CN105903468A - Preparation method and application of eggshell type precious metal catalyst used for polyvinyl ether lubricating oil base oil hydrogenation and impurity removal - Google Patents
Preparation method and application of eggshell type precious metal catalyst used for polyvinyl ether lubricating oil base oil hydrogenation and impurity removal Download PDFInfo
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- CN105903468A CN105903468A CN201610256384.2A CN201610256384A CN105903468A CN 105903468 A CN105903468 A CN 105903468A CN 201610256384 A CN201610256384 A CN 201610256384A CN 105903468 A CN105903468 A CN 105903468A
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- catalyst
- base oil
- glymes
- eggshell type
- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 67
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 67
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 67
- 239000002199 base oil Substances 0.000 title claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 55
- 239000012535 impurity Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010970 precious metal Substances 0.000 title claims abstract description 13
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 12
- 229920001289 polyvinyl ether Polymers 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 64
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 239000011609 ammonium molybdate Substances 0.000 claims description 17
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims description 17
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 17
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000012696 Pd precursors Substances 0.000 claims description 6
- 238000009738 saturating Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 239000002923 metal particle Substances 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 3
- 230000008021 deposition Effects 0.000 abstract 1
- 150000002751 molybdenum Chemical class 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 6
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 pH value Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Lubricants (AREA)
Abstract
The invention provides a preparation method and an application of an eggshell type precious metal catalyst used for polyvinyl ether lubricating oil base oil hydrogenation and impurity removal, and belongs to the technical field of industrial catalysis. The preparation method comprises the following steps: adding a carrier to a precious metal salt and a metal molybdenum salt solution, controlling deposition of precious metal nano-particles and metal molybdenum nano-particles on the surface of the carrier through a rapid reduction reaction and controlling the viscosity of the solution, filtering the above obtained material, washing the filtered material, and drying the washed material in inert atmosphere to form the eggshell type PdMo catalyst. The reaction is carried out at room temperature without introducing a heating source, and the process is simple, so prepared metal particles have small and uniformly distributed particle size and good stability; and Pd particles and Mo nano-particles in the prepared eggshell type PdMo catalyst are uniformly distributed on the surface of the carrier, so the use amount of precious metals is reduced, the cost of the catalyst is effectively reduced, and the catalyst has good industrial application prospect. The eggshell type PdMo catalyst has excellent catalysis performance and good life in the hydrogenation reaction of polyvinyl ether lubricating oil base oil.
Description
Technical field
The invention belongs to lube oil hydrogenation technical field, relate to a kind of for glymes lube base
The preparation method of the eggshell type noble metal catalyst of oil hydrogenation remove impurity.
Background technology
Loaded noble metal catalyst is widely used in the field such as petrochemical industry and fine chemistry industry.The use of carrier
The dispersion of noble metal can be increased, improve the utilization rate of noble metal thus reduce the cost of noble metal catalyst.
In recent years, substantial amounts of research relates to noble metal granularity on carrier and distributed controll.Wherein metal in carrier
Selecting of Optimal Distribution is main according to the activity required by catalytic reaction, selectivity and other response parameter
Determine.Your gold the main integrated distribution of active metal of egg-shell catalyst, at carrier surface, can effectively reduce
Belong to the consumption of active component, improve the activity of catalyst；The catalyst of eggshell type distribution is conducive to product
It is desorbed from catalyst surface, it is to avoid the further reaction of target product, can improve irreversible cascade reaction
During the selectivity of intermediate product.The preparation of egg-shell catalyst, based on infusion process, is by urging mostly
The dipping of agent and being dried controls, including: change dip time, the concentration of impregnation liquid, pH value, solvent
The factors such as kind and interpolation competitive adsorbate all have a major impact preparing egg-shell catalyst.Polyvinylether
Class lubricating oil is due to raw material and the difference of polymerizing condition, containing undersaturated double bond, aldehyde and acetal in base oil,
Under the effect of catalyst, make it be able to by hydrogenation saturated, and remove the chlorine element of residual in polymerization process,
And then improve colourity and the photo and thermal stability etc. of base oil, and ehter bond can not be destroyed in hydrogenation process, enter
And ensure its viscosity, improve the quality of product.Therefore, glymes lube base oil hydrogenation is carried out
Research and development and heavy industrialization application are particularly important.Add as glymes lube base oil
Catalyst during hydrogen, most important to this technique, it determines production cost and subsequent product quality.Phase
Compared with oil hydrogenation, the difficulty of glymes lube base oil hydrogenation is bigger, owing to glymes moistens
Lubricant base oil chain structure, molecular weight is between 200～4000, sterically hindered relatively big, lives needed for hydrogenation reaction
Change and can improve, so needing research and development to have the hydrogenation catalyst of high catalytic activity.
