CN108816223B - Catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and preparation method thereof - Google Patents
Catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- -1 polyoxyethylene nonyl cyclohexanol Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [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 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000009903 catalytic hydrogenation reaction Methods 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
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002736 nonionic surfactant Substances 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000005303 weighing Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000011265 semifinished product Substances 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000001816 cooling Methods 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
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HPQKGWKGZNXUEF-UHFFFAOYSA-N 1-nonylcyclohexan-1-ol Chemical compound CCCCCCCCCC1(O)CCCCC1 HPQKGWKGZNXUEF-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- LBVWYGNGGJURHQ-UHFFFAOYSA-N dicarbon Chemical compound [C-]#[C+] LBVWYGNGGJURHQ-UHFFFAOYSA-N 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- 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
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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
- B01J37/08—Heat treatment
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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 catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and a preparation method thereof, which belong to the field of nonionic surfactants. The invention firstly treats the carrier, then impregnates the active element and reduces, washes and dries the catalyst, then impregnates the auxiliary agent, finally activates the catalyst, the catalyst has high activity and good selectivity.
Description
Technical Field
The invention belongs to the field of nonionic surfactants, and particularly relates to a catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and a preparation method thereof.
Background
Nonylphenol Polyoxyethylene Ether (NPE) is an important nonionic surfactant, has good penetrating, emulsifying, dispersing, acid-resisting, alkali-resisting, hard water-resisting, reduction-resisting and oxidation-resisting capabilities, and has wide application in the fields of detergents, printing and dyeing and chemical industry. However, polyoxyethylene nonylphenol ethers rapidly decompose to Nonylphenol (NP) to the environment. Nonyl phenol is a well-recognized environmental hormone which is difficult to degrade in the environment, has a bioaccumulation and amplification effect, and countries have come to regulate the production of nonyl phenol-containing environmental hormones. The polyoxyethylene ether alcohol of nonyl cyclohexanol has performance similar to that of polyoxyethylene nonyl phenyl ether to the maximum extent, is an important nonionic surfactant, and has the advantages of no environmental toxicity, no biological accumulation and biodegradability.
The core of the catalyst used in the preparation of polyoxyethylene nonyl cyclohexanol ether by hydrogenating polyoxyethylene nonyl phenyl ether is the selection and treatment of the carrier, and the silica is used as the main catalyst carrier, and the treatment method is more, for example, patent CN125180lC provides a preparation method of the catalyst using macroporous silica gel as the carrier, which comprises the steps of placing the granular silica gel produced by a sol method into an alkaline solution, heating, drying or roasting to prepare the macroporous silica gel carrier, wherein the alkaline solution is one or more of a solution of hydroxides of alkali metals and ammonium, a mixed solution of carbonates, bicarbonates, formates and acetate solutions of alkali metals and ammonium, impregnating the silica gel carrier with a solution of germanium salt and metal salt used as a cocatalyst, drying and roasting to prepare the germanium-based catalyst using the macroporous silica gel as the carrier. The catalyst has higher activity and selectivity in the reaction of synthesizing the dicarbon oxygen-containing compound by CO hydrogenation.
The carrier obtained by the method achieves certain effect, but is only suitable for a few catalysts, and the commercially available silicon dioxide and gamma-alumina carriers often cannot meet the requirements, so the carrier needs to be specially treated before use so as to meet the requirements of different reactions on the catalysts; on the other hand, for the catalyst for preparing the polyoxyethylene nonyl cyclohexanol by catalytic hydrogenation of the polyoxyethylene nonyl phenyl ether, the used catalyst requires a larger specific surface, a larger pore diameter and higher mechanical strength due to larger reactant molecules.
Disclosure of Invention
The invention provides a catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and a preparation method thereof, the prepared catalyst has the characteristics of high activity, large aperture, difficult blockage of pore channels, long service life and the like, and the preparation method has the advantages of simple process and low cost and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst for preparing polyoxyethylene nonyl cyclohexanol ether has carrier of gamma-alumina or silica, active element of Pd or Pt in 0.2-1 wt%, assistant of K or Na in 0.2-0.5 wt%.
A preparation method of a catalyst for preparing polyoxyethylene nonyl phenyl ether comprises the following steps:
(1) pretreating the carrier;
(2) measuring the water absorption rate of the carrier obtained in the step (1), preparing palladium chloride or chloroplatinic acid solutions with different concentrations according to the content requirement of the catalyst according to the result, impregnating the catalyst by adopting an isometric impregnation method, and drying at 70-90 ℃;
(3) slowly adding the catalyst obtained in the step (2) into a hydrazine hydrate or sodium borohydride water solution, filtering out the catalyst, washing with ionized water, and drying;
(4) measuring the water absorption rate of the catalyst obtained in the step (3), preparing alkali solutions with different concentrations according to the alkali metal content requirement according to the result, impregnating the catalyst by adopting an isometric impregnation method, and drying at 70-90 ℃ after impregnation;
(5) the catalyst is activated.
