CN108273506A - A kind of metalNicatalyst of high load and its preparation method and application - Google Patents
A kind of metalNicatalyst of high load and its preparation method and application Download PDFInfo
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- CN108273506A CN108273506A CN201810032991.XA CN201810032991A CN108273506A CN 108273506 A CN108273506 A CN 108273506A CN 201810032991 A CN201810032991 A CN 201810032991A CN 108273506 A CN108273506 A CN 108273506A
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 69
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 13
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims abstract description 11
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 241000370738 Chlorion Species 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- -1 Ethyl alcohol Chemical compound 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003643 water by type Substances 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DCQQZLGQRIVCNH-UHFFFAOYSA-N 2-methoxycyclohexan-1-ol Chemical class COC1CCCCC1O DCQQZLGQRIVCNH-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000000508 aqueous-phase reforming Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is first by by Ni (NO3)2·6H2O and TiCl4Ethanol solution and Na2SiO3·9H2O is co-precipitated, and is then removed water under the low surface tension of n-butanol, has been made with SiO2‑TiO2Composite oxides are as carrier, using metallic nickel as the high load type metalNicatalyst of active component, TiO in composite oxides2Presence make L acid acid amount increase, and produce B acid, enhance the interaction between carrier and metal component, increase the surface area of catalyst, the temperature needed for reduction is reduced, the reproducibility and dispersibility of metallic nickel is improved, the quantity in surface-active nickel site is made to dramatically increase, even if under high load, SiO2‑TiO2Reduction nickel particle on carrier can also as low as 4nm.Therefore, catalyst obtained has good low-temperature deoxidation activity, has high activity to o-methoxyphenol and to the highly selective of hexamethylene.
Description
Technical field
The invention belongs to catalysis technical fields, and in particular to one kind is for being catalyzed o-methoxyphenol selective hydrogenation deoxidation
Catalyst and preparation method thereof.
Background technology
Fossil energy reserves are limited and non-renewable, meanwhile, a large amount of greenhouse gas can be discharged while consuming fossil energy
The flue gas of body and pollution has caused the environment and ecocrisis of global range.Fossil energy is depended on unduly in order to break away from,
It must seek alternative energy source with alleviating energy crisis.Biomass energy can be converted directly because it is extensive with raw material, is easy to get
For the advantage of liquid fuel, become the first choice for substituting fossil energy.But since biomass is complicated and degradation process break key
Arbitrariness it is larger, oxygenatedchemicals type is various in bio-oil, therefore high oxygen content, leads to that its energy density is low, viscosity
Height, thermally and chemically stability is poor, cannot directly be reconciled with petroleum distillate, can not be directly used in engine fuel.Bio-oil
The method of upgrading includes hydrogenation deoxidation (HDO), catalytic pyrolysis and aqueous phase reforming, wherein HDO is to study most also most to answer extensively
With the method for foreground.In order to preferably study the deoxidation process of bio-oil, the specific oxygenatedchemicals of generally use is model
Reactant is studied, and phenol, methyl phenyl ethers anisole and o-methoxyphenol are usually selected.
