CN105903468B - A kind of preparation method and applications for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil - Google Patents
A kind of preparation method and applications for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil Download PDFInfo
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- CN105903468B CN105903468B CN201610256384.2A CN201610256384A CN105903468B CN 105903468 B CN105903468 B CN 105903468B CN 201610256384 A CN201610256384 A CN 201610256384A CN 105903468 B CN105903468 B CN 105903468B
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- hydrogen
- base oil
- glymes
- lube base
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000001257 hydrogen Substances 0.000 title claims abstract description 87
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 87
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 65
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 65
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 65
- 239000002199 base oil Substances 0.000 title claims abstract description 58
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 46
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003921 oil Substances 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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 15
- 150000001241 acetals Chemical class 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010970 precious metal Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- -1 Alkene ethers Chemical class 0.000 claims description 6
- 239000012696 Pd precursors Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 230000009467 reduction Effects 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 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010931 gold Substances 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 239000002082 metal nanoparticle Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000009938 salting Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 9
- 229920001289 polyvinyl ether Polymers 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000007598 dipping method 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
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004913 activation Effects 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
- 239000012687 aluminium precursor Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Lubricants (AREA)
Abstract
The present invention provides a kind of preparation method and applications for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil, belong to industrial catalysis technical field.Carrier is added in noble metal metal salt and Jin Shu Molybdenum salting liquids, pass through quick reduction reaction and solution viscosity, it controls noble metal nano particles and gold belongs to Molybdenum nano-particles and deposited in carrier surface, it is dry in inert atmosphere to form eggshell type Pd Mo catalyst through filtration washing.The present invention carries out at room temperature, heating source need not be introduced, it is simple for process, the metal grain size of preparation is small, is evenly distributed, and stability is good, Pd particles and Mo nano-particles are evenly distributed on carrier surface in the eggshell type Pd Mo catalyst of preparation, the dosage of noble metal is reduced, catalyst cost is effectively reduced, there is good prospects for commercial application.Eggshell type Pd Mo catalyst is used for glymes lube base oil hydrogenation reaction, has excellent catalytic performance and good catalyst life.
Description
Technical field
The invention belongs to lube oil hydrogenation technical fields, are related to one kind and adding hydrogen for glymes lube base oil
The preparation method of the eggshell type noble metal catalyst of removal of impurities.
Background technology
Loaded noble metal catalyst is widely used in the fields such as petrochemical industry and fine chemistry industry.The use of carrier can increase
The dispersion degree for adding noble metal improves the utilization rate of noble metal to reduce the cost of noble metal catalyst.In recent years, it largely grinds
Study carefully the granularity and distributed controll for being related to noble metal on carrier.The selection of metal Optimal Distribution is mainly according to catalysis wherein in carrier
The required activity of reaction, selectivity and other response parameters determine.The active metal of egg-shell catalyst mainly collects
In be distributed in carrier surface, the dosage of noble metal active component can be effectively reduced, improve the activity of catalyst；Eggshell type distribution
Catalyst is conducive to reaction product and is desorbed from catalyst surface, avoids the further reaction of target product, can improve can not
The selectivity of intermediate product in inverse tandem reactor process.The preparation of egg-shell catalyst is by urging mostly based on infusion process
The dipping of agent and it is dry control, including：Change dip time, the concentration of maceration extract, pH value, the factors such as solvent type and
Addition competitive adsorbate all has a major impact to preparing egg-shell catalyst.Polyvinylether class lubricating oil is due to raw material and polymerization item
The difference of part contains undersaturated double bond, aldehyde and acetal in base oil, under the effect of the catalyst, by adding hydrogen to enable it
Saturation, and coloration and the photo and thermal stability etc. for removing remaining chlorine element in polymerization process, and then improving base oil, and adding
Ehter bond cannot be destroyed during hydrogen, and then ensures its viscosity, improves the quality of product.Therefore, polyvinylether class lubricating oil is carried out
Base oil adds the research and development of hydrogen and heavy industrialization application to be particularly important.As glymes lube base oil
Catalyst in hydrogenation process, most important to the technique, it determines production cost and subsequent product quality.Compared to oil product plus
Hydrogen, glymes lube base oil add the difficulty bigger of hydrogen, due to glymes lube base oil chain structure, divide
For son amount between 200~4000, steric hindrance is larger, and activation energy needed for hydrogenation reaction improves, so needing to research and develop has high catalysis
Active hydrogenation catalyst.