For glymes lube base oil Utilizing question, we successfully develop eggshell type noble metal and urge
Agent is reacted for glymes lube base oil fixed bed continuously hydrogen adding, due to egg-shell catalyst
Use, it is ensured that the service life of load type metal catalyst.Obtained glymes lube base oil
Form and aspect are improved the most water-white and have good heat stability.Following known technology, all comes with some shortcomings:
Chinese patent, publication number: CN102451722A, introduce the preparation method of a kind of egg-shell catalyst,
The method uses the conventional carrier of active metal dipping solution leaching containing thickening agent and active metal dispersant, and
Impregnate under conditions of being passed through air bubbling, then drying and roasting, obtain eggshell hydrogenation catalyst.Its
Operation is more, comparatively laborious, and noble metal waste is serious.
Chinese patent, publication number: CN102451722B, introduce the preparation method of a kind of egg-shell catalyst,
Being aluminium oxide precursor to be mixed homogeneously with Gemini surface active agent, adhesive, kneading makes catalyst carrier,
Then impregnate carrier with the dipping solution containing thickening agent, and impregnate under conditions of being passed through air bubbling, then
Drying and roasting, obtain eggshell hydrogenation catalyst.Its operation is more, comparatively laborious, and noble metal
Waste is serious.
Chinese patent, publication number: CN1736604 introduces a kind of egg shell type metal and preparation thereof and application, should
Patent is the eggshell type metal supported catalyst with hollow silicon dioxide as carrier, described hollow silicon dioxide
Carrier is the mesoporous material with certain wall thickness and certain pore size, uses infusion process or original position load method to be prepared as
Egg shell type metal catalyst.But having strict demand for carrier, reactions steps is loaded down with trivial details, and manufacturing cycle is longer.
Summary of the invention
The invention discloses a kind of eggshell type noble metal for the hydrogenation remove impurity of glymes lube base oil
The preparation method of catalyst, belongs to Industrial Catalysis technical field.The method is that carrier is joined Precious Metals-Gold
Belong in salt and metal salt solution, reacted by fast restore, and solution viscosity, control noble metal nano grain
Son and metal nanoparticle deposit at carrier surface, and through filtering, washing, in inert atmosphere, heat drying is i.e.
Form stable eggshell type Pd Mo catalyst.Carry out under room temperature of the present invention, it is not necessary to introduce heating source, work
Skill is simple, and the metal particle diameter of preparation is little, is evenly distributed, good stability, the eggshell type Pd Mo catalysis of preparation
In agent, precious metals pd particle and Mo nanoparticle are evenly distributed on carrier surface, reduce the consumption of noble metal,
Effectively reduce catalyst cost, there is good prospects for commercial application.This eggshell type Pd Mo catalyst can be used
In glymes lube base oil hydrogenation reaction, this catalyst has the catalytic performance and good of excellence
Catalyst life, and there is good economic benefit and prospects for commercial application.