Currently, multiple catalysts have been applied to HDO processes.As sulfide catalyst, noble metal, transition metal phosphide,
Carbide, nitride and other bifunctional catalysts etc..However, in HDO reaction process, the sulphur on sulfide catalyst surface
Atom can be substituted with an oxygen and sulphur is caused to lose, and cause catalyst inactivation, to avoid catalyst inactivation, usually be added in the feed few
Measure sulfur-containing compound (such as H2S) to make up surface sulphur loss.Catalyst structure can be kept to stablize although sulfur containing species are added,
The HDO activity of catalyst can be reduced because of competitive Adsorption, and can bring harmful sulphur into fuel, due to the above reasons,
The exploitation of unsulfided HDO catalyst starts to be taken seriously.Although noble metal catalyst has higher HDO activity and selection
Property, the especially selectivity of cycloalkane, but since its price is high, resource-constrained and constrain its in the industrial production extensive
Using.Transition metal phosphide, nitride and carbide catalyst show in the reactions such as the deoxidation of hydro carbons, hydrogenolysis and isomerization
Go out to be similar to the catalytic performance of precious metals pt, Ir etc., there is preferable H transfer abilities, be known as " quasi- platinum catalyst ".But mistake
It crosses metal carbides and when nitride makees HDO catalyst, existing greatest problem is that surface N and C are gradually replaced by O and cause to urge
Agent activity reduces.MetalNicatalyst activity is high, resourceful to be easy to get, cheap, is widely used in catalytic hydrogenation reaction
In.Since loaded catalyst has anti-sintered, and it is more advantageous to the contact with reactant during the reaction, therefore, industry
On using it is more be load type metal Raney nickel, usually metallic nickel particle height is dispersed in the oxide of high-specific surface area
On material.But since different carriers has different physics and chemical property, and the property of carrier can influence to load Ni catalysis
The catalytic performance of agent, so the activity of metalNicatalyst is also due to carrier of different nature and different from.In addition metal
The load capacity of Raney nickel is a key factor, because it can influence the quantity and acidity in catalyst surface active nickel site,
And then influence catalyst hydrogenation deoxidation activity, load capacity be more than 50% Ni catalyst commonly used in industry hydrogenation process, so
And it is difficult at present the metalNicatalyst for being prepared with simple method high load and high dispersive.
Invention content
The purpose of the present invention:The present invention for hydrogenation deoxidation during improving quality of biomass oil in the prior art there are the shortcomings that
With deficiency, the research of hydrogenation deoxidation is carried out to o-methoxyphenol using relatively inexpensive metalNicatalyst.The present invention passes through
Coprecipitation prepares high load, polymolecularity, using composite oxides as the metalNicatalyst of carrier, which is reducing
While o-methoxyphenol hydrogenation deoxidation reaction temperature, the conversion ratio of reaction and the selectivity to hexamethylene are improved.
The present invention uses following technical scheme:Provide a kind of metallic nickel carrying out hydrogenation deoxidation for o-methoxyphenol
Catalyst, the catalyst carrier are SiO2-TiO2, active component is metallic nickel, wherein active component is in terms of metallic nickel quality
The 50%~80% of catalyst quality is accounted for, the molar ratio of silicon and titanium is 0.5~2 in complex carrier:1.
The catalyst uses coprecipitation, by the salting liquid of metallic nickel and sodium carbonate and sodium silicate solution and TiCl4-
Ethanol solution is mixed to form precipitation, by precipitation by suction filtration, deionized water washing, n-Butanol soluble, water-bath, drying, H2Reduction,
N2Passivation is made.
Steps are as follows for the coprecipitation:
A. by the desired amount of Ni (NO3)2·6H2O、TiCl4Ethanol solution, which is dissolved in deionized water, to be stirred, and Ni is formed
(NO3)2And TiCl4The mixed solution of ethyl alcohol;
B. by the desired amount of Na2SiO3·9H2O and slightly excessive anhydrous Na2CO3It is dissolved in deionized water and stirring, form silicon
The mixed solution of sour sodium and sodium carbonate;
C. by mixed solution that the mixed solution that step (a) obtains is obtained with step (b) while a certain amount of go is added drop-wise to
It in ionized water, is vigorously stirred in a water bath, forms green precipitate;
D. precipitation step (c) obtained filters, and the pH value of gained filtrate is 8~9, and precipitation is fully washed with deionized water
To neutral and thoroughly wash away the chlorion in solution, precipitation is added in a certain amount of n-butanol, water-bath for a period of time, then
It dries in an oven, finally uses H2Reduction, N2Passivation obtains the metalNicatalyst of high load;
Wherein, the quality of activity component metal nickel accounts for the 50%~80% of catalyst quality, silicon and titanium in complex carrier
Molar ratio is 0.5-2.