For glymes lube base oil Utilizing question, we successfully develop eggshell type noble metal catalyst use
It is reacted in glymes lube base oil fixed bed continuously hydrogen adding, due to the use of egg-shell catalyst, it is ensured that load
The service life of type metallic catalyst.Obtained glymes lube base oil form and aspect improve to water-white and with good
Thermal stability.Following known technologies, all comes with some shortcomings：
Chinese patent, publication number：CN102451722A, introduces a kind of preparation method of egg-shell catalyst, and this method is adopted
Conventional carrier is soaked with the active metal dipping solution containing thickener and active metal dispersant, and in the item for being passed through air bubbling
It is impregnated under part, then through dry and roasting, obtains eggshell hydrogenation catalyst.Its process is more, comparatively laborious, and noble metal wave
Take serious.
Chinese patent, publication number：CN102451722B introduces a kind of preparation method of egg-shell catalyst, it is that will aoxidize
Aluminium precursor is uniformly mixed with Gemini surface active agent, adhesive, and catalyst carrier is made in kneading, then with containing thickener
Dipping solution impregnated carrier, and impregnated under conditions of being passed through air and being bubbled, then through dry and roasting, obtain eggshell type and hydrogen is added to urge
Agent.Its process is more, comparatively laborious, and noble metal waste is serious.
Chinese patent, publication number：CN1736604 introduces a kind of egg shell type metal and its preparation and application, the patent be with
Hollow silicon dioxide is the eggshell type metal supported catalyst of carrier, and the hollow silicon dioxide carrier is that have certain wall thickness
With the mesoporous material of certain pore size, egg shell type metal catalyst is prepared into using infusion process or load method in situ.But for carrier
There is strict demand, reaction step is cumbersome, and manufacturing cycle is longer.
Invention content
Adding the eggshell type precious metal catalyst that hydrogen cleans for glymes lube base oil the invention discloses a kind of
The preparation method of agent, belongs to industrial catalysis technical field.This method is that carrier is added to noble metal metal salt and Jin Shu Molybdenum salt
In solution, by quick reduction reaction and solution viscosity, noble metal nano particles and Jin Shu Molybdenum nano-particles are controlled in carrier table
Face deposits, and through being filtered, washed, heat drying forms stable eggshell type Pd Mo catalyst in inert atmosphere.Room temperature of the present invention
Lower progress need not introduce heating source, simple for process, and the metal grain size of preparation is small, is evenly distributed, and stability is good, the egg of preparation
Precious metals pd particle and Mo nano-particles are evenly distributed on carrier surface in shell mould PdMo catalyst, reduce the use of noble metal
Amount effectively reduces catalyst cost, has good prospects for commercial application.Eggshell type Pd Mo catalyst can be used for polyvinylether
Class lubricating oil base oil hydrogenation reaction, the catalyst have excellent catalytic performance and good catalyst life, and with good
Good economic benefit and prospects for commercial application.
Technical scheme of the present invention：
A kind of preparation method for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil,
Steps are as follows：
Precious metal palladium precursor and ammonium molybdate are dissolved in glycerine water solution, a concentration of 0.001- of precious metal palladium precursor
The molar ratio of 0.02mol/L, a concentration of 0.0001-0.002mol/L of ammonium molybdate, palladium and molybdenum is 10:1-20:1, by ball-type or
Column like catalyst carrier is added in mixed solution, adds strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction, when being impregnated by controlling
Between, reduction rate and solution viscosity, prepare egg-shell catalyst；Dip time is 5-100s, by into glycerine water solution
It is 50-200mPa.s that Sodium Polyacrylate control solution viscosity, which is added, by controlling NaBH4Concentration of aqueous solution and addition speed control
Former reaction rate deposits to control Ba He Molybdenum metals in carrier surface, and using filter, washing, inert atmosphere drying, which is formed, stablizes
Eggshell type Pd Mo catalyst.
The precious metal palladium precursor is that one or more of palladium nitrate, palladium bichloride, palladium, chlorine palladium acid are mixed
It closes.
The carrier is SiO2Or Al2O3, the average pore size of carrier is in 40nm or more.