Technical scheme:
A kind of preparation of the eggshell type noble metal catalyst for the hydrogenation remove impurity of glymes lube base oil
Method, step is as follows:
Precious metal palladium precursor and ammonium molybdate being dissolved in glycerine water solution, the concentration of precious metal palladium precursor is
0.001-0.02mol/L, the concentration of ammonium molybdate is 0.0001-0.002mol/L, and palladium exists with the mol ratio of molybdenum
10:1-20:1, adds ball-type or column like catalyst carrier in mixed solution, adds strong reductant NaBH4Aqueous solution,
Atmospheric pressure at room is reacted, and by controlling dip time, reduction rate and solution viscosity, prepares eggshell type catalysis
Agent；Dip time is 5-100s, by adding sodium polyacrylate control solution viscosity in glycerine water solution is
50-200mPa.s, by controlling NaBH4Concentration of aqueous solution and the addition former reaction rate of speed controlling control palladium
Deposit at carrier surface with metal, then through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell
Type PdMo catalyst.
Described precious metal palladium precursor is one or both in Palladous nitrate., Palladous chloride., palladium, chlorine palladium acid
Mixed above.
Described carrier is SiO2Or Al2O3, the average pore size of carrier is at more than 40nm.
Described eggshell type Pd Mo catalyst is continuous for two sections of fixed beds of glymes lube base oil
Hydrogenation, first dilutes glymes lube base oil with solvent, glymes lube base oil
Account for volume ratio 40%-80% of solvent, then mix with hydrogen and carry out being hydrogenated with saturated removal glymes lubrication
Double bond in oil base oil, feeding temperature 120-150 DEG C, hydrogen partial pressure 12-18MPa, volume space velocity
0.2-0.5h-1, hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is eggshell type Pd catalyst；It is hydrogenated with saturated
Rear glymes lube base oil solution carries out being hydrogenated with de-acetal, and feeding temperature 140-150 DEG C, hydrogen divide
Pressure 15-18MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400:1；The de-acetal of hydrogenation is made
Catalyst be eggshell type Pd Mo catalyst, the loading eggshell type Pd Mo catalyst of metal Pd is
0.8-1.0%；Glymes lube base oil form and aspect after hydrogenation remove impurity are improved to water white, heat stability
Improving, viscosity slightly reduces.
Beneficial effects of the present invention: carry out under the method room temperature of the present invention, to carrier not requirement, and not
Needing to introduce heating source, technique is simple, and the metal particle diameter of preparation is little, is evenly distributed, good stability, preparation
Eggshell type Pd Mo catalyst in precious metals pd particle and Mo nanoparticle be evenly distributed on carrier surface,
Reduce the consumption of noble metal, effectively reduce catalyst cost, be beneficial to amplify production, at polyether class lubricating oil
Base oil remove impurity reaction has good prospects for commercial application.
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme.
Embodiment 1: the acid of chlorine palladium and ammonium molybdate are dissolved in glycerine water solution, the concentration of chlorine palladium acid is
0.01mol/L, the concentration of ammonium molybdate is 0.001mol/L, and regulation solution ph is more than carrier isoelectric point, IP, by ball
Type or column like catalyst carrier Al2O3Adding in above-mentioned solution, control dip time is 20s, and solution viscosity is 50mPa.s,
Add and add strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction 0.5h, NaBH4Mol ratio with metal
More than 5, through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell type Pd Mo catalyst, Pd
Loading is 0.8%.Generating PdMo thickness of the shell is 200 μm, and the particle diameter of PdMo is 4.2nm.By preparation
Eggshell type Pd Mo catalyst, for the hydrogenation remove impurity reaction of glymes lube base oil, adds as two-stage nitration
The catalyst of hydrogen remove impurity, first dilutes glymes lube base oil with solvent, the work of solvent dilution
With being, one is to reduce reactant liquor viscosity；Two is to take away reaction liberated heat；Three is rushing as catalyst
Lotion.Ratio 50% shared by glymes lube base oil, then mixes with hydrogen to carry out being hydrogenated with and satisfies
With the double bond removed in glymes lube base oil, feeding temperature 140 DEG C, hydrogen partial pressure 15MPa,
Volume space velocity 0.4h-1, hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is eggshell type Pd catalyst, gold
The loading belonging to Pd is 0.5%；It is hydrogenated with saturated rear glymes lube base oil by infrared detection double bond
Being saturated, ehter bond does not destroy.It is hydrogenated with saturated rear glymes lube base oil solution to be hydrogenated with
De-acetal, feeding temperature 145 DEG C, hydrogen partial pressure 15MPa, volume space velocity 0.5h-1, hydrogen to oil volume ratio 200:
1；It is eggshell type Pd Mo catalyst that hydrogenation takes off the catalyst that acetal used, the loading of metal Pd
It is 0.8%；Glymes lube base oil form and aspect after hydrogenation remove impurity are improved to water white, by infrared
Detection acetal and aldehyde radical are removed, and the glymes lube base heat stability after hydrogenation remove impurity improves,
Viscosity slightly reduces.