TiCl described in step (a)4TiCl in ethanol solution4Mass concentration is 0.2~0.5%;
Slightly excessive anhydrous Na described in step (b)2CO3Dosage be more than desired amount of 5~20%;
The dosage of deionized water described in step (c) is 100~300ml, and bath temperature is 50~100 DEG C, when stirring
Between be 0.5~2h;
The dosage of n-butanol described in step (d) is 100~300ml, and bath temperature is 50~100 DEG C, water bath time 4
~16h, oven drying temperature are 60~150 DEG C, and drying time is 4~16h.
Presoma H2Reducing condition is:It is first that 5~10 DEG C/min rises to from room temperature with heating rate under the atmosphere of hydrogen
It 450 DEG C, is kept for 2~5 hours under 450 DEG C of final temperatures, is finally down to room temperature in N220~48h is passivated under atmosphere.
Prepared catalyst is reacted for being catalyzed o-methoxyphenol hydrogenation deoxidation, and concrete operation step includes:
Catalyst is fitted into tubular fixed-bed reactor, tubular fixed-bed both ends, which are packed into quartz sand, makes catalyst be placed in
Intermediate flat-temperature zone, is arranged temperature program after reactor is sealed, o-methoxyphenol solution is transported to fixation at 240 DEG C
It is passed through H in bed reactor21~3h is reacted, a condensate liquid is taken per 30min, before and after gas chromatography test reaction
The content of o-methoxyphenol is repeatedly tested, is averaged, and conversion ratio and selectivity of product are calculated.
Preferably, the reaction condition is:Reaction temperature is 140~260 DEG C, and hydrogen reaction pressure is 1~4MPa.
Preferably, the solvent in the o-methoxyphenol solution is decane, o-methoxyphenol and solvent matter
Amount is than being 1: 50~1: 100.
Preferably, the liquid hourly space velocity (LHSV) (LHSV) of reaction raw materials is 2~10h-1.The dosage of catalyst is 0.1~0.5g.
The technique effect of the present invention:Compared with prior art, hydrogenation deoxidation of the catalyst of the present invention to o-methoxyphenol
Catalysis reaction has the following advantages that:
1, the n-butanol that the method for the present invention uses surface tension low in the drying process substitutes water, due to the surface of n-butanol
Tension is low, can effectively reduce the possibility that chemical bond is formed between metal nickel particle, and prevent that it from forming hard agglomeration and
Caused catalyst surface area and porosity reduce, and the problem of the activity of catalyst are influenced, to improve the dispersion of metallic nickel
Property and reproducibility, and by n-butanol processing catalyst its reduction needed for temperature it is lower, the quantity in surface-active nickel site
It dramatically increases.
2, by Ni (NO in precipitation process3)2·6H2O and TiCl4Ethanol solution and Na2SiO3·9H2O is co-precipitated,
One kind has been made with SiO2-TiO2Composite oxides are as catalyst carrier, using metallic nickel as the high load type metal of active component
TiO is added in composite oxides in Raney nickel2So that L acid acid amounts is increased, and produce B acid, enhance carrier and metal component it
Between interaction, increase the surface area of catalyst, meanwhile, overcome single carrier loaded metalNicatalyst and exist
It is the problems such as quality difference and unstable crystalline phase, more preferable to the selectivity of hexamethylene to improve the hydrogenation deoxidation activity of catalyst.
3、TiO2Introducing strengthen load component Ni and carrier interaction, further can promote Ni on carrier
Dispersion reduces active nickel crystallite dimension.TiO existing for catalyst surface2It had both mutually been modified with NiO, and had also partly been compounded to form Ti-
O-Ni structures, and the introducing of NiO improves TiO2In the degree of scatter of carrier surface.Simultaneously as TiO in carrier2With can also
Originality so that TiO2There is certain modification, this effect to generate actively meaning to the catalytic performance of catalyst catalyst
Justice.