The eggshell type Pd Mo catalyst is used for two sections of fixed bed continuously hydrogen addings of glymes lube base oil, first
First glymes lube base oil is diluted with solvent, glymes lube base oil accounts for the volume ratio of solvent
Then 40%-80% mixes the double bond for add in hydrogen saturation removal glymes lube base oil, into material temperature with hydrogen
120-150 DEG C of degree, hydrogen partial pressure 12-18MPa, volume space velocity 0.2-0.5h-1, hydrogen to oil volume ratio 200：1；Hydrocatalyst for saturating
For eggshell type Pd catalyst；Glymes lube base oil solution carries out after adding hydrogen to be saturated plus hydrogen takes off acetal, feeding temperature
140-150 DEG C, hydrogen partial pressure 15-18MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400：1；Hydrogen is added to take off acetal institute
The catalyst used is eggshell type Pd Mo catalyst, and the loading eggshell type Pd Mo catalyst of metal Pd is 0.8-1.0%；Add hydrogen
Glymes lube base oil form and aspect after removal of impurities improve to water white, and thermal stability improves, and viscosity slightly reduces.
Beneficial effects of the present invention：The method of the present invention carries out at room temperature, does not require carrier, and need not introduce
Heating source, simple for process, the metal grain size of preparation is small, is evenly distributed, and stability is good, expensive in the eggshell type Pd Mo catalyst of preparation
Metal Pd particle and Mo nano-particles are evenly distributed on carrier surface, reduce the dosage of noble metal, effectively reduce catalyst at
This, is conducive to amplification production, has good prospects for commercial application in the removal of impurities reaction of polyether class lubricating oil base oil.
Specific implementation mode
Specific embodiments of the present invention are described in detail below in conjunction with technical solution.
Embodiment 1：Chlorine palladium acid and ammonium molybdate are dissolved in glycerine water solution, a concentration of 0.01mol/L of chlorine palladium acid, molybdenum
A concentration of 0.001mol/L of sour ammonium adjusts solution ph and is more than carrier isoelectric point, by ball-type or column like catalyst carrier Al2O3In addition
It states in solution, control dip time is 20s, and solution viscosity 50mPa.s adds and adds strong reductant NaBH4Aqueous solution, normal pressure
React at room temperature 0.5h, NaBH4It is more than 5 with the molar ratio of metal, through being filtered, washed, inert atmosphere drying forms stable egg
Shell mould PdMo catalyst, Pd loadings are 0.8%.It is 200 μm to generate PdMo thickness of the shells, and the grain size of PdMo is 4.2nm.It will prepare
Eggshell type Pd Mo catalyst for glymes lube base oil add hydrogen removal of impurities reaction, as secondary hydrogenation removal of impurities urge
Agent is first diluted glymes lube base oil with solvent, and the diluted effect of solvent is, first, it is viscous to reduce reaction solution
Degree；Second is that taking away the heat that reaction is released；Third, the irrigation as catalyst.Shared by glymes lube base oil
Then ratio 50% mixes the double bond for add in hydrogen saturation removal glymes lube base oil, into material temperature with hydrogen
140 DEG C of degree, hydrogen partial pressure 15MPa, volume space velocity 0.4h-1, hydrogen to oil volume ratio 200：1；Hydrocatalyst for saturating is eggshell type Pd
The loading of catalyst, metal Pd is 0.5%；Glymes lube base oil passes through infrared detection double bond after adding hydrogen to be saturated
It has been be saturated that, ehter bond does not destroy.Glymes lube base oil solution carries out after adding hydrogen to be saturated plus hydrogen takes off acetal, charging
145 DEG C of temperature, hydrogen partial pressure 15MPa, volume space velocity 0.5h-1, hydrogen to oil volume ratio 200：1；Hydrogenation takes off used in acetal
Catalyst is eggshell type Pd Mo catalyst, and the loading of metal Pd is 0.8%；Polyvinylether class lubricating oil base after adding hydrogen to clean
Plinth oil colours mutually improves to water white, has been removed by infrared detection acetal and aldehyde radical, the glymes profit after adding hydrogen to clean
Lubricant base thermal stability improves, and viscosity slightly reduces.