In the above steps, the pretreatment method in step (1) is: treating carrier microsphere gamma-alumina or silicon dioxide in water at 150-200 ℃ for 2-4 hours, then adding sodium hydroxide, adjusting the weight percentage of alkali to be 0.5-2%, soaking for 2.0-4.0 hours at 40-60 ℃, washing, drying or roasting to obtain a carrier, wherein the water content of the carrier is lower than 0.2%, and the specific surface of the silicon dioxide carrier is 200-300 m2The average pore diameter is 5-8 nm, the average pore volume is 0.30-1.0 ml/g, and the specific surface area of the gamma-alumina carrier is 100-200 m2(ii)/g, the average pore diameter is 6-10 nm, and the average pore volume is 0.30-0.6 ml/g; the activation method of the catalyst in the step (5) comprises the following steps: the catalyst is loaded into a closed fixed bed reactor at 5-10% H2-N2The temperature is gradually increased to 450 ℃, the temperature rising rate is lower than 30 ℃/h, and the temperature is reduced after the temperature is maintained for 2 hours to obtain the catalyst.
The invention has the beneficial effects that: the invention has provided a catalyst for preparing polyoxyethylene nonyl cyclohexanol ether and its preparation method, process the carrier at first, carry on the dipping of the active element and reduction, washing and drying of the catalyst, then carry on the dipping of the compounding chemicals, activate the catalyst finally, introduce alkali metal K or Na in carrier preconditioning and catalyst, lower the acid center on the surface of catalyst effectively, reduce dehydroxylation and condensation reaction in the course of hydrogenation reaction, has improved the selectivity of the product, avoid introducing multicomponent component in the catalyst at the same time, the catalyst prepared has high activity, pore size is large, the pore channel is difficult to stop up, characteristics such as having long performance life; the preparation method has the advantages of continuous production, convenient operation, low production cost and the like, is suitable for large-scale industrial production, and is particularly suitable for the catalytic hydrogenation reaction of low-molecular-weight nonylphenol polyoxyethylene ether NP-1 to NP-5 to generate corresponding polyoxyethylene nonyl cyclohexanol ether.
Detailed Description
The following examples are given in detail, and the silica carrier used in the following examples is spherical with a diameter of 2mm to 3mm and a specific surface of 268.7m2The pore volume is 0.97ml/g, and the average pore diameter is 5.7 nm; the gamma-alumina carrier is spherical with the diameter of 2 mm-3 mm and the specific surface of 168.5m2The pore volume is 0.36ml/g and the average pore diameter is 6.4 nm.
Example 1
Adding 500ml of water and 150g of a commercial silicon dioxide carrier into a 1.5L reaction kettle with a stirrer, sealing, heating to 150 ℃, keeping for 6 hours, cooling to below 40 ℃, filtering out water, adding 0.5% of sodium hydroxide, soaking at 50 ℃ for 3.0 hours, washing the materials until the materials are neutral, and drying to obtain the carrier A.
Example 2
Adding 500ml of water and 150g of a commercial silicon dioxide carrier into a 1.5L reaction kettle with a stirrer, sealing, heating to 200 ℃ for 2 hours, cooling to below 40 ℃, filtering out water, adding 1.5% of sodium hydroxide, soaking at 40 ℃ for 2.0 hours, washing the materials until the materials are neutral, and drying to obtain a carrier B.
Example 3
Adding 400ml of water and 150g of a commercially available gamma-alumina carrier into a 1.5L reaction kettle with a stirrer, sealing, heating to 180 ℃ for 4 hours, cooling to below 40 ℃, filtering out water, adding 0.8% of sodium hydroxide, soaking at 40 ℃ for 4.0 hours, washing the materials until the materials are neutral, drying, and roasting at 700 ℃ for 3 hours to obtain a carrier C.
Example 4
Adding 400ml of water and 150g of a commercially available gamma-alumina carrier into a 1.5L reaction kettle with a stirrer, sealing, heating to 160 ℃, keeping for 3 hours, cooling to below 40 ℃, filtering out water, adding 2.0% of sodium hydroxide, soaking for 2.0 hours at 60 ℃, washing the materials until the materials are neutral, drying, and roasting for 2 hours at 750 ℃ to obtain a carrier D.
