Embodiment 3
Using H2Temperature-programmed reduction method and H2Plasma method prepares Ni3P/SiO2Catalyst.
0.5 gram of Ni (NO are weighed first3)2·6H2O and 0.376 gram of (NH4)2HPO4It is dissolved in the dilute HNO of 2mL3In be made leaching
Stain liquid, then by above-mentioned maceration extract in 2 grams of white carbon is slowly dropped under being stirred continuously, still aging 12h at room temperature,
Then 12h is dried at 120 DEG C in an oven, precursor A is obtained.Precursor B is obtained after precursor A is calcined 3 hours at 500 DEG C again.
(Ni/P mol ratios are 3 in precursor)
A and B are respectively placed in tubular reactor, under conditions of normal pressure, hydrogen flowing quantity 150mL/min, with 2 DEG C/min
Temperature programming to 400 DEG C again with the temperature programming of 1 DEG C/min to 500 DEG C, in the prepared catalyst of 500 DEG C of reductase 12s hour, respectively
It is designated as TPR-NC-Ni3P/SiO2And TPR-C-Ni3P/SiO2；Weigh 1g A or B precursors, it is ground, compressing tablet, broken and be sized to
20-40 mesh particles, are loaded in reactor between electrode.Discharge frequency is fixed on 10kHz, input voltage 70V, H2Gas velocity is
150mL/min, normal pressure, the prepared catalyst of reductase 12 hour is designated as PR-NC-Ni respectively3P/SiO2And PR-C-Ni3P/SiO2.It is logical
Cross the XRD spectra and Ni of these catalyst3P standard spectrograms (PDF 65-1605) contrast (Fig. 3) are as can be seen that use program
Heating reduction method and plasma deoxidization method successfully prepare Ni3P/SiO2Catalyst.
Embodiment 4
Using H2Temperature-programmed reduction method and H2Plasma method prepares Ni3P/HZSM-5 catalyst.
0.5 gram of Nickelous nitrate hexahydrate (Ni (NO are weighed first3)2·6H2) and 0.376 gram of (NH O4)2HPO4It is dissolved in 2mL dilute
HNO3In be made maceration extract, then by above-mentioned maceration extract in 2 grams of HZSM-5 is slowly dropped under being stirred continuously, at room temperature
Still aging 12h, then dries 12h at 120 DEG C in an oven, and precursor A is obtained.Precursor A is calcined 3 hours at 500 DEG C again
Precursor B is obtained afterwards.(Ni/P mol ratios are 3 in precursor)
A and B are respectively placed in tubular reactor, under conditions of normal pressure, hydrogen flowing quantity 150mL/min, with 2 DEG C/min
Temperature programming to 400 DEG C again with the temperature programming of 1 DEG C/min to 500 DEG C, catalyst is obtained in 500 DEG C of reductase 12 h, remember respectively
It is TPR-NC-Ni3P/HZSM-5 and TPR-C-Ni3P/HZSM-5；Weigh 1g A or B precursors, it is ground, compressing tablet, broken and sieve
To 20-40 mesh particles, it is loaded in reactor between electrode.Discharge frequency is fixed on 10kHz, input voltage 70V, H2Gas velocity is
150mL/min, normal pressure, the prepared catalyst of reductase 12 hour is designated as PR-NC-Ni respectively3P/HZSM-5 and PR-C-Ni3P/HZSM-
5.By by the XRD spectra and Ni of these catalyst3P standard spectrograms (PDF 65-1605) contrast (Fig. 4) are as can be seen that use
Temperature-programmed reduction method and plasma deoxidization method successfully prepare Ni3P/HZSM-5 catalyst.
Embodiment 5
Phenol and its derivatives are in TPR-C-Ni3Water on P is mutually hydrogenated with deoxygenation.