Embodiment 2: investigate metal Mo effect in the reaction, first with solvent by polyvinylether class lubricating oil
Base oil dilutes, and then the ratio 50% shared by glymes lube base oil mixes with hydrogen and carry out
It is hydrogenated with the double bond in saturated removal glymes lube base oil, feeding temperature 140 DEG C, hydrogen partial pressure
15MPa, volume space velocity 0.4h-1, hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is that eggshell type Pd is urged
Agent, the loading of metal Pd is 0.5%；It is hydrogenated with saturated rear glymes lube base oil by infrared
Detection double bond is saturated, and ehter bond does not destroy.It is hydrogenated with saturated rear glymes lube base oil solution
Carry out secondary hydrogenation, feeding temperature 145 DEG C, hydrogen partial pressure 15MPa, volume space velocity 0.5h-1, hydrogen oil volume
Compare 200:1；The catalyst that secondary hydrogenation is used is eggshell type Pd catalyst, and the loading of metal Pd is
0.8%；Glymes lube base oil form and aspect after hydrogenation are improved to water white, molten by infrared detection
Also having acetal and aldehyde to exist in liquid, the glymes lube base heat stability after hydrogenation increases,
But high-temperature stability is bad, 170 DEG C of heating quickly turn yellow, and viscosity slightly reduces.By contrast test, we obtain
To it was concluded that Mo metal there was added beneficially acetal and the hydrogenation of aldehyde, be primarily due to metal Mo be conducive to
The scission of link of C-H bond.
Embodiment 3: the acid of chlorine palladium and ammonium molybdate are dissolved in glycerine water solution, the concentration of chlorine palladium acid is
0.01mol/L, the concentration of ammonium molybdate is 0.001mol/L, and regulation solution ph is more than carrier isoelectric point, IP, by ball
Type or column like catalyst carrier Al2O3Adding in above-mentioned solution, control dip time is 20s, and solution viscosity is 50mPa.s,
Add and add strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction 0.5h, NaBH4Mol ratio with metal
Being respectively 5,10,15,20, through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell type Pd Mo
Catalyst, Pd loading is 0.8%.Generate PdMo thickness of the shell and be respectively 200 μm, 190 μm, 170
μm and 160 μm, the particle diameter of PdMo is respectively 4.2nm, 3.5nm, 3.0nm and 2.8nm.According to poly-
Vinyl Ether class lubricating oil base oil hydrogenation remove impurity result understands: NaBH4The biggest prepared with the mol ratio of metal
Metallic particle diameter the least, metal shell layer thickness is the thinnest, glymes lube base oil hydrogenation remove
Miscellaneous hydrogenation activity is more preferable, is primarily due to reaction and accelerates, and metal nucleation is faster.