Example 5
Adding 400ml of water and 150g of a commercially available gamma-alumina carrier into a 1.5L reaction kettle with a stirrer, sealing, heating to 180 ℃ for 4 hours, cooling to below 40 ℃, filtering out water, adding 2.0% of sodium hydroxide, soaking at 60 ℃ for 2.0 hours, washing the materials until the materials are neutral, drying, and roasting at 780 ℃ for 1.5 hours to obtain a carrier E.
Physical and chemical properties of pretreated carriers under different conditions
| Sample (I) | Specific surface m2/g | Pore volume ml/g | Average pore diameter nm |
| Silicon dioxide | 268.7 | 0.97 | 5.7 |
| Gamma-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 |
Example 6
Weighing 50g of carrier A, determining that the water absorption rate of the carrier A is 101.3%, weighing 0.17g of palladium chloride, dissolving the palladium chloride into 1% of 50.5g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; will be provided withSlowly adding the dried catalyst into a 5% sodium borohydride aqueous solution, reacting for 2 hours, filtering out a product, washing, and detecting with silver nitrate to determine that Cl can not be generated-1Then putting the mixture into an oven to dry for more than 12 hours; 0.43g of sodium hydroxide is weighed and dissolved in 50.2g of water, the sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain a catalyst F.
Example 7
Weighing 50g of carrier B, measuring the water absorption rate of the carrier B to be 102.6%, weighing 0.42g of palladium chloride, dissolving the palladium chloride into 1% of 50.3g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into 2% hydrazine hydrate solution, reacting for 3 hours, filtering out the product, washing, and detecting with silver nitrate to determine no Cl-1Then putting the mixture into an oven to dry for more than 12 hours; 0.18G of sodium hydroxide is weighed and dissolved in 50.4G of water, the sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain a catalyst G.
Example 8
Weighing 50g of carrier A, measuring the water absorption rate of the carrier A to be 101.3%, weighing 0.83g of palladium chloride, dissolving the palladium chloride into 1% of 50.5g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into 3% sodium borohydride water solution, reacting for 4 hours, filtering out the product, washing, and detecting with silver nitrate to determine that no Cl is produced-1Then putting the mixture into an oven to dry for more than 12 hours; weighing 0.26g of sodium hydroxide, dissolving into 50.2g of water, slowly dripping the sodium hydroxide aqueous solution into the catalyst under the condition of continuous overturning, overturning for 30 minutes after the completion of the impregnation, and then drying in an oven for 12 hours to obtain the catalystThereby obtaining a catalyst H.
Example 9
Weighing 50g of carrier C, measuring the water absorption rate of the carrier C to be 42.4%, weighing 0.17g of palladium chloride, dissolving the palladium chloride into 1% of 21.2g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into a 5% sodium borohydride aqueous solution, reacting for 3 hours, filtering out a product, washing, and detecting with silver nitrate to determine that no Cl is generated-1Then putting the mixture into an oven to dry for more than 12 hours; 0.33g of potassium hydroxide is weighed and dissolved in 21.2g of water, sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain the catalyst I.
Example 10
Weighing 50g of carrier D, measuring the water absorption rate of the carrier D to be 46.3%, weighing 1.02g of chloroplatinic acid, dissolving the chloroplatinic acid into 22.1g of 2% acetic acid aqueous solution, continuously overturning the carrier, slowly adding a palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into a 4% sodium borohydride aqueous solution, reacting for 3 hours, filtering out a product, washing, and detecting with silver nitrate to determine that no Cl is generated-1Then putting the mixture into an oven to dry for more than 12 hours; 0.28g of potassium hydroxide is weighed and dissolved in 22.2g of water, sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain a catalyst J.
Example 11
Weighing 50g of carrier E, measuring the water absorption rate of the carrier E to be 51.0%, weighing 0.34g of palladium chloride, dissolving the palladium chloride into 1% of 25.5g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; will be driedSlowly adding the catalyst into 4% hydrazine hydrate solution, reacting for 3 hours, filtering out the product, washing, and detecting with silver nitrate to determine that no Cl is produced-1Then putting the mixture into an oven to dry for more than 12 hours; 0.43g of sodium hydroxide is weighed and dissolved in 25.2g of water, the sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain the catalyst K.
Example 12
Weighing 50g of carrier D, measuring the water absorption rate of the carrier D to be 46.3%, weighing 0.32g of palladium chloride, dissolving the palladium chloride into 1% of 22.8g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into a 4% sodium borohydride aqueous solution, reacting for 2 hours, filtering out a product, washing, and detecting with silver nitrate to determine that no Cl is generated-1Then putting the mixture into an oven to dry for more than 12 hours; 0.28g of potassium hydroxide is weighed and dissolved in 22.4g of water, sodium hydroxide aqueous solution is slowly dripped into the catalyst under the condition of continuous overturning, the catalyst is overturned for 30 minutes after the completion of the impregnation, and then the catalyst is dried in an oven for more than 12 hours to obtain a catalyst L.