React is carried out in the high pressure fixed-bed tube reactor of 10 millimeters of internal diameter.It is obtained in the reactor by embodiment 1
After corresponding catalyst, temperature of reactor is adjusted to reaction temperature (350 DEG C), stagnation pressure increases to 4MPa, is squeezed into high pressure constant flow pump
Reaction raw materials (mass concentration is the aqueous solution of 5% phenol or derivatives thereof), weight (hourly) space velocity (WHSV) 30h-1, hydrogen/oil volume compares 1000,
DNA vaccine is calculated with corresponding hydrocarbon yield.Fluid sample is taken after stable reaction, organic phase product is extracted with dichloromethane, then with nothing
Water MgSO4The minor amount of water of residual is removed, in Aglient 6890N type gas chromatographic analysis, chromatographic column is commercially available INNO-WAX maos
Capillary column, hydrogen flame detector, reaction result is listed in table 1 and (phenol at 350 DEG C, orthoresol, metacresol, catechol and more creates
Wooden phenol is in non-loading type Ni3Conversion ratio and DNA vaccine when the enterprising water-filling phase HDO of P catalyst reacts).As can be seen from Table 1,
At 350 DEG C, phenol is in Ni3The upper conversion ratios of P (99.8%) with Pd/SiO2On conversion ratio (99.9%) approach, and use conversion
Frequency (TOF) calculates Ni3The TOF values of P catalysis of phenol HDO are Pd/SiO21.3 times, illustrate prepared non-loading type Ni3P
Catalyst activity is better than Pd/SiO2.In Ni3On P, catechol conversion ratio is close to 100%, and orthoresol and metacresol conversion ratio are big
In 85%, and guaiacol conversion ratio illustrates Ni also close to 80%3There is P catalyst water very high to be mutually hydrogenated with deoxy activity.It is right
Can be seen that the crystal formation of catalyst keeps constant than the XRD spectra (Fig. 5) of catalyst before and after reaction, illustrate obtained TPR-C-
Ni3P catalyst has good stability under the conditions of water is mutually hydrogenated with deoxygenation.
The phenol of table 1 and its unitary substituent water are mutually hydrogenated with deoxygenation performance
| Reaction substrate | Phenol | Catechol | Orthoresol | Metacresol | Guaiacol |
| Conversion ratio (%) | 99.8 | 99.5 | 85.9 | 88.7 | 79.0 |
| DNA vaccine (%) | 82.6 | 80.7 | 72.3 | 78.7 | 66.1 |
Embodiment 6
Phenol and its derivatives are in TPR-C-Ni3Oil phase hydrogenation deoxidation reaction on P.
React is carried out in the high pressure fixed-bed tube reactor of 10 millimeters of internal diameter.It is obtained in the reactor by embodiment 1
After corresponding catalyst, temperature of reactor is adjusted to reaction temperature (350 DEG C), stagnation pressure increases to 4MPa, is squeezed into high pressure constant flow pump
Reaction raw materials (mass concentration is the decahydronaphthalene solution of 1% phenol or derivatives thereof), weight (hourly) space velocity (WHSV) 26.7h-1, hydrogen/oil volume
Than 1000, DNA vaccine is calculated with corresponding hydrocarbon yield.Fluid sample is taken after stable reaction, in Aglient6890N type gas-chromatographies
Analysis, chromatographic column is commercially available INNO-WAX capillary columns, and hydrogen flame detector, reaction result is listed in table 2 (phenol, benzene first at 350 DEG C
Ether, orthoresol, metacresol and guaiacol are in non-loading type Ni3Conversion ratio when HDO reacts and deoxidation are carried out on P catalyst
Rate).As can be seen from Table 2,350 DEG C when, phenol is in Ni3The upper conversion ratios of P (99.8%) close to Duan et al. (J.Catal.,
2009,261:232-240) report in Ni2Conversion ratio (98.9%) on P/MCM-41, illustrates prepared Ni3P catalyst
Activity is close to Ni2P/MCM-41.In addition, methyl phenyl ethers anisole, orthoresol, metacresol and guaiacol are in Ni3Also have on P catalyst
Conversion ratio higher, illustrates the non-loading type Ni for preparing3P catalyst has oil phase hydrogenation deoxidation activity very high.Contrast reaction
The XRD spectra (Fig. 5) of front and rear catalyst can be seen that the crystal formation of catalyst keeps constant, illustrate obtained TPR-C-Ni3P is catalyzed
Agent also has good stability under oil phase hydrogenation deoxidation reaction condition.