Embodiment 4: the acid of chlorine palladium and ammonium molybdate are dissolved in glycerine water solution, the concentration of chlorine palladium acid is
0.01mol/L, the concentration of ammonium molybdate is 0.0001mol/L, 0.001mol/L, 0.002mol/L, 0.005mol/L,
Regulation solution ph is more than carrier isoelectric point, IP, by ball-type or column like catalyst carrier Al2O3Add in above-mentioned solution, control
Dip time processed is 20s, and solution viscosity is 50mPa.s, adds and adds strong reductant NaBH4Aqueous solution, often
Pressure room temperature reaction 0.5h, NaBH4Being equal in 5 with the mol ratio of metal, through filtering, washing, inert atmosphere is done
Dry i.e. forming stable eggshell type Pd Mo catalyst, Pd loading is 0.8%.Generating PdMo thickness of the shell is
About 200 μm, the particle diameter of PdMo is about 4.2nm.The eggshell type Pd Mo catalyst of preparation is used for
The hydrogenation remove impurity reaction of glymes lube base oil, as the catalyst of secondary hydrogenation remove impurity.According to poly-
Vinyl Ether class lubricating oil base oil hydrogenation remove impurity result understands: along with ammonium molybdate concentration increases, eggshell type Pd Mo
Catalyst shell thickness and particle diameter are basically unchanged, but the polyvinylether when Mo concentration is too small, after hydrogenation remove impurity
Class lubricating oil base oil, still with the presence of acetal, affects its high-temperature stability.But when Mo excessive concentration, hydrogenation
Glymes lube base oil ehter bond after remove impurity destroys serious, and viscosity declines many, product yield ground.
Therefore the addition of Mo strictly to control.
Embodiment 5: compare the dip time impact on preparing egg-shell catalyst.By molten to the acid of chlorine palladium and ammonium molybdate
Solution is in glycerine water solution, and the concentration of chlorine palladium acid is 0.01mol/L, and the concentration of ammonium molybdate is 0.001mol/L,
Regulation solution ph is more than carrier isoelectric point, IP, by ball-type or column like catalyst carrier Al2O3Add in above-mentioned solution, control
Dip time processed is respectively 5s, 20s, 40s, 100s, and solution viscosity is 50mPa.s, adds and adds strong reduction
Agent NaBH4Aqueous solution, atmospheric pressure at room reaction 0.5h, NaBH4It is equal to 5 with the mol ratio of metal, through filtering,
Washing, inert atmosphere is dried and i.e. forms stable eggshell type Pd Mo catalyst, and Pd loading is about 0.8%.
Generating PdMo thickness of the shell and be respectively 170,200,210 and 280 μm, the particle diameter of PdMo is 4.2nm.
According to characterization result: the longest prepared metal shell layer thickness of dip time is the thickest, and metal particle diameter is basic
Constant, in the hydrogenation remove impurity reaction of glymes lube base oil, metal hydrogenation activity is basically identical,
Illustrate that metal shell layer thickness is little to hydrogenation reaction activity influence.Therefore, for egg-shell catalyst, should control
Egg-shell catalyst metal particle diameter processed.
Embodiment 6: the acid of chlorine palladium and ammonium molybdate are dissolved in glycerine water solution, the concentration of chlorine palladium acid is
0.01mol/L, the concentration of ammonium molybdate is 0.001mol/L, and regulation solution ph is more than carrier isoelectric point, IP, by ball
Type or column like catalyst carrier Al2O3 add in above-mentioned solution, and control dip time is 20s, and solution viscosity is respectively
20,50,100 and 200mPa.s, add and add strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction 0.5h,
NaBH4Being equal to 5 with the mol ratio of metal, through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell
Type PdMo catalyst, Pd loading is about 0.8%.Generate PdMo thickness of the shell and be respectively 250,200,
180 and 170 μm, the particle diameter of PdMo is about 4.2nm.According to characterization result: solution viscosity is more
Little prepared metal shell layer thickness is the thickest, and metal particle diameter is basically unchanged, at glymes lube base
In oil hydrogenation remove impurity reaction, metal hydrogenation activity is basically identical, illustrates that hydrogenation reaction is lived by metal shell layer thickness
Property impact little.Therefore, for egg-shell catalyst, egg-shell catalyst metal particle diameter should be controlled.
Embodiment 7: the acid of chlorine palladium and ammonium molybdate are dissolved in glycerine water solution, the concentration of chlorine palladium acid is respectively
0.001mol/L, 0.005mol/L and 0.01mol/L；It is 0.0001mol/L that the concentration of ammonium molybdate is respectively,
0.0005mol/L and 0.001mol/L, ball-type or column, more than carrier isoelectric point, IP, are carried by regulation solution ph
Body Al2O3Adding in above-mentioned solution, control dip time is 20s, and solution viscosity is 50mPa.s, adds and adds
Enter strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction 0.5h, NaBH4It is equal to 5 with the mol ratio of metal,
Through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell type Pd Mo catalyst, and Pd loading is
About 0.8%.Generating PdMo thickness of the shell and be respectively 170,190 and 200 μm, the particle diameter of PdMo is 4.2nm
Left and right.Ion concentration affects shell thickness, and the dilutest shell thickness of ion concentration is the thinnest.