Embodiment 2：The effects of metal Mo in the reaction are investigated, it is with solvent that glymes lube base oil is dilute first
It releases, the ratio 50% shared by glymes lube base oil, is then mixed with hydrogen and add hydrogen saturation removal polyethylene
Double bond in ethers lube base oil, 140 DEG C of feeding temperature, 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, and the loading of metal Pd is 0.5%；Polyvinylether after adding hydrogen to be saturated
Class lubricating oil base oil has been saturated by infrared detection double bond, and ehter bond does not destroy.Glymes lubricate after adding hydrogen to be saturated
Oil base oil solution carries out secondary hydrogenation, 145 DEG C of feeding temperature, hydrogen partial pressure 15MPa, volume space velocity 0.5h-1, hydrogen to oil volume ratio
200：1；Catalyst used in secondary hydrogenation is eggshell type Pd catalyst, and the loading of metal Pd is 0.8%；Add poly- after hydrogen
Vinethene class lubricating oil base oil form and aspect improve to water white, by also having acetal and aldehyde to exist in infrared detection solution, add hydrogen
Glymes lube base thermal stability afterwards increases, but high-temperature stability is bad, and 170 DEG C of heating turn yellow quickly,
Viscosity slightly reduces.By contrast test, we obtain, it was concluded that the addition of Mo metals is conducive to acetal and aldehyde plus hydrogen, main
To be conducive to the scission of link of C-H bond because of metal Mo.
Embodiment 3：Chlorine palladium acid and ammonium molybdate are dissolved in glycerine water solution, a concentration of 0.01mol/L of chlorine palladium acid, molybdenum
A concentration of 0.001mol/L of sour ammonium adjusts solution ph and is more than carrier isoelectric point, by ball-type or column like catalyst carrier Al2O3In addition
It states in solution, control dip time is 20s, and solution viscosity 50mPa.s adds and adds strong reductant NaBH4Aqueous solution, normal pressure
React at room temperature 0.5h, NaBH4Molar ratio with metal is respectively 5,10,15,20, and through being filtered, washed, inert atmosphere drying is shape
At stable eggshell type Pd Mo catalyst, Pd loadings are 0.8%.It is respectively 200 μm to generate PdMo thickness of the shells, 190 μm, 170 μ
M and 160 μm, the grain size of PdMo is respectively 4.2nm, 3.5nm, 3.0nm and 2.8nm.According to glymes lube base oil
Add known to hydrogen removal of impurities result：NaBH4Smaller, the metal shell layer thickness with the bigger prepared metallic grain size of the molar ratio of metal
It is thinner, add hydrogen removal of impurities hydrogenation activity more preferable in glymes lube base oil, is primarily due to reaction and accelerates, metal nucleation is more
Soon.
Embodiment 4：Chlorine palladium acid and ammonium molybdate are dissolved in glycerine water solution, a concentration of 0.01mol/L of chlorine palladium acid, molybdenum
A concentration of 0.0001mol/L, 0.001mol/L, 0.002mol/L, the 0.005mol/L of sour ammonium adjust solution ph and are more than carrier
Isoelectric point, by ball-type or column like catalyst carrier Al2O3It is added in above-mentioned solution, control dip time is 20s, and solution viscosity is
50mPa.s adds and adds strong reductant NaBH4Aqueous solution, atmospheric pressure at room react 0.5h, NaBH4With the molar ratio of metal be equal in
5, through being filtered, washed, inert atmosphere drying forms stable eggshell type Pd Mo catalyst, and Pd loadings are 0.8%.It generates
PdMo thickness of the shells are 200 μm or so, and the grain size of PdMo is 4.2nm or so.The eggshell type Pd Mo catalyst of preparation is used for poly- second
Alkene ethers lube base oil adds hydrogen removal of impurities reaction, the catalyst as secondary hydrogenation removal of impurities.According to polyvinylether class lubricating oil
Base oil adds known to hydrogen removal of impurities result：As molybdic acid ammonium concentration increases, eggshell type Pd Mo catalyst shell thickness and grain size are basic
It is constant, but when Mo concentration is too small, the glymes lube base oil after adding hydrogen to clean influences its height still with the presence of acetal
Temperature stability.But when Mo excessive concentrations, the glymes lube base oil ehter bond after adding hydrogen to clean destroys serious, viscosity
Decline is more, product yield.Therefore the addition of Mo will be controlled strictly.