The phenol of table 2 and its unitary substituent oil phase hydrogenation deoxidation reactivity worth
| Reaction substrate | Phenol | Methyl phenyl ethers anisole | Orthoresol | Metacresol | Guaiacol |
| Conversion ratio (%) | 99.9 | 82.6 | 84.2 | 99.7 | 77.6 |
| DNA vaccine (%) | 98.4 | 80.7 | 83.9 | 97.7 | 77.1 |
Result according to table 1 and 2 is visible：1) for water phase HDO, reactivity is reduced to successively by substitution base：-OH>-
CH3>-OCH3；By the position of substitution：m->o-；2) for oil phase HDO, reactivity is reduced to successively by substitution base：-CH3>-
OCH3；By the position of substitution：m->o->P-OH；3) for same reaction substrate, from the point of view of DNA vaccine, oil phase reactivity is better than water
Phase reaction
Embodiment 7
Phenol is in TPR-C-Ni3Water on P is mutually hydrogenated with the investigation of deoxygenation temperature.
React is carried out in the high pressure fixed-bed tube reactor of 10 millimeters of internal diameter.It is obtained in the reactor by embodiment 1
After corresponding catalyst, temperature of reactor is adjusted to initial reaction temperature (150 DEG C), stagnation pressure increases to 4MPa, uses high pressure constant flow pump
Squeeze into reaction raw materials (mass concentration is the aqueous solution of 5% phenol or derivatives thereof), weight (hourly) space velocity (WHSV) 30h-1, hydrogen/oil volume ratio
1000, investigate reaction temperature (150-350 DEG C) is influenceed on it, and DNA vaccine is calculated with corresponding hydrocarbon yield.Liquid is taken after stable reaction
Body sample, extracts organic phase product, then use anhydrous MgSO with dichloromethane4The minor amount of water of residual is removed, in Aglient 6890N
Type gas chromatographic analysis, chromatographic column is commercially available INNO-WAX capillary columns, and hydrogen flame detector, reaction result is listed in the (phenol of table 3
In non-loading type Ni3Enter the conversion ratio and DNA vaccine when water-filling phase HDO reacts on P catalyst under different temperatures).Can be with by table 3
Find out, with the rising (rising to 350 DEG C by 150 DEG C) of reaction temperature, phenol conversion rises to 99.8% by 91.4%, and deoxidation
Rate also rises to 82.6% by 0.2%.
The phenol of table 3 enters water-filling and is added hydrogen deoxygenation performance at different temperatures
| Reaction temperature (DEG C) | 150 | 200 | 250 | 300 | 350 |
| Conversion ratio (%) | 91.4 | 97.8 | 98.4 | 99.0 | 99.8 |
| DNA vaccine (%) | 0.2 | 0.7 | 1.2 | 24.6 | 82.6 |
Embodiment 8
Phenol is in TPR-C-Ni3Oil phase hydrogenation deoxidation reaction temperature on P is investigated.
