CN108816223A - A kind of catalyst and preparation method thereof preparing nonyl cyclohexanol polyoxyethylene ether - Google Patents
A kind of catalyst and preparation method thereof preparing nonyl cyclohexanol polyoxyethylene ether Download PDFInfo
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- CN108816223A CN108816223A CN201810742818.9A CN201810742818A CN108816223A CN 108816223 A CN108816223 A CN 108816223A CN 201810742818 A CN201810742818 A CN 201810742818A CN 108816223 A CN108816223 A CN 108816223A
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- catalyst
- carrier
- dipping
- polyoxyethylene ether
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 22
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 22
- HPQKGWKGZNXUEF-UHFFFAOYSA-N 1-nonylcyclohexan-1-ol Chemical compound CCCCCCCCCC1(O)CCCCC1 HPQKGWKGZNXUEF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001994 activation Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002736 nonionic surfactant Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- 239000011265 semifinished product Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VIJKGBZMANAGQI-UHFFFAOYSA-M benzyl(triethyl)azanium;hydrogen carbonate Chemical compound OC([O-])=O.CC[N+](CC)(CC)CC1=CC=CC=C1 VIJKGBZMANAGQI-UHFFFAOYSA-M 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
-
- 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
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
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Abstract
The invention discloses a kind of catalyst and preparation method thereof for preparing nonyl cyclohexanol polyoxyethylene ether, belong to nonionic surfactant field, it is preparation method simple process, at low cost, the features such as suitable industrial production, catalyst obtained is active high, aperture is big, duct is not easy to plug, long service life.The present invention is first handled carrier, then carries out reduction, washing and the drying of the dipping and catalyst of active element, is then carried out the dipping of auxiliary agent, is finally activated to catalyst, and catalyst activity obtained is high, selectivity is good.
Description
Technical field
The invention belongs to nonionic surfactant fields more particularly to a kind of nonyl cyclohexanol polyoxyethylene ether for preparing to use
Catalyst and preparation method thereof.
Background technique
Nonylphenol polyoxyethylene ether（NPE）A kind of important nonionic surfactant has good infiltration, emulsification, divides
Scattered, antiacid, alkali resistant, hard water resistance, anti-reduction, oxidation resistance, have been widely used in detergent, printing and dyeing, chemical field.But
Nonylphenol polyoxyethylene ether can resolve into rapidly nonyl phenol into environment（NP）.Nonyl phenol is a kind of generally acknowledged environmental hormone,
It is difficult to be degraded in environment, there is bioaccumulation and enlarge-effect, various countries put into effect regulation limitation in succession contains nonylphenol class environment
The product of hormone.And nonyl cyclohexanol polyoxyethylene ether alcohol can be one utmostly close to the performance of nonylphenol polyoxyethylene ether
Kind important nonionic surfactant has the advantages that no environmental toxicity, inanimate object cumulative bad, biodegradable.
Catalyst core used in the process of nonylphenol polyoxyethylene ether adds hydrogen to prepare nonyl cyclohexanol polyoxyethylene ether exists
In the selection and processing of carrier, and silica is as main catalyst carrier, more for its processing method, such as patent
CN125180lC provides the preparation method that a kind of macro porous silica gel makees the catalyst of carrier, the graininess that will be produced by sol method
Silica gel is placed in alkaline solution, heating, dry or roasting, and macro porous silica gel carrier is made, and alkaline solution is the hydrogen of alkali metal and ammonium
One or more mixing in the solution of oxide, the carbonate of alkali metal and ammonium, bicarbonate, formates and Acetate Solution
Solution, with germanium salt and the solution of the metal salt as co-catalyst impregnates silica-gel carrier, dry, roasting, and obtained macro porous silica gel is
The germanium base catalyst of carrier.The catalyst in the reaction of CO hydrogenation synthesis c_2-oxygen compound have it is higher activity and
Selectivity.
Although the carrier obtained using above method has achieved the effect that certain, but be suitable only for a small number of catalyst, and
Commercially available silica and gamma-aluminium oxide carrier tend not to reach requirement, so carrier needs particularly to be located before use
Reason, to be suitble to differential responses to the needs of catalyst；And it is poly- to prepare nonyl cyclohexanol with regard to nonylphenol polyoxyethylene ether catalytic hydrogenation
For the catalyst of ethylene oxide ether, since reactant molecule is larger, used in catalyst then require to have biggish specific surface, compared with
Big aperture, higher mechanical strength.
Summary of the invention
It is obtained the present invention provides a kind of catalyst and preparation method thereof for preparing nonyl cyclohexanol polyoxyethylene ether
The features such as catalyst is active high, aperture is big, duct is not easy to plug, long service life, the preparation method simple process,
It is at low cost, it is suitble to industrial production.
In order to achieve the above object, the present invention uses following technical scheme：
A kind of catalyst preparing nonyl cyclohexanol polyoxyethylene ether, carrier are gama-alumina or silica, and active element is
Pd or Pt, the active element content are 0.2% ~ 1%, and auxiliary agent is K or Na, and the auxiliary agent content is 0.2% ~ 0.5%.
A kind of preparation method for the catalyst preparing nonyl cyclohexanol polyoxyethylene ether, includes the following steps：
(1) carrier is pre-processed；
(2) determination step (1) obtains the water absorption rate of carrier, requires the chlorine of configuration various concentration according to catalyst content according to result
Change palladium or platinum acid chloride solution, the dipping of catalyst, 70 DEG C ~ 90 DEG C drying after dipping are carried out using equi-volume impregnating；
(3) catalyst that step (2) obtains is slowly added into the aqueous solution of hydrazine hydrate or sodium borohydride, filters out catalyst,
Ion water washing, it is dry；
(4) water absorption rate for the catalyst that determination step (3) obtains requires configuration various concentration according to alkali metal content according to result
Aqueous slkali, the dipping of catalyst is carried out using equi-volume impregnating, 70 DEG C ~ 90 DEG C drying after dipping；
(5) catalyst is activated.
In step described above, the preprocess method of step (1) is：Carrier microballoons gama-alumina or silica are existed
It is handled 2 ~ 4 hours in 150 DEG C ~ 200 DEG C of water, sodium hydroxide is then added wherein, adjusted alkali concentration weight percent and exist
0.5% ~ 2%, it is impregnated 2.0 ~ 4.0 hours at 40 DEG C ~ 60 DEG C, washed, dry or roasting obtains carrier, and carrier water content is lower than
0.2%, 200 ~ 300m of specific surface of the silica supports2/ g, 5 ~ 8nm of average pore size, average hole hold 0.30 ~ 1.0ml/g,
100 ~ 200 m of specific surface of gamma-aluminium oxide carrier2/ g, 6 ~ 10nm of average pore size, average hole hold 0.30 ~ 0.6ml/g；Step (5)
The activation method of catalyst is：Catalyst is fitted into closed fixed bed reactors, in 5% ~ 10%H2-N2Gas atmosphere in,
Temperature is gradually raised to 450 DEG C, heating rate is lower than 30 DEG C/h, and cooling obtains catalyst after maintaining 2 hours.
Beneficial effects of the present invention：The present invention provides a kind of catalyst for preparing nonyl cyclohexanol polyoxyethylene ether and
Preparation method is first handled carrier, then carries out reduction, washing and the drying of the dipping and catalyst of active element,
Then carry out auxiliary agent dipping, finally catalyst is activated, all introduced in Vehicle element and catalyst alkali metal K or
Person Na, the effectively lower acid centre of catalyst surface, reduces the hair of dehydroxylation and condensation reaction in hydrogenation process
It is raw, improve the selectivity of product, while avoiding introducing multicomponent mixture in the catalyst, catalyst obtained it is active it is high,
The features such as aperture is big, duct is not easy to plug, long service life；Preparation method of the invention have production serialization, it is easy to operate,
The advantages such as production cost is low, are suitble to high-volume industrial production, which is particularly suitable for low molecular weight Nonyl pheno
Ether NP-1 to NP-5 carries out catalytic hydrogenation reaction and generates corresponding nonyl cyclohexanol polyoxyethylene ether.
Specific embodiment
It is specifically described below with reference to embodiment, silica supports used are diameter 2mm ~ 3mm in following embodiment
Spherical shape, specific surface 268.7m2/ g, Kong Rongwei 0.97ml/g, average pore size 5.7nm；Gamma-aluminium oxide carrier used is straight
The spherical shape of diameter 2mm ~ 3mm, specific surface 168.5m2/ g, Kong Rongwei 0.36ml/g, average pore size 6.4nm.
Embodiment 1
500ml water and the commercially available silica supports of 150g are added in the 1.5L reaction kettle with stirring, 150 DEG C are warming up to after sealing
It is kept for 6 hours, is down to 40 DEG C hereinafter, then filter out water, then 0.5% sodium hydroxide is added wherein to temperature, is impregnated at 50 DEG C
3.0 hours, material is washed, until it is neutral, it is dried to obtain carrier A.
Embodiment 2
500ml water and the commercially available silica supports of 150g are added in the 1.5L reaction kettle with stirring, 200 DEG C are warming up to after sealing
It is kept for 2 hours, is down to 40 DEG C hereinafter, then filter out water, then 1.5% sodium hydroxide is added wherein to temperature, is impregnated at 40 DEG C
2.0 hours, material is washed, until it is neutral, it is dried to obtain carrier B.
Embodiment 3
400ml water and the commercially available gamma-aluminium oxide carrier of 150g are added in the 1.5L reaction kettle with stirring, 180 are warming up to after sealing
It DEG C is kept for 4 hours, is down to 40 DEG C hereinafter, then filter out water, then 0.8% sodium hydroxide is added wherein to temperature, is soaked at 40 DEG C
Bubble 4.0 hours, material is washed, until neutral, 700 DEG C of roastings obtain support C in 3 hours after drying.
Embodiment 4
400ml water and the commercially available gamma-aluminium oxide carrier of 150g are added in the 1.5L reaction kettle with stirring, 160 are warming up to after sealing
It DEG C is kept for 3 hours, is down to 40 DEG C hereinafter, then filter out water, then 2.0% sodium hydroxide is added wherein to temperature, is soaked at 60 DEG C
Bubble 2.0 hours, material is washed, until neutral, 750 DEG C of roastings obtain carrier D in 2 hours after drying.
Embodiment 5
400ml water and the commercially available gamma-aluminium oxide carrier of 150g are added in the 1.5L reaction kettle with stirring, 180 are warming up to after sealing
It DEG C is kept for 4 hours, is down to 40 DEG C hereinafter, then filter out water, then 2.0% sodium hydroxide is added wherein to temperature, is soaked at 60 DEG C
Bubble 2.0 hours, material is washed, until neutral, 780 DEG C of roastings obtain carrier E in 1.5 hours after drying.
The physical and chemical performance of different condition pretreated carrier
| Sample | Specific surface m2/g | Hole holds ml/g | Average pore size nm |
| Silica | 268.7 | 0.97 | 5.7 |
| Gama-alumina | 168.5 | 0.36 | 6.4 |
| A | 203.7 | 1.18 | 7.6 |
| B | 198.3 | 1.25 | 8.3 |
| C | 129.6 | 0.44 | 7.7 |
| D | 118.4 | 0.48 | 8.3 |
| E | 100.1 | 0.52 | 9.2 |
Embodiment 6
50g carrier A is weighed, its water absorption rate is 101.3% after measured, weighs the 50.5g acetic acid water that palladium chloride 0.17g is dissolved into 1%
In solution, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, overturning 30 minutes after the completion of dipping, then
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added
Enter into 5% sodium borohydride aqueous solution, after reaction 2 hours, filters out product and washed, do not gone out using silver nitrate detection assay
Cl-1, it is then placed in baking oven 12 hours dry or more；It weighs sodium hydroxide 0.43g to be dissolved into 50.2g water, constantly overturn
Under conditions of, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in after the completion of dipping
Dry 12 hours catalyst F derived above in baking oven.
Embodiment 7
50g carrier B is weighed, its water absorption rate is 102.6% after measured, weighs the 50.3g acetic acid water that palladium chloride 0.42g is dissolved into 1%
In solution, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, overturning 30 minutes after the completion of dipping, then
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added
Enter into 2% hydrazine hydrate solution, after reaction 3 hours, filter out product and washed, Cl is not gone out using silver nitrate detection assay-1,
It is then placed in baking oven 12 hours dry or more；It weighs sodium hydroxide 0.18g to be dissolved into 50.4g water, in the item constantly overturn
Under part, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking oven after the completion of dipping
12 hours catalyst G derived above of middle drying.
Embodiment 8
50g carrier A is weighed, its water absorption rate is 101.3% after measured, weighs the 50.5g acetic acid water that palladium chloride 0.83g is dissolved into 1%
In solution, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, overturning 30 minutes after the completion of dipping, then
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added
Enter into 3% sodium borohydride aqueous solution, after reaction 4 hours, filters out product and washed, do not gone out using silver nitrate detection assay
Cl-1, it is then placed in baking oven 12 hours dry or more；It weighs sodium hydroxide 0.26g to be dissolved into 50.2g water, constantly overturn
Under conditions of, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in after the completion of dipping
Dry 12 hours catalyst H derived above in baking oven.
Embodiment 9
Weigh 50g support C, after measured its water absorption rate be 42.4%, weigh palladium chloride 0.17g be dissolved into 1% 21.2g acetic acid it is water-soluble
In liquid, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, then overturning 30 minutes after the completion of dipping will
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added to
It into 5% sodium borohydride aqueous solution, after reaction 3 hours, filters out product and is washed, Cl is not gone out using silver nitrate detection assay-1, it is then placed in baking oven 12 hours dry or more；It weighs potassium hydroxide 0.33g to be dissolved into 21.2g water, what is constantly overturn
Under the conditions of, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking after the completion of dipping
Dry 12 hours catalyst I derived above in case.
Embodiment 10
Weigh 50g carrier D, after measured its water absorption rate be 46.3%, weigh chloroplatinic acid 1.02g be dissolved into 2% 22.1g acetic acid it is water-soluble
In liquid, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, then overturning 30 minutes after the completion of dipping will
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added to
It into 4% sodium borohydride aqueous solution, after reaction 3 hours, filters out product and is washed, Cl is not gone out using silver nitrate detection assay-1, it is then placed in baking oven 12 hours dry or more；It weighs potassium hydroxide 0.28g to be dissolved into 22.2g water, what is constantly overturn
Under the conditions of, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking after the completion of dipping
Dry 12 hours catalyst J derived above in case.
Embodiment 11
Weigh 50g carrier E, after measured its water absorption rate be 51.0%, weigh palladium chloride 0.34g be dissolved into 1% 25.5g acetic acid it is water-soluble
In liquid, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, then overturning 30 minutes after the completion of dipping will
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added to
It into 4% hydrazine hydrate solution, after reaction 3 hours, filters out product and is washed, Cl is not gone out using silver nitrate detection assay-1, so
After be placed in oven and dried 12 hours or more；It weighs sodium hydroxide 0.43g to be dissolved into 25.2g water, in the condition constantly overturn
Under, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking oven after the completion of dipping
Dry 12 hours catalyst K derived above.
Embodiment 12
Weigh 50g carrier D, after measured its water absorption rate be 46.3%, weigh palladium chloride 0.32g be dissolved into 1% 22.8g acetic acid it is water-soluble
In liquid, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, then overturning 30 minutes after the completion of dipping will
Semi-finished product are put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added to
It into 4% sodium borohydride aqueous solution, after reaction 2 hours, filters out product and is washed, Cl is not gone out using silver nitrate detection assay-1, it is then placed in baking oven 12 hours dry or more；It weighs potassium hydroxide 0.28g to be dissolved into 22.4g water, what is constantly overturn
Under the conditions of, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking after the completion of dipping
Dry 12 hours catalyst L derived above in case.
Embodiment 13
50g carrier E is weighed, its water absorption rate is 51% after measured, weighs the 24.6g aqueous acetic acid that palladium chloride 0.83g is dissolved into 1%
In, carrier is constantly overturn to palladium chloride solution simultaneously and is slowly added on carrier, overturning 30 minutes after the completion of dipping, then by half
Finished product is put into baking oven 12 hours dry or more under conditions of 70 ~ 90 DEG C of temperature；Catalyst after drying is slowly added into
It in 5% sodium borohydride aqueous solution, after reaction 2 hours, filters out product and is washed, Cl is not gone out using silver nitrate detection assay-1,
It is then placed in baking oven 12 hours dry or more；It weighs sodium hydroxide 0.35g to be dissolved into 25.2g water, in the item constantly overturn
Under part, sodium hydrate aqueous solution is slowly dropped in above-mentioned catalyst, overturning 30 minutes, are then placed in baking oven after the completion of dipping
12 hours catalyst M derived above of middle drying.
Comparative example
Embodiment 6 ~ 13 is obtained into catalyst prod, carries out catalytic hydrogenation reaction in specification ￠ 32 × 3mm fixed bed reactors,
Catalyst loading is 20ml, and preheating, which enters, after hydrogen is mixed by metering pump with hydrogen by mass flowmenter, NP product adds hydrogen
Reactor carries out catalytic hydrogenation, and product is after condensing and separating, hydrogen gas automatic blow down, and liquid product collection is analyzed, and adds production before and after hydrogen
Product are analyzed using the method for UV absorption and hydroxy value measuring, calculate conversion ratio and selectivity.Specific catalyst and technique
Condition and test result is as follows：
Data can be seen that from table, a series of catalyst conversion ratio with higher of preparation, while product with higher selects
Selecting property, prospects for commercial application are fine.
The above is only a preferred embodiment of the present invention, it should be pointed out that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications should also regard
For protection scope of the present invention.
Claims (6)
1. a kind of catalyst for preparing nonyl cyclohexanol polyoxyethylene ether, which is characterized in that including carrier be gama-alumina or
Silica, active element are Pd or Pt, and the active element content is 0.2% ~ 1%, and auxiliary agent is K or Na, and the auxiliary agent content is
0.2%~0.5%。
2. a kind of preparation method for the catalyst for preparing nonyl cyclohexanol polyoxyethylene ether, which is characterized in that including following step
Suddenly：
(1) carrier is pre-processed；
(2) determination step (1) obtains the water absorption rate of carrier, requires the chlorine of configuration various concentration according to catalyst content according to result
Change palladium or platinum acid chloride solution, carries out the dipping of catalyst, 70 DEG C ~ 90 DEG C drying after dipping；
(3) catalyst that step (2) obtains is slowly added into the aqueous solution of hydrazine hydrate or sodium borohydride, filters out catalyst,
Ion water washing, it is dry；
(4) water absorption rate for the catalyst that determination step (3) obtains requires configuration various concentration according to alkali metal content according to result
Aqueous slkali, carry out the dipping of catalyst, 70 DEG C ~ 90 DEG C drying after dipping；
(5) catalyst is activated.
3. the preparation method of the catalyst according to claim 2 for preparing nonyl cyclohexanol polyoxyethylene ether, feature
It is, preprocess method described in step (1) is：Carrier is handled 2 ~ 4 hours in 150 DEG C ~ 200 DEG C of water, is then existed
Sodium hydroxide is wherein added, adjusts alkali concentration weight percent 0.5% ~ 2%, is impregnated 2.0 ~ 4.0 hours at 40 DEG C ~ 60 DEG C,
Washed, dry or roasting obtains carrier, and carrier water content is lower than 0.2%.
4. the preparation method of the catalyst according to claim 2 or 3 for preparing nonyl cyclohexanol polyoxyethylene ether, special
Sign is that the carrier is microballoon gama-alumina or silica, 200 ~ 300m of specific surface of the silica supports2/ g,
5 ~ 8nm of average pore size, average hole hold 0.30 ~ 1.0ml/g；100 ~ 200 m of specific surface of the gamma-aluminium oxide carrier2/ g, it is average
6 ~ 10nm of aperture, average hole hold 0.30 ~ 0.6ml/g.
5. the preparation method of the catalyst according to claim 2 for preparing nonyl cyclohexanol polyoxyethylene ether, feature
It is, the dipping of catalyst described in step (2) and step (4) uses equi-volume impregnating.
6. the preparation method of the catalyst according to claim 2 for preparing nonyl cyclohexanol polyoxyethylene ether, feature
It is, catalyst activation process described in step (5) is：Catalyst is fitted into closed fixed bed reactors, 5% ~
10%H2-N2Atmosphere in, heating rate is lower than 30 DEG C/h, and temperature is gradually raised to 450 DEG C, cools down after maintaining 2 hours and is urged
Agent.
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