Embodiment 5：Compare dip time to preparing the influence of egg-shell catalyst.Chlorine palladium acid and ammonium molybdate are dissolved in sweet
In oil solution, a concentration of 0.01mol/L, a concentration of 0.001mol/L of ammonium molybdate of chlorine palladium acid adjust solution ph and are more than
Carrier isoelectric point, by ball-type or column like catalyst carrier Al2O3It being added in above-mentioned solution, control dip time is respectively 5s, 20s, 40s,
100s, solution viscosity 50mPa.s add and add strong reductant NaBH4Aqueous solution, atmospheric pressure at room react 0.5h, NaBH4With gold
The molar ratio of category is equal to 5, and through being filtered, washed, inert atmosphere drying forms stable eggshell type Pd Mo catalyst, Pd loadings
It is 0.8% or so.It is respectively 170,200,210 and 280 μm to generate PdMo thickness of the shells, and the grain size of PdMo is 4.2nm.According to characterization
As a result known to：Dip time is longer, and prepared metal shell layer thickness is thicker, and metal grain size is basically unchanged, and moistens in glymes
Lubricant base oil adds in hydrogen removal of impurities reaction, and metal hydrogenation activity is almost the same, illustrates metal shell layer thickness to hydrogenation reaction activity
It influences little.Therefore, for egg-shell catalyst, egg-shell catalyst metal grain size should be controlled.
Embodiment 6：Chlorine palladium acid and ammonium molybdate are dissolved in glycerine water solution, a concentration of 0.01mol/L of chlorine palladium acid, molybdenum
A concentration of 0.001mol/L of sour ammonium adjusts solution ph and is more than carrier isoelectric point, will be on ball-type or column like catalyst carrier Al2O3 additions
It states in solution, control dip time is 20s, and solution viscosity is respectively 20,50,100 and 200mPa.s, adds and adds strong reductant
NaBH4Aqueous solution, atmospheric pressure at room react 0.5h, NaBH4It is equal to 5 with the molar ratio of metal, through being filtered, washed, inert atmosphere drying
Stable eggshell type Pd Mo catalyst is formed, Pd loadings are 0.8% or so.It is respectively 250,200 to generate PdMo thickness of the shells,
180 and 170 μm, the grain size of PdMo is 4.2nm or so.According to characterization result：The smaller prepared metal-back of solution viscosity
Layer thickness is thicker, and metal grain size is basically unchanged, and in glymes lube base oil adds hydrogen removal of impurities reaction, metal hydrogenation is lived
Property is almost the same, illustrates that metal shell layer thickness is little to hydrogenation reaction activity influence.Therefore, it for egg-shell catalyst, should control
Egg-shell catalyst metal grain size processed.
Embodiment 7：Chlorine palladium acid 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；The concentration of ammonium molybdate is respectively for 0.0001mol/L, 0.0005mol/L
And 0.001mol/L, it adjusts solution ph and is more than carrier isoelectric point, by ball-type or column like catalyst carrier Al2O3It is added in above-mentioned solution, controls
Dip time processed is 20s, and solution viscosity 50mPa.s adds and adds strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction
0.5h, NaBH4It is equal to 5 with the molar ratio of metal, through being filtered, washed, inert atmosphere drying forms stable eggshell type Pd Mo
Catalyst, Pd loadings are 0.8% or so.It is respectively 170,190 and 200 μm to generate PdMo thickness of the shells, and the grain size of PdMo is
4.2nm left and right.Ion concentration influences shell thickness, and ion concentration is diluter, and shell thickness is thinner.
Embodiment 8：On the basis of embodiment 1,140 DEG C of feeding temperature, 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, and the loading of metal Pd is 0.5%；Hydrogen is added to be saturated
Glymes lube base oil solution carries out afterwards plus hydrogen takes off acetal, and 145 DEG C of feeding temperature, hydrogen partial pressure 15MPa, volume are empty
Fast 0.5h-1, hydrogen to oil volume ratio 200：1；It is eggshell type Pd Mo catalyst, the load of metal Pd to add hydrogen to take off catalyst used in acetal
Carrying capacity is 0.8%, Pd and the molar ratio of Mo is 10:1 investigates catalyst stability.