4, the load capacity and drying process of nickel are to determine two key factors of catalyst activity and surface nickel atoms quantity,
The increase of nickel loading can improve its reproducibility, but can reduce the dispersion degree of nickel-loaded.In the present invention, using coprecipitation
The Ni/SiO of high load is prepared for n-butanol drying process2-TiO2Catalyst dramatically increases catalyst after being handled with n-butanol
Surface area and nickel dispersion degree, cause the quantity in active surface nickel site to dramatically increase, and which thereby enhance the work of catalyst
Property.
Specific implementation mode
The present invention is described in further detail with reference to embodiment:
Embodiment 1:
(1) by 29.7g Ni (NO3)2·6H2O、23g TiCl4Ethyl alcohol (0.3g/g) solution is dissolved in 100ml deionized waters
In, form nickel nitrate and TiCl4The mixed solution of ethyl alcohol;
(2) by 5.2g Na2SiO3·9H2O and 18.2g anhydrous Nas2CO3It is dissolved in 100ml deionized waters, is formed
Na2SiO3·9H2O and Na2CO3Mixed solution;
(3) above two mixed solution is slowly dropped in 200ml deionized waters simultaneously under 80 DEG C of water-baths, is acutely stirred
1h is mixed, green precipitate is formed.The pH value of gained filtrate is 8~9 after suction filtration, is fully washed and is precipitated to during filtrate is in deionized water
Property simultaneously thoroughly washes away the chlorion in solution, and precipitation is added in 200ml n-butanols.12h is evaporated under 80 DEG C of water-baths, then
In 120 DEG C of baking ovens the presoma of catalyst is obtained after dry 12h;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/SiO2-TiO2(nSi/nTi=0.5) catalyst.
Embodiment 2
(1) by 29.7g Ni (NO3)2·6H2O、18.1g TiCl4Ethyl alcohol (0.3g/g) solution is dissolved in 100ml deionizations
In water, nickel nitrate and TiCl are formed4The mixed solution of ethyl alcohol;
(2) by 8.1g Na2SiO3·9H2O and 15.3g anhydrous Nas2CO3It is dissolved in 100ml deionized waters, is formed
Na2SiO3·9H2O and Na2CO3Mixed solution;
(3) above two solution is slowly dropped in 200ml deionized waters simultaneously under 80 DEG C of water-baths, is vigorously stirred
1h forms green precipitate.The pH value of gained filtrate is 8~9 after suction filtration, is fully washed with deionized water and is precipitated to filtrate and is in neutrality
And the chlorion in solution is thoroughly washed away, precipitation is added in 200ml n-butanols.12h is evaporated under 80 DEG C of water-baths, is then existed
In 120 DEG C of baking ovens the presoma of catalyst is obtained after dry 12h;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/SiO2-TiO2(nSi/nTi=1) catalyst.
Embodiment 3
(1) by 29.7g Ni (NO3)2·6H2O、13g TiCl4Ethyl alcohol (0.3g/g) solution is dissolved in 100ml deionized waters
In, form nickel nitrate and TiCl4The mixed solution of ethyl alcohol;
(2) by 11.4g Na2SiO3·9H2O and 11.9g anhydrous Nas2CO3It is dissolved in 100ml deionized waters, is formed
Na2SiO3·9H2O and Na2CO3Mixed solution;
(3) above two solution is slowly dropped in 200ml deionized waters simultaneously under 80 DEG C of water-baths, is vigorously stirred
1h forms green precipitate.The pH value of gained filtrate is 8~9 after suction filtration, is fully washed with deionized water and is precipitated to filtrate and is in neutrality
And the chlorion in solution is thoroughly washed away, precipitation is added in 200ml n-butanols.12h is evaporated under 80 DEG C of water-baths, is then existed
In 120 DEG C of baking ovens the presoma of catalyst is obtained after dry 12h;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/SiO2-TiO2(nSi/nTi=2) catalyst.
Embodiment 4
The reduction temperature of catalyst in 1 step of embodiment (4) is adjusted to 400 DEG C by 450 DEG C, the same embodiment of other steps
1。
Embodiment 5
The reduction temperature of catalyst in 1 step of embodiment (4) is adjusted to 500 DEG C by 450 DEG C, the same embodiment of other steps
1。
Embodiment 6
The reduction temperature of catalyst in 1 step of embodiment (4) is adjusted to 350 DEG C by 450 DEG C, the same embodiment of other steps
1。
Embodiment 7
The reduction temperature of catalyst in 1 step of embodiment (4) is adjusted to 550 DEG C by 450 DEG C, the same embodiment of other steps
1。
Comparative example 1
By SiO used in embodiment 12-TiO2Composite oxide carrier is changed to SiO2Carrier, other same embodiments of step
1。
(1) by 29.7g Ni (NO3)2·6H2O, which is dissolved in 100ml deionized waters, to be stirred, and nickel nitrate solution is formed;
(2) by 18.9g Na2SiO3·9H2O and 4.2g anhydrous Nas2CO3It is dissolved in 100ml deionized waters and stirring, form silicon
The mixed solution of sour sodium and sodium carbonate;
(3) above two solution is slowly dropped in 200ml deionized waters simultaneously under 80 DEG C of water-baths, is vigorously stirred
1h forms green precipitate.The pH value of gained filtrate is 8~9 after suction filtration, is fully washed and is precipitated to during filtrate is in deionized water
Property, precipitation is added in 200ml n-butanols.12h is evaporated under 80 DEG C of water-baths, is then after dry 12h in 120 DEG C of baking ovens
Obtain the presoma of catalyst;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/SiO2Catalyst.
Comparative example 2
By SiO used in embodiment 12-TiO2Composite oxide carrier is changed to TiO2Carrier, the same embodiment of other steps
1。
(1) by 29.7g Ni (NO3)2·6H2O、32g TiCl4Ethyl alcohol (0.3g/g) solution is dissolved in 100ml deionized waters
In, form nickel nitrate and TiCl4The mixed solution of ethyl alcohol;
(2) by 25.7g anhydrous Nas2CO3It is dissolved in 100ml deionized waters, forms Na2CO3Solution;
(3) above two solution is slowly dropped in 200ml deionized waters simultaneously under 80 DEG C of water-baths, is vigorously stirred
1h forms green precipitate.The pH value of gained filtrate is 8~9 after suction filtration, is fully washed with deionized water and is precipitated to filtrate and is in neutrality
And the chlorion in solution is thoroughly washed away, precipitation is added in 200ml n-butanols.12h is evaporated under 80 DEG C of water-baths, is then existed
In 120 DEG C of baking ovens the presoma of catalyst is obtained after dry 12h;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/TiO2Catalyst.
Comparative example 3
By SiO used in embodiment 12-TiO2Composite oxide carrier is changed to MC carriers, other steps are the same as embodiment 1.
(1) by 29.7g Ni (NO3)2·6H2O is dissolved in 100ml deionized waters, forms nickel nitrate solution;
(2) by 13g anhydrous Nas2CO3It is dissolved in 100ml deionized waters, forms Na2CO3Solution;
(3) 4g mesoporous carbons are dispersed in 200ml deionized waters, under 80 DEG C of water-baths simultaneously by above two solution
It is slowly dropped in mesoporous carbon solution, is vigorously stirred 1h, form black precipitate.The pH value of gained filtrate is 8~9 after suction filtration, is used
Deionized water, which is fully washed, to be precipitated to filtrate and is in neutrality, and precipitation is added in 200ml n-butanols.It is evaporated under 80 DEG C of water-baths
Then 12h obtains the presoma of catalyst in 120 DEG C of baking ovens after dry 12h;
(4) it is that 7 DEG C/min rises to from room temperature presoma to be positioned in tube furnace under the atmosphere of hydrogen with heating rate
It 450 DEG C, is kept for 3 hours under 450 DEG C of final temperatures, is finally down to room temperature in N2It is 60% to be passivated under atmosphere and obtain load capacity for 24 hours
Ni/MC catalyst.
Comparative example 4
The n-butanol in embodiment 1 is replaced with deionized water, other steps are the same as embodiment 1.
Comparative example 5
The n-butanol in embodiment 1 is replaced with absolute ethyl alcohol, other steps are the same as embodiment 1.
Performance test:
The content for measuring product in hydrogenation deoxidation reaction, chromatographiccondition are analyzed as internal standard using six alkane of epoxy:Agilent
CP-7821 chromatographic columns, High Purity Nitrogen are carrier gas, and FID detections, detection room temperature is 260 DEG C.It is detected and is found by reaction product:It is main
Product is wanted to have hexamethylene, 2- methoxycyclohexanols.
In fixed bed reactors, 60%Ni/SiO is added2-TiO2Quartz is added in catalyst 2ml, tubular fixed-bed both ends
Sand makes catalyst be placed on intermediate flat-temperature zone, fixed bed reactors is sealed.Material liquid is transported to using high pressure constant flow pump
It is reacted in fixed bed reactors, liquid hourly space velocity (LHSV) (LHSV) 3h of reaction raw materials-1, being filled with hydrogen makes the reaction pressure of reaction system reach
To 2.0MPa, temperature program is set, heating reaction furnace makes reaction temperature reach 240 DEG C of reactions, it is anti-that different temperature can be arranged
It answers, finally takes out reaction product, using the content of o-methoxyphenol before and after gas chromatography test reaction, repeatedly survey
Examination, is averaged, and calculates conversion ratio and product yield, as shown in table 1.
1 embodiment catalyst of table compares the performance of o-methoxyphenol hydrogenation deoxidation
Serial number | O-methoxyphenol conversion ratio (%) | Hexamethylene yield (%) |
Embodiment 1 | 100 | 91 |
Embodiment 2 | 100 | 90 |
Embodiment 3 | 100 | 92 |
Embodiment 4 | 92 | 80 |
Embodiment 5 | 93 | 80 |
Embodiment 6 | 82 | 69 |
Embodiment 7 | 85 | 71 |
Comparative example 1 | 73 | 40 |
Comparative example 2 | 68 | 38 |
Comparative example 3 | 59 | 31 |
Comparative example 4 | 54 | 24 |
Comparative example 5 | 66 | 37 |
As shown in Table 1:(1) due to TiO2Introducing strengthen load component Ni and carrier interaction, can further
Promote dispersions of the Ni on carrier, reduces active nickel crystallite dimension, therefore, with composite oxides SiO2-TiO2For the metal of carrier
The activity of Raney nickel is higher than the catalyst activity of single carrier;(2) since n-butanol can effectively reduce metal nickel particle
Between formed chemical bond possibility, and prevent its formed hard agglomeration, therefore when without n-butanol handle precipitate when, preparation
Catalyst effect is greatly lowered;(3) high load type metalNicatalyst prepared by the present invention adds o-methoxyphenol
Hydrogen deoxygenation is with higher activity and to hexamethylene with higher selectivity.(4) reduction temperature of hydrogen is to catalyst
Performance has a significant impact, 450 DEG C of best reduction temperatures for catalyst in the present invention.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of metalNicatalyst of high load, it is characterised in that:The catalyst using metallic nickel as active component, with
SiO2-TiO2As catalyst carrier, wherein active component accounts for the 50%~80% of catalyst quality in terms of metallic nickel quality.