Embodiment 8: on the basis of embodiment 1, feeding temperature 140 DEG C, hydrogen partial pressure 15MPa, body
Long-pending air speed 0.4h-1, hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is eggshell type Pd catalyst, metal
The loading of Pd is 0.5%；It is hydrogenated with saturated rear glymes lube base oil solution to carry out being hydrogenated with de-acetal,
Feeding temperature 145 DEG C, hydrogen partial pressure 15MPa, volume space velocity 0.5h-1, hydrogen to oil volume ratio 200:1；Hydrogenation
The catalyst that de-acetal is used is eggshell type Pd Mo catalyst, and the loading of metal Pd is 0.8%, Pd
It is that 10:1 investigates catalyst stability with the mol ratio of Mo.
Shown by each phase experiments result of this process operation 500h, full with eggshell type Pd catalyst for hydrogenation
And catalyst, eggshell type Pd Mo catalyst is the de-aldolization catalyst of hydrogenation, uses two sections of fixed bed hydrogenation sides
Formula carries out hydrogenation reaction to glymes lube base, prepares the polyvinylether class lubricating oil base after remove impurity
Plinth form and aspect are improved to the most water-white, and viscosity slightly reduces and have good high-temperature hot stability, then 200 DEG C long-time
Invariant color.The above results shows that the technology of the present invention has good stability, and catalyst is long for service life.
Claims (5)
1. the preparation side for the eggshell type noble metal catalyst of glymes lube base oil hydrogenation remove impurity
Method, it is characterised in that step is as follows:
Precious metal palladium precursor and ammonium molybdate being dissolved in glycerine water solution, the concentration of precious metal palladium precursor is
0.001-0.02mol/L, the concentration of ammonium molybdate is 0.0001-0.002mol/L, and palladium exists with the mol ratio of molybdenum
10:1-20:1, adds ball-type or column like catalyst carrier in mixed solution, adds strong reductant NaBH4Aqueous solution,
Atmospheric pressure at room is reacted, and by controlling dip time, reduction rate and solution viscosity, prepares eggshell type catalysis
Agent；Dip time is 5-100s, by adding sodium polyacrylate control solution viscosity in glycerine water solution is
50-200mPa.s, by controlling NaBH4Concentration of aqueous solution and the addition former reaction rate of speed controlling control palladium
Deposit at carrier surface with metal, then through filtering, washing, inert atmosphere is dried and i.e. forms stable eggshell
Type PdMo catalyst.
Preparation method the most according to claim 1, it is characterised in that described precious metal palladium precursor be Palladous nitrate.,
One or more mixing in Palladous chloride., palladium, chlorine palladium acid.
Preparation method the most according to claim 1 and 2, it is characterised in that described carrier is SiO2Or Al2O3,
The average pore size of carrier is at more than 40nm.
4. the application of the eggshell type noble metal catalyst that the preparation method described in claim 1 or 2 obtains, its feature exists
In, described eggshell type Pd Mo catalyst is continuous for two sections of fixed beds of glymes lube base oil
Hydrogenation, first dilutes glymes lube base oil with solvent, glymes lube base oil
Account for volume ratio 40%-80% of solvent, then mix with hydrogen and carry out being hydrogenated with saturated removal glymes lubrication
Double bond in oil base oil, feeding temperature 120-150 DEG C, hydrogen partial pressure 12-18MPa, volume space velocity
0.2-0.5h-1, hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is eggshell type Pd catalyst；It is hydrogenated with saturated
Rear glymes lube base oil solution carries out being hydrogenated with de-acetal, and feeding temperature 140-150 DEG C, hydrogen divide
Pressure 15-18MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400:1；The de-acetal of hydrogenation is made
Catalyst be eggshell type Pd Mo catalyst, the loading eggshell type Pd Mo catalyst of metal Pd is
0.8-1.0%；Glymes lube base oil form and aspect after hydrogenation remove impurity are improved to water white, heat stability
Improving, viscosity slightly reduces.
5. the application of the eggshell type noble metal catalyst that the preparation method described in claim 3 obtains, it is characterised in that
Described eggshell type Pd Mo catalyst is used for two sections of fixed bed continuously hydrogen addings of glymes lube base oil,
First being diluted by glymes lube base oil with solvent, glymes lube base oil accounts for solvent
Volume ratio 40%-80%, then mix with hydrogen and carry out being hydrogenated with saturated removal glymes lube base
Double bond in oil, feeding temperature 120-150 DEG C, hydrogen partial pressure 12-18MPa, volume space velocity 0.2-0.5h-1、
Hydrogen to oil volume ratio 200:1；Hydrocatalyst for saturating is eggshell type Pd catalyst；It is hydrogenated with saturated rear polyvinylether
Class lubricating oil base oil solution carries out being hydrogenated with de-acetal, feeding temperature 140-150 DEG C, hydrogen partial pressure 15-18
MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400:1；The catalysis that the de-acetal of hydrogenation is used
Agent is eggshell type Pd Mo catalyst, and the loading eggshell type Pd Mo catalyst of metal Pd is 0.8-1.0%；
Glymes lube base oil form and aspect after hydrogenation remove impurity are improved to water white, and heat stability improves, viscous
Degree slightly reduces.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551522A (en) * | 2018-05-31 | 2019-12-10 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN110607199A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Method for removing impurities from polyvinyl ether by hydrogenation |
| CN111073602A (en) * | 2019-12-05 | 2020-04-28 | 鸿蒙科技(浙江)有限公司 | Composition for improving refrigeration energy efficiency of HFO1234yf |
| CN112126503A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Method for removing impurities from polyvinyl ether by liquid-phase hydrogenation |
| CN114849701A (en) * | 2022-06-01 | 2022-08-05 | 北京化工大学 | Hollow spherical catalyst for fixed bed with particle internal fluidization and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339561A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
| CN101618320A (en) * | 2009-07-16 | 2010-01-06 | 大连理工大学 | Eggshell type Pd catalyst prepared by reaction deposition method |
| CN102451685A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN104959136A (en) * | 2015-06-30 | 2015-10-07 | 大连理工大学 | Preparation method for resin hydrogenation eggshell type catalyst |
-
2016
- 2016-04-22 CN CN201610256384.2A patent/CN105903468B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339561A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
| CN101618320A (en) * | 2009-07-16 | 2010-01-06 | 大连理工大学 | Eggshell type Pd catalyst prepared by reaction deposition method |
| CN102451685A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN104959136A (en) * | 2015-06-30 | 2015-10-07 | 大连理工大学 | Preparation method for resin hydrogenation eggshell type catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551522A (en) * | 2018-05-31 | 2019-12-10 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN110551522B (en) * | 2018-05-31 | 2021-12-17 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN110607199A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Method for removing impurities from polyvinyl ether by hydrogenation |
| CN110607199B (en) * | 2018-06-14 | 2022-07-15 | 中国石油化工股份有限公司 | Method for removing impurities by hydrogenating polyvinyl ether |
| CN112126503A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Method for removing impurities from polyvinyl ether by liquid-phase hydrogenation |
| CN111073602A (en) * | 2019-12-05 | 2020-04-28 | 鸿蒙科技(浙江)有限公司 | Composition for improving refrigeration energy efficiency of HFO1234yf |
| CN114849701A (en) * | 2022-06-01 | 2022-08-05 | 北京化工大学 | Hollow spherical catalyst for fixed bed with particle internal fluidization and preparation method thereof |
| CN114849701B (en) * | 2022-06-01 | 2023-02-28 | 北京化工大学 | Hollow spherical catalyst for fixed bed with internal particle fluidization and preparation method thereof |
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