By each phase experiments of this process operation 500h the results show that being to add hydrogen saturation catalysis with eggshell type Pd catalyst
Agent, eggshell type Pd Mo catalyst is plus hydrogen takes off aldolization catalyst, is lubricated glymes using two sections of fixed bed hydrogenation modes
Oil base plinth carries out hydrogenation reaction, and the glymes lube base form and aspect after removal of impurities, which are made, to be improved to water-white, viscosity slightly drop
It is low and non-discolouring with good high temperature thermostability, then 200 DEG C of long-times.It is good that the above results show that the technology of the present invention has
Stability, catalyst service life is long.
Claims (5)
1. a kind of preparation method for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil,
It is characterized in that, steps are as follows：
Precious metal palladium precursor and ammonium molybdate are dissolved in glycerine water solution, a concentration of the 0.001-of precious metal palladium precursor
The molar ratio of 0.02mol/L, a concentration of 0.0001-0.002mol/L of ammonium molybdate, palladium and molybdenum is 10:1-20:1, by ball-type or
Column like catalyst carrier is added in mixed solution, adds strong reductant NaBH4Aqueous solution, atmospheric pressure at room reaction, when being impregnated by controlling
Between, reduction rate and solution viscosity, prepare egg-shell catalyst；Dip time is 5-100s, by into glycerine water solution
It is 50-200mPa.s that Sodium Polyacrylate control solution viscosity, which is added, by controlling NaBH4Concentration of aqueous solution and addition speed control
Former reaction rate deposits to control palladium and molybdenum in carrier surface, and using filter, washing, inert atmosphere drying, which is formed, stablizes
Eggshell type Pd Mo catalyst.
2. preparation method according to claim 1, which is characterized in that the precious metal palladium precursor is palladium nitrate, chlorination
One or more of palladium, palladium, chlorine palladium acid mix.
3. preparation method according to claim 1 or 2, which is characterized in that the carrier is SiO2Or Al2O3, carrier
Average pore size is in 40nm or more.
4. the application for the eggshell type noble metal catalyst that preparation method as claimed in claim 1 or 2 obtains, which is characterized in that institute
The eggshell type Pd Mo catalyst stated is used for two sections of fixed bed continuously hydrogen addings of glymes lube base oil, first will with solvent
Glymes lube base oil dilutes, and glymes lube base oil accounts for the volume ratio 40%-80% of solvent, then with
Hydrogen mixing carries out plus hydrogen saturation removes the double bond in glymes lube base oil, feeding temperature 120-150oC, hydrogen
Divide 12-18MPa, volume space velocity 0.2-0.5h-1, hydrogen to oil volume ratio 200：1；Hydrocatalyst for saturating is catalyzed for eggshell type Pd
Agent；Glymes lube base oil solution carries out after adding hydrogen to be saturated plus hydrogen takes off acetal, feeding temperature 140-150oC, hydrogen
Divide 15-18 MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400：1；Hydrogen is added to take off catalyst used in acetal
Loading for eggshell type Pd Mo catalyst, metal Pd is 0.8-1.0% in eggshell type Pd Mo catalyst；After adding hydrogen to clean
Glymes lube base oil form and aspect improve to water white, and thermal stability improves, and viscosity slightly reduces.
5. the application for the eggshell type noble metal catalyst that the preparation method described in claim 3 obtains, which is characterized 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 with solvent by poly- second
Alkene ethers lube base oil dilutes, and glymes lube base oil accounts for the volume ratio 40%-80% of solvent, then with hydrogen
Mixing carries out plus hydrogen saturation removes the double bond in glymes lube base oil, feeding temperature 120-150oC, 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；Add
Glymes lube base oil solution carries out after hydrogen saturation plus hydrogen takes off acetal, feeding temperature 140-150oC, hydrogen partial pressure
15-18 MPa, volume space velocity 0.4-0.6h-1, hydrogen to oil volume ratio 200-400：1；It is egg to add hydrogen to take off catalyst used in acetal
The loading of shell mould PdMo catalyst, metal Pd is 0.8-1.0% in eggshell type Pd Mo catalyst；Poly- second after adding hydrogen to clean
Alkene ethers lube base oil form and aspect improve to water white, and thermal stability improves, and viscosity slightly reduces.
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| 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 |
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