2. a kind of preparation method of the metalNicatalyst of high load as described in claim 1, it is characterised in that:The preparation
Method is as follows:
A. by Ni (NO3)2·6H2O and TiCl4Ethanol solution is dissolved in deionized water, obtains nickel nitrate and TiCl4Ethyl alcohol mixes
Close solution;
B. by Na2SiO3·9H2O and anhydrous Na2CO3It is dissolved in deionized water, obtains Na2SiO3And anhydrous Na2CO3Mixed solution;
C. it by mixed solution that mixed solution that step (a) obtains is obtained with step (b) while being added drop-wise in deionized water, in water
It is vigorously stirred in bath, forms green precipitate;
D. precipitation step (c) obtained filters, and the pH value of gained filtrate is 8~9, is fully washed with deionized water in being precipitated to
Property simultaneously thoroughly washes away the chlorion in solution, then precipitation is added in n-butanol, water-bath, is then dried in an oven, most
After use H2Reduction, N2Passivation obtains the metalNicatalyst of high load.
3. the preparation method of the metalNicatalyst of high load as claimed in claim 2, it is characterised in that:Institute in step (a)
The TiCl stated4TiCl in ethanol solution4Mass concentration be 0.2~0.5%.
4. the preparation method of the metalNicatalyst of high load as claimed in claim 2, it is characterised in that:Institute in step (b)
The anhydrous Na stated2CO3Dosage be more than desired amount of 5~20%.
5. the preparation method of the metalNicatalyst of high load as claimed in claim 2, it is characterised in that:Institute in step (c)
The dosage for the deionized water stated is 100~300ml, and bath temperature is 50~100 DEG C, and mixing time is 0.5~2h.
6. the preparation method of the metalNicatalyst of high load as claimed in claim 2, it is characterised in that:Institute in step (d)
The dosage for stating n-butanol is 100~300ml, and bath temperature is 50~100 DEG C, and water bath time is 4~16h, oven drying temperature
It it is 60~150 DEG C, drying time is 4~16h.
7. the preparation method of the metalNicatalyst of high load as claimed in claim 2, it is characterised in that:Institute in step (d)
State H2Reduction, N2Passivating conditions are:450 DEG C are risen to from room temperature with the heating rate of 5~10 DEG C/min under the atmosphere of hydrogen,
It is kept for 2~5 hours under 450 DEG C of final temperatures, is finally down to room temperature in N220~48h is passivated under atmosphere.
8. a kind of application of the metalNicatalyst of high load as described in claim 1, it is characterised in that:The catalyst is used
It is catalyzed reaction in the hydrogenation deoxidation of o-methoxyphenol, Catalytic processes are:At 240 DEG C, using o-methoxyphenol as raw material,
Under the conditions of existing for decane and catalyst, hydrogen being added and carries out catalysis 1~3h of reaction, reaction temperature is 140~260 DEG C,
Hydrogen Vapor Pressure is 1~4MPa, and the mass ratio of o-methoxyphenol and decane is 1: 50~1: 100, the liquid space-time of reaction raw materials
Fast (LHSV) is 2~10h-1。
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CN111111679A (en) * | 2020-01-06 | 2020-05-08 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
CN112090443A (en) * | 2019-06-17 | 2020-12-18 | 中国石油化工股份有限公司 | Hydrodeoxygenation catalyst, application thereof and preparation method of cyclohexane |
CN113019379A (en) * | 2021-03-18 | 2021-06-25 | 中国海洋石油集团有限公司 | Catalyst for liquid-phase hydrogenation of olefine aldehyde and preparation method and application thereof |
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CN112090443A (en) * | 2019-06-17 | 2020-12-18 | 中国石油化工股份有限公司 | Hydrodeoxygenation catalyst, application thereof and preparation method of cyclohexane |
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CN111111679A (en) * | 2020-01-06 | 2020-05-08 | 湘潭大学 | Sulfur-free nickel-molybdenum bimetallic hydrodeoxygenation catalyst |
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