React is carried out in the high pressure fixed-bed tube reactor of 10 millimeters of internal diameter.It is obtained in the reactor by embodiment 1
After corresponding catalyst, temperature of reactor is adjusted to initial reaction temperature (150 DEG C), stagnation pressure increases to 4MPa, uses high pressure constant flow pump
Squeeze into reaction raw materials (mass concentration is the decahydronaphthalene solution of 1% phenol or derivatives thereof), weight (hourly) space velocity (WHSV) 26.7h-1, hydrogen/oil
Volume ratio 1000, investigate reaction temperature (150-350 DEG C) is influenceed on it, and DNA vaccine is calculated with corresponding hydrocarbon yield.Stable reaction
After take fluid sample, in Aglient 6890N type gas chromatographic analysis, chromatographic column is commercially available INNO-WAX capillary columns, hydrogen flame
Detector, reaction result is listed in table 4, and (phenol is in non-loading type Ni3When oil phase HDO reactions are carried out on P catalyst under different temperatures
Conversion ratio and DNA vaccine).As can be seen from Table 4, with the rising (rising to 350 DEG C by 150 DEG C) of reaction temperature, phenol conversion
Rate is slightly elevated to 99.9% by 97.4%, and DNA vaccine drastically rises to 98.4% by 0.5%.
The phenol of table 4 carries out oil phase hydrogenation deoxidation reactivity worth at different temperatures
| Reaction temperature (DEG C) | 150 | 200 | 250 | 300 | 350 |
| Conversion ratio (%) | 97.4 | 98.5 | 99.0 | 99.5 | 99.9 |
| DNA vaccine (%) | 0.5 | 19.4 | 45.3 | 96.9 | 98.4 |
Result according to table 3 and 4 is visible：For phenol HDO, no matter water phase or oil phase, phenol conversion is with anti-
Answer temperature to raise to be increased slightly, and DNA vaccine is significantly increased with temperature.Comprehensive descision, the most preferred scope of reaction temperature is
300-350℃。
Embodiment 9
Phenol is in TPR-C-Ni3P/SiO2And TPR-C-Ni3Water on P/HZSM-5 is mutually hydrogenated with deoxygenation.
React is carried out in the high pressure fixed-bed tube reactor of 10 millimeters of internal diameter.Made in the reactor by embodiment 3 and 4
After obtaining corresponding catalyst, temperature of reactor is adjusted to reaction temperature (300 DEG C), stagnation pressure increases to 4MPa, is beaten with high pressure constant flow pump
Enter reaction raw materials (mass concentration is 5% phenol solution), liquid hourly space velocity (LHSV) 30h-1, hydrogen/oil volume compares 1000, and DNA vaccine is with phase
The hydrocarbon yield answered is calculated.Fluid sample is taken after stable reaction, organic phase product is extracted with dichloromethane, then use anhydrous MgSO4It is de-
Except the minor amount of water of residual, in Aglient 6890N type gas chromatographic analysis, chromatographic column is commercially available INNO-WAX capillary columns, hydrogen fire
Flame detector, reaction result is listed in table 5, and (phenol is in TPR-C-Ni at 300 DEG C3P/SiO2、TPR-C-Ni3P/HZSM-5 and TPR-
C-Ni3The conversion ratio and DNA vaccine of phenol when the enterprising water-filling phase HDO of P catalyst reacts).As can be seen from Table 5,300 DEG C when, benzene
Phenol conversion ratio on three kinds of catalyst is suitable, close to 100%.In TPR-C-Ni3P/SiO2Upper DNA vaccine (27.9%) is slightly better than
In TPR-C-Ni3On P, and in TPR-C-Ni3The upper DNA vaccines of P/HZSM-5 are up to 94.5%, illustrate prepared TPR-C-Ni3P/
HZSM-5 catalyst has reactivity higher.
Table 5
| Catalyst | |||
| Phenol conversion (%) | 99.3 | 99.6 | 99.2 |
| DNA vaccine (%) | 27.9 | 94.5 | 24.6 |
The present invention has explicitly disclosed catalyst composition of the present invention and preparation condition by the description above.But, this
Technical staff in field is fully aware of, and some modification and improvement can be carried out to the present invention.So, as long as without departing from the present invention
Spirit, all should be within the scope of the invention to any modification and improvement for being carried out of the present invention.The scope of the present invention is attached
Claims in propose.
Claims (10)
1.Ni3Application of the P bases catalyst in the reaction of phenol and its derivatives hydrogenation deoxidation.
2. application according to claim 1, it is characterised in that described phenol and its derivatives include phenol and substituted benzene
Phenol, described fortified phenol is arbitrarily replaced by following radicals：Methyl, hydroxyl or methoxyl group.
3. application according to claim 2, it is characterised in that described fortified phenol is unitary substituted compound.
4. application according to claim 3, it is characterised in that described phenol and its derivatives include phenol, methyl phenyl ethers anisole,
Orthoresol, catechol and guaiacol.
5. application according to claim 1, it is characterised in that described hydrogenation deoxidation reaction temperature is 100-400 DEG C, instead
It is 1.0-5.0MPa to answer pressure.
6. application according to claim 1, it is characterised in that described hydrogenation deoxidation reaction is that aqueous phase reactions or oil phase are anti-
Should, wherein：
The reaction medium of aqueous phase reactions is deionized water, and the mass fraction of reaction substrate is 1-10%, and product is extracted with dichloromethane
Dried with anhydrous magnesium sulfate after taking；
The reaction medium of oil phase reaction is decahydronaphthalene, and the mass fraction of reaction substrate is 0.1-5%.
7. application according to claim 6, it is characterised in that described hydrogenation deoxidation reaction is connected using fixed bed reactors
Continuous charging reaction.
8. application according to claim 1, it is characterised in that described Ni3P bases catalyst activity is mutually Ni3P, is load
Type or unsupported catalyst.
9. application according to claim 1, it is characterised in that the carrier of described loaded catalyst is SiO2Or HZSM-
5, the load capacity of metal is the 5-45% of catalyst quality.
10. application according to claim 1, it is characterised in that described Ni3P bases catalyst is prepared by following methods：
(1) catalyst precarsor that Ni/P mol ratios are 3 is prepared；
(2) catalyst precarsor is activated through hydrogen temperature programmed reduction or hydrogen plasma reduction is activated, wherein,
The condition of described temperature programmed reduction activation includes：Hydrogen flowing quantity 150mL/min, heating schedule be from room temperature with 2 DEG C/
After min rises to 400 DEG C, then rise to 500 DEG C with 1 DEG C/min and keep 120min, then cooling；
The condition of described hydrogen gas plasma reduction activation is hydrogen flowing quantity 150mL/min, using dielectric barrier discharge, electric discharge
Frequency is 10kHz, tube voltage 70V, reductase 12 h.
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| CN107684919A (en) * | 2017-08-03 | 2018-02-13 | 大连理工大学 | Support type Ni3P catalyst and its preparation method and application |
| CN109647457A (en) * | 2018-12-06 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene adds the catalyst and preparation method and application of hydrogen naphthane and decahydronaphthalene |
| CN110694656A (en) * | 2019-09-11 | 2020-01-17 | 天津大学 | Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion |
| CN112237931A (en) * | 2020-09-07 | 2021-01-19 | 大连理工大学 | Bulk phase nickel phosphide catalyst, preparation method and application in phenol hydrodeoxygenation |
| CN113413889A (en) * | 2021-07-06 | 2021-09-21 | 辽宁师范大学 | Preparation method of amorphous vanadium catalyst for preparing phenol by benzene hydroxylation |
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| CN113413889A (en) * | 2021-07-06 | 2021-09-21 | 辽宁师范大学 | Preparation method of amorphous vanadium catalyst for preparing phenol by benzene hydroxylation |
| CN115055195A (en) * | 2022-06-10 | 2022-09-16 | 清华大学 | Bifunctional catalyst for ethyl levulinate hydrogenation reaction |
| CN116374954A (en) * | 2023-03-22 | 2023-07-04 | 大连理工大学 | Ni 3 P/SiO 2 Application of catalyst in DBD plasma methane dry reforming |
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