Example 13
Weighing 50g of carrier E, measuring the water absorption rate of the carrier E to be 51%, weighing 0.83g of palladium chloride, dissolving the palladium chloride into 1% of 24.6g of acetic acid aqueous solution, continuously overturning the carrier, slowly adding the palladium chloride solution onto the carrier, overturning for 30 minutes after the impregnation is finished, and then putting the semi-finished product into an oven to dry for more than 12 hours at the temperature of 70-90 ℃; slowly adding the dried catalyst into a 5% sodium borohydride aqueous solution, reacting for 2 hours, filtering out a product, washing, and detecting with silver nitrate to determine that no Cl is generated-1Then putting the mixture into an oven to dry for more than 12 hours; weighing 0.35g of sodium hydroxide, dissolving into 25.2g of water, slowly dripping the sodium hydroxide aqueous solution into the catalyst under the condition of continuous overturning, overturning for 30 minutes after the completion of the impregnation, and then putting into an oven to dry for more than 12 hours to obtain the catalystAnd (3) a catalyst M.
Comparative examples
And (3) carrying out catalytic hydrogenation reaction on the catalyst product obtained in the embodiment 6-13 in a fixed bed reactor with the specification of phi 32 multiplied by 3mm, wherein the loading of the catalyst is 20ml, passing hydrogen through a mass flow meter, mixing NP product with hydrogen through a metering pump, preheating, entering a hydrogenation reactor for catalytic hydrogenation, condensing and separating the product, discharging hydrogen, collecting liquid product for analysis, analyzing the product before and after hydrogenation by adopting an ultraviolet absorption and hydroxyl value determination method, and calculating the conversion rate and the selectivity. The specific catalyst and process conditions and test results are as follows:
as can be seen from the data in the table, the prepared series of catalysts have higher conversion rate, higher product selectivity and good industrial application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. A preparation method of a catalyst for preparing polyoxyethylene nonyl cyclohexanol ether is characterized in that the catalyst is used for catalytic hydrogenation of low-molecular-weight polyoxyethylene nonyl phenyl ether NP-1 to NP-5 to generate corresponding polyoxyethylene nonyl cyclohexanol ether; the catalyst comprises: the catalyst is prepared from a carrier of gamma-alumina or silicon oxide, an active element of Pd or Pt, 0.2-1% of the active element, an auxiliary agent of K or Na and 0.2-0.5% of the auxiliary agent, and the preparation method comprises the following steps:
(1) pretreating the carrier: treating the carrier in water at 150-200 ℃ in a reaction kettle for 2-4 hours, then adding sodium hydroxide, adjusting the weight percentage of alkali to be 0.5-2%, soaking for 2.0-4.0 hours at 40-60 ℃, washing and drying to obtain the carrier or washing, drying and roasting to obtain the carrier, wherein the water content of the carrier is lower than 0.2%;
(2) measuring the water absorption rate of the carrier obtained in the step (1), preparing palladium chloride or chloroplatinic acid solutions with different concentrations according to the content requirement of the catalyst according to the result, impregnating the catalyst by adopting an isometric impregnation method, and drying at 70-90 ℃;
(3) slowly adding the catalyst obtained in the step (2) into a hydrazine hydrate or sodium borohydride water solution, filtering out the catalyst, washing with ionized water, and drying;
(4) measuring the water absorption rate of the catalyst obtained in the step (3), preparing alkali solutions with different concentrations according to the content requirements of the auxiliary agent according to the results, impregnating the catalyst by adopting an isometric impregnation method, and drying at 70-90 ℃ after impregnation;
(5) activating the catalyst, and filling the catalyst into a closed fixed bed reactor at 5-10% H2-N2In the atmosphere, the temperature rising rate is lower than 30 ℃/h, the temperature is gradually raised to 450 ℃, and the temperature is reduced after the temperature is maintained for 2 hours to obtain the catalyst.
2. The method for preparing the catalyst for polyoxyethylene nonyl cyclohexanol ether of claim 1, wherein the carrier is microsphere γ -alumina or silica, and the specific surface of the silica carrier is 200-300 m2(ii)/g, the average pore diameter is 5-8 nm, and the average pore volume is 0.30-1.0 mL/g; the specific surface of the gamma-alumina carrier is 100-200 m2(iv)/g, average pore diameter is 6-10 nm, and average pore volume is 0.30-0.6 mL